A Practical Manual on

Microbiologically
Influenced
Corrosion
Volume 2

John G. Stoecker II
Editor
 NACE International
The Corrosion Society

0 1993, 2001 by NACE International

Second Edition 2001. All rights reserved.

Library of Congress Catalog Number 93-85751

ISBN 1-877914-56-8 (Volume 1)

ISBN 1-57590-113-7 (Volume 2)

Printed in the United States of America. All rights reserved. This book, or parts thereof, may not be reproduced in
any form without permission of the copyright owners.

Neither NACE International, its officers, directors, or members thereof accept any responsibility for the use of the
methods and materials discussed herein. The information is advisory only and the use of the materials and methods
is solely at the risk of the user.

Cover Art Clockwise from Top Right: Figure 9.4, Figure 4.1, Figure 11.33, and Figure 4.6.
Cover Design by Michele Sandusky, NACE Graphics Department, and Techbooks.

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 CONTENTS

About the Editor ....................................................................................... v

Tasks and Acknowledgments. ....................................................................... vii
Glossary ............................................................................................... ix

1. Introduction
9. Little, R. Ray, and S. Dexter.. .......................................................... 1.1
2. Fungal-Influenced Corrosion of Metals in Humid Environments
B. Little and R. Ray ....................................................................... .2.1
3. Biodegradation of Nonmetallic Engineering Materials
9. Little, R. RaH and P Wagner........................................................... 3.1
4. The Biodeterioration of Building Materials
C. Saiz-Jimenez.. ......................................................................... .4.1
5. Microbiologically Influenced Corrosion in Fire Protection Sprinkler Systems
D.H. Pope and R.M. Pope ................................................................ .5.1
6. MIC in Underground Environments: External Corrosion
in the Gas Pipeline Industry
Part I
TR. Jack.. .................................................................................. 6.1
Part II - Microbiologically Influenced Corrosion of Internal Aspects of Natural Gas
Industry Pipelines and Associated Equipment: Mechanisms, Diagnosis,
and Mitigation
D.H. Pope ................................................................................. 6.13
Part Ill - A Case Study-Microbially Induced Organic Acid Attack
in a Natural Gas Gathering System
J. W Dusseault and J.H. Schulz.. ....................................................... 6.27
7. MIC in the Power Industry
G.J. Licina ................................................................................. .7.1
Color Plate Section . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . CP.1

iii
i\i Contents

8. MIC in the Waste Treatment Industries

J.B. Soebbing. .............................................................................. 8.1
9. Treatment for the Mitigation of MIC
R. W Lutey .................................................................................. 9.1
10. Techniques for MIC Monitoring
T.P Zintel, G.J. Licina, and T.R. Jack ................................................... 10.1
11. MIC Case Histories
Compiled by H.A. Videla, ................................................................ 11.l
CS-3 Marine Microbial Corrosion
1.B. Beech, S.A. Campbell, and EC. Walsh..................................... 11.3
CS-4 The Detection and Mitigation of MIC
T.E. Cloete, PJ. Allison, and W I .J. Poulton., .................................. 1 1 -15
MM-3 Microbiologically Influenced Corrosion in Geothermal Fields in Mexico
B. Valdez Salas, L. Rioseco de la Peha, G. Hernandez-Duque Delgadillo,
and N. Rosas Gonzalez ........................................................ 1 1.21
S-I Microbial Corrosion of Cultural Heritage Stoneworks
C. Saiz-Jimenez and X. Ariho .................................................. 11.25
SS-13 Localized Corrosion of Stainless Steel Milk Sterilizers
H.A. Videla....................................................................... 11.35
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1

Corrosion associated with microorganisms
has been recognized for over 50 years, and yet
the study of microbiologically influenced corrosion
(MIC) is a relatively new, multidisciplinary field
in which there has been a continuum of inno-
vations and contributions. A Practical Manual on
Microbiologically Influenced Corrosion Volume 2
edited by John Stoecker is a compilation of pa-
pers by internationally recognized authorities in
the field of MIC, including contributing authors from
Argentina, Mexico, Spain, England, Canada, and
the United States. The primary purpose of Vol-
ume 2 is to document the incidence of MIC and
the control measures in industries, environments,
and materials not covered in Volume 1. Volume 2
includes chapters or case histories from the food
processing, fire protection, waste treatment, and
natural gas industries. There are also chapters on
nonmetallic materials affected by MIC, including
polymer-coated metals, masonry building materi-
als, heritage stoneworks, fiber-reinforced compos-
ites, paints, caulks, and sealants.
Secondary objectives for Volume 2 are to up-
date the information from Volume 1 in areas where
significant new information is available and to
present additional case histories. In this regard
chapters are presented on MIC in the electric
power and marine industries, as well as informa-
tion on MIC monitoring and mitigation, including
chemical treatments and biocides. Color plates are
included as an aid for plant personnel in recogniz-
ing the signs of MIC.
Several chapters demonstrate the diverse en-
vironments in which MIC can be a problem as well
as the diversity of causative organisms. MIC is
not limited to aqueous corrosion under submerged
1.1
CHAPTER 1
Introduction
By B. Little, R,Ray,and S, Dexter
conditions but also takes place in humid atmo-
spheres. One chapter is devoted to the role of
fungi in atmospheric corrosion'and coating deteri-
oration.
The variety of environments and industries
in which MIC is encountered and controlled has
inevitably led to some contradictions in recom-
mendations for mitigation from one situation to
another. The reader should note that such con-
tradictions can be found between the recommen-
dations for treatment in several of the chapters
in this volume. Sometimes materials or methods
recommended for controlling MIC in one indus-
try may be specifically identified as not working
well in another. This may be due to obvious or
even slight changes in chemical or physical op-
erating conditions between the two industries. In
other cases the particular constraints in one in-
dustry may cause the most effective control tech-
nologies to be rejected in favor of ones considered
less effective or even ineffective in another. Thus,
the reader should be careful in taking the recom-
mendations for MIC control from one industry and
applying them to another without a thorough analy-
sis of detailed operating conditions. Nevertheless,
it is hoped that the methods for recognizing, mon-
itoring, and controlling MIC presented in this vol-
ume will result in cross-fertilization of ideas to the
benefit of all.
Since Volume 1' was published three major
developments have contributed to our understand-
ing of MIC: (1) a redefinition of biofilm architecture,
( 2 ) the realization that MIC of metals can best be
understood as biomineralization, and (3) the limi-
tation to interpretation of cell numbers determined
by microscopy or microbiological testing.
1.2 Introduction

BULK WATER FeZt

MnZt

FIGURE 1.1
Conceptual model of stratified biofilm.

Biofilm Architecture of confocal laser scanning microscopy it became

apparent that multi- and single species biofilms
form complex structures containing voids, chan-
In aquatic environments, microbial cells attach
nels, cavities, pores, and filaments, with cells ar-
to solids. "Immobilized cells grow, reproduce and
ranged in clusters (Figure 1.2). Such complex
produce extracellular polymers which frequently structures have been reported in a wide vari-
extend from the cell forming a tangled matrix
ety of biofilms including methanogenic films from
of fibers which provide structure to the assem-
fixed-bed reactors,' aerobic films from wastewa-
blage termed a biofilm."2 The most devastating ter plant^,^,^ nitrifying biofilms,1° and pure culture
MIC takes place in the presence of microbial con-
biofilms of Vibrio parahaemolyticus' and Pseu-
sortia in which many physiological types of bac- dornonas aeruginosa. Lewandowski et al.
te r ia , including s uIfate-reducing bacteria (SR B) ,
further refined the model by demonstrating an
acid-producing bacteria, metal-oxidizing bacteria,
intricate interplay between hydrodynamics and
and metal-reducing bacteria (MRB), interact in
viscoelastic biopolymers leading to formation of
complex ways within the structure of b i ~ f i l m s . ~ , ~"streamers" and characteristic biofilm matrix os-
When images were limited to those produced by
cillation. The new conceptual model assumes an
light and electron microscopy, biofilms most often inherent biofilm heterogeneity and constitutes the
appeared to be composed of bacterial cells en- foundation for studying biofilm structure and its
closed in an exopolymeric substance (EPS) ma-
consequences, including MIC.
trix of uniform thickness and consistency (Figure
1.1). Conceptual and numerical models treated
biofilms as layers of matrix material within which Biomineralization
bacterial cells were randomly distributed, and
these models appeared to be predictive of reac- Microorganisms influence corrosion of met-
tion rates in b i o r e a ~ t o r s .However,
~,~ with the use als by both forming and dissolving minerals.14
Introduction 1.3

Biomineralization that results in mineral deposition

FIGURE 1.2
Updated model of a biofilm showing microbial micro-
colonies and interstitial voids filled with water. Arrows
indicate convective flow. (From Lewandowski et aI.l3)
on a metal surface can shift the corrosion potential
in either a positive or negative direction, depend-
ing on the nature of the mineral. Manganese oxide
biodeposition on stainless steel surfaces exposed
in fresh water forces a shift in the positive, more no-
ble direction, moving the corrosion potential to the
pitting potential and potentially making some stain-
less steels more vulnerable to pitting and crevice
corrosion (Figure 1.3a,b,c).15 Iron oxide forma-
tion/deposition by microorganisms can initiate a
sequence of events that results in underdeposit
corrosion of susceptible metals (Figure 1 .4a,b).16
In the absence of oxygen, the metabolic ac-
tivity of SRB causes accumulation of hydrogen
sulfide near metal surfaces. This is particularly

(c) 0.5

0.4
1

0.3
h

>
3 0.2
Y
w 0.1

-0.1

-0.2 '
0
I
100
I

200
I
300
I

400 500
time ( h )

FIGURE 1.3
Annular deposits on stainless steel after 13-day exposure to fresh water. (a) Reflected light micrograph, (b) SEM micro-
graph, and ( c ) €, vs. time for 31 6-L stainless steel coupons during manganese oxide deposition in fresh river water.
(From Dickinson and L e w a n d o w ~ k i . ' ~ )
1.4 Introduction

(b)
uM2' t 2H2O -+ M (OH),

HYDROLYSIS REACTION
t 2Ht

EQUILIBRIUM pH

Fez+t 2Hz0 $ Fe(OH)2 t 2Ht pH = 6.64 - 112 log aFeZt

C+'t 3H20 Cr(OH)3 t 3H + pH = 1.53 - 1/3 log aC?+

Ni2' t 2H20 Ni(0H)z t 2H' pH = 6.5 - 1/2 log aN,2'

MnZt t 2H20 Mn(OH)z t 2Ht pH = 7.66 - 112 log aMnzt

FIGURE 1.4
(a) Possible reactions under tubercles created by metal-depositing bacteria and (b) specific hydrolysis reactions that
produce acidity under tubercles.

evident when metal surfaces are covered with

3500 I 1 biofilms (Figure 1.5).17 The concentration of sul-
3000 - 0 DISSOLVED OXYGEN fide is highest near the metal surface. Bioprecip-
f?
2
a
2500 - A SULFIDE itated sulfides stimulate the cathodic reaction so
g 2000 - m o H that sulfide formation on metal surfaces moves
'E
I 1500 the corrosion potential in a negative, more active
w direction, resulting in accelerated corrosion of
g 1000
some metals and alloys. The corrosion rate of
500
G iron in the presence of hydrogen sulfide is accel-
n o erated by the formation of iron sulfide minerals.
-500 Once electrical contact is established, mild steel
-1 0 1 2 3 4 5 6
behaves as an anode and electron transfer oc-
DISSOLVED OXYGEN CONCENTRATION (mglL)
curs through the iron sulfide. At low ferrous ion
concentrations, adherent and temporarily protec-
-9 -8 -7 4 -5 -4 -3 -2 -1
tive films of iron sulfides are formed on the steel
LOG OF TOTAL SULFIDE CONCENTRATION (mol/L)
surface with a consequent reduction in corrosion
FIGURE 1.5 rate. High rates of SRB-induced corrosion of mild
Concentration profiles of sulfide, oxygen, and p H in a steel are maintained only in high concentrations of
biofilm on mild steel. (From Lee et al.") ferrous ion.17
Introduction
(a) Thick sulfide-rich scale
/
Corrosion
Thin
subscale
product
-_.-_.
Metal
Thick scale containing sulfide,
partially converted sulfide, and oxide
/ because of the large number of stable copper sul-
FIGURE 1.6
(a) Schematic of thick, sulfide-rich scale on copper alloy
(top) and disruption of sulfide film (bottom, from Syrett
1981 ”) and (b) encrustations of copper sulfide on bac-
terial cells.
The impact of sulfides on the corrosion of cop-
per alloys has received considerable attention, in-
cluding published reports documenting localized
corrosion of copper alloys by SRB in estuarine
environments.18 A porous layer of cuprous sulfide
with the general stoichiometry C U ~ - ~ 0S < , x<1
forms in the presence of sulfide ions.lg Copper
ions migrate through the layer, react with more
sulfide, and produce a thick, black scale (Figure
1.6a,b). It has been argued that if the copper sul-
fide layer were djurelite, the sulfide layer would be
protective.20 Even if such a sulfide film were tech-
nically passivating, the mechanical stability of the
film is so poor that copper sulfide films are use-
1.5
less for corrosion protection. In the presence of
turbulence, the loosely adherent sulfide film is re-
moved, exposing a fresh copper surface to react
with sulfide ions. For these reasons, turbulence-
induced corrosion and sulfide attack of copper
alloys cannot easily be decoupled. In the pres-
ence of oxygen, the possible corrosion reactions
in a copper sulfide system are extremely complex
fides, their differing electrical conductivities, and
catalytic effects . Transform at io ns between s uI-
fides or of sulfides to oxides result in changes
in volume that weaken the attachment scale and
oxide subscale, leading to spalling. Bared areas
repassivate forming cuprous oxide.
Biomineral dissolution reactions remove pas-
sive layers or force mineral replacement reactions
that lead to further dissolution. Biofilm formation of
copper alloys often results in selective dealloying
as zinc is incorporated in corrosion products.22
Dissimilatory iron and/or manganese reduction oc-
curs in several microorganisms, including anaer-
obic and facultative aerobic bacteria. MRB use
Mn(lV) and Fe(lll) oxides as the terminal electron
acceptors in anaerobic respiration, thereby con-
verting solid metal oxides to soluble metal ions.
Inhibitor and competition experiments suggest that
Mn(lV) and Fe(lll) are efficient electron acceptors
similar to nitrate in redox ability and are capable of
outcompeting electron acceptors of lower poten-
tial, such as sulfate or carbon dioxide.23 Obuekwe
et al.24 evaluated corrosion of mild steel under
conditions of simultaneous formation of ferrous
and sulfide ions. They reported extensive pitting
when both processes were active. When only sul-
fide was produced, initial corrosion rates increased
but later declined due to formation of a protective
FeS film. High amounts of soluble iron prevent
formation of protective sulfide layers on ferrous
metals.
Microorganisms within biofilms are capable
of maintaining environments at biofilm/surface
interfaces that are radically different from the
bulk in terms of pH, dissolved oxygen, and other
organic and inorganic species.25 In some cases,
these interfacial conditions could not be main-
tained in the bulk medium at room temperature
near atmospheric pressure. As a consequence,
1.6 Introduction

microorganisms within biofilms produce minerals

and mineral replacement reactions that are not
predicted by thermodynamic arguments based
on the chemistry of the bulk medium.26 For
that reason, minerals within corrosion products
can often be used as fingerprints for MIC. For
example, even though the region of stability
predicted for mackinawite (tetragonal Fel - x S )
using stability diagrams is wholly outside the
region defined by surface water Eh/pH condi-
tions (Figure 1.7), excluding waters influenced by
peat bogs, coal mines, volcanic activity, and indus-
trial effluents, mackinawite is easily produced from
iron and iron oxides in surface waters by consor-
tia of microorganisms that include SRB. The pres-
ence of mackinawite in corrosion products formed
in shallow-water environments, with the exclusions
previously delineated, is proof that corrosion was
S RB-induced .27

Limited Interpretation of
Cell Numbers

Because the diagnosis of MIC can be contro-

versial, it is extremely important that interpretation
of spatial relationships between microorganisms
and corrosion products be cautiously interpreted.
Until recently, a standard procedure for evaluat-
ing MIC has been the enumeration of specific
types of microorganisms, particularly SRB, either
in bulk liquids or in surface deposits, using a
liquid medium. Growth media tend to be strain-
specific and a single incubation temperature is
further selective. The problem with all techniques
that attempt to quantify specific populations within
biofilms is their overinterpretation to confirm or re-
fute the possibility of MIC. Little et a1.28 recently
demonstrated that anodic and cathodic polariza-
tions influence the numbers and types of bacteria
associated with surfaces. In the case of anodic po-
larization, large numbers of marine bacteria were
found in association with iron corrosion products
resulting from abiotic mechanisms. The organisms
had not caused the corrosion, but their numbers
and spatial relationship with the corrosion products
FIGURE 1.7
Iron stability diagram: water without chloride ions; to-
tal sulfide 1OV2 M. Parallelograms superimposed on the
diagram are bounded by the highest and lowest pH Val-
ues commonly found in natural fresh and saline surface
waters. The upper portion of the hatched area applies to
waters less than 10 m from the surface; the lower portion
(oppositely hatched) represents waters at depths greater
than 10 m. Conditions in the upper hatched parallelo-
gram represent those readily achieved in stagnant wa-
ters. The lower portion indicates conditions not found in
near-su rface environments.
could be easily misinterpreted. Dexter29 cited a
case in which corrosion products surrounding a
pit on an aluminum sample immersed in seawater
were more densely colonized by bacteria than the
Introduction
surrounding surface, but there was no evidence
that bacteria had caused the attack. Franklin
et reported that bacterial cells were associ-
ated with anodic regions on carbon steel detected
using scanning vibrating electrode microscopy.
They were cautious not to interpret their data to
indicate that the cells caused the anodic sites.
They did observe that once bacteria were asso-
ciated with anodic regions those areas remained
anodic for the duration of the experiments. Anodic
sites not associated with bacteria were transient.
Little et aL3’ made similar observations of the spa-
tial relationships between Oceanospiri//umand an-
odic regions on copper surfaces. De Sanchez and
Schiffrin3* demonstrated chemotaxis of a marine
Pseudomonas induced by transiton metal ion con-
centration gradients from corroding copper and ti-
tanium surfaces.
In the case of cathodic polarization, several in-
vestigators have made the observation that SRB
are attracted to cathodically polarized surfaces in
the absence of corrosion. Angel1 et al.33and Licina
et al.34 independently developed techniques for
measuring currents sustained by bacteria. Both
techniques require cathodic polarizations and
Licina et al.34 stated that polarization “encour-
aged biofilm formation.” Neither group has specif-
ically addressed differences in the microflora re-
sulting from the polarization. Gomez de Saravia
et and Videla et al.36 demonstrated that
cathodic polarization in a seawater medium in-
creased numbers of SRB and decreased numbers
of aerobic bacteria on carbon steel surfaces rel-
ative to unpolarized controls. They hypothesized
that preferential increases or decreases in cell
types were due to differences in cell isoelectric
points.
In summary, reliable test methods for identi-
fying or predicting MIC cannot be based on en-
numeration of organisms or their spatial relation-
ship to corrosion products. There is no correlation
between numbers and types of cells and localized
corrosion. Moreover, MIC does not have a sin-
gle diagnostic manifestation. The presence and
metabolic activities of bacteria heterogeneously
colonizing metal surfaces can produce pitting, un-
derdeposit corrosion, dealloying, and enhanced
1.7
galvanic3’ and crevice38corrosion. All can be pro-
duced by abiotic reactions and have a similar ap-
pearance whether or not they were influenced by
m i c r o ~ r g a n i s m s .Cause
~~ and effect need to be
proven using evidence from complementary tech-
niques before the most effective mitigation mea-
sures can be specified.
Acknowledgments
The work for this chapter was performed un-
der NRL Program Element 0601 153N and is NRL
Contribution Number NRL/BA/7333-97-0001.
References
1. G. Kobrin, ed., A Practical Manual on Microbiolog-
ically Influenced Corrosion (Houston, TX: NACE,
1993).
2. W.G. Characklis and K.C. Marshall, “Biofilms: A Ba-
sis for an Interdisciplinary Approach,” in Biofilms,
eds. W.G. Characklis and K.C. Marshall (New York,
NY: Wiley, 1990), p. 4.
3. D.H. Pope, D.J. Duquette, P.C. Wayner, and A.H.
Johannes, Microbiologically Influenced Corrosion:
A State of the Art Review (Columbus, OH: Mate-
rials Technology Institute of the Chemical Process
Industries, 1984).
4. B. Little, P. Wagner, and F. Mansfeld, “Microbiolog-
ically Influenced Corrosion of Metals and Alloys,”
Int. Mat. Rev. 36, 6(1991): 253-272.
5. 0. Wanner and W. Gujer, “A Multi-Species Biofilm
Model,” Biotech. Bioeng. 28(1986): 314-328.
6. B.E. Rittmann and J.A. Manem, “Development
and Experimental Evaluation of a Steady-State,
MuItispecies Biof iIm ModeI,” Biot ec hnoI. Bioeng.
39(1992): 914-922.
7. R.W. Robinson, D.E. Akin, R.A. Nordstedt, M.
Thomas, and H.C. Aldrich, “Light and Electron
Microscopic Examinations of Methane-Producing
Biofilms from Anaerobic Fixed-Bed Reactors,” Appl.
Environ. Microbiol. 48(1984): 127-1 36.
8. T. Eighmy, D. Maratea, and P.L. Bishop, “Electron
Microscopic Examination of Wastewater Biofilm
Formation and Structural Components,” Appl. Env-
iron. Microbiol. 45(1983): 1921-1931.
1.8
9. W.N. Mack, J.P. Mack, and A.O. Ackerson, “Micro-
bial Film Development in Trickling Filters,” Microb.
EcoI. 2(1975): 21 5-31 6.
10. S. Kugaprasatham, H. Nagaoka, and S. Ohgaki,
“Effect of Turbulence on Nitrifying Biofilms at Non-
Limiting Substrate Conditions,” Water Res. 26,
12(1992): 1629-1 638.
11. J.R. Lawrence, D.R. Korber, B.D. Hoyle, J.W.
Costerton, and D.E. Caldwell, “Optical Sectioning of
Microbial Biofilms,” J. Bacteriol. 173(1991):6558-
6567.
12. P.S. Stewart, B.M. Peyton, W.J. Drury, and
R. Murga, “Quantitative Observations of Hetero-
geneities in Pseudomonas aeruginosa Biofilms,”
Appl. Environ. Microbiol. 59, l(1993):327-329.
13. Z. Lewandowski, P. Stoodley, and S. Altobelli,
“Experimental and Conceptual Studies on Mass
Transport in Biofilms,” Water Sci. Technol.
31 (1 995): 153-1 62.
14. B. Little, P. Wagner, K. Hart, R. Ray, D. Lavoie,
K. Nealson, and C. Aguilar, “The Role of Biorniner-
alization in Microbiologically Influenced Corrosion,”
Biodeterioration 9(1998): 1-1 0.
15. W.H. Dickinson and Z. Lewandowski, “Manganese
Biofouling and the Corrosion Behavior of Stainless
Steel,” Biofouling 1O(1996): 79-93.
16. B. Little, P. Wagner, and F. Mansfeld, “Microbiolog-
ically Influenced Corrosion of Metals and Alloys,”
Int. Mat. Rev. 36, 6(1991): 253-272.
17. W. Lee, Z. Lewandowski, M. Morrison, W.G.
Characklis, R. Avci, and P.H. Nielsen, “Corrosion
of Mild Steel Underneath aerobic Biofilms con-
taining Sulfate-Reducing Bacteria-Part II: At High
Dissolved Oxygen Concentration,” Biofouling 7
(1993):217-239.
18. B. Little, P. Wagner, J. Jacobus, and L. Janus, “Eval-
uation of Microbiologically Induced Corrosion in an
Estuary,” Estuaries 12, 3(1989): 138-1 41.
19. B.C. Syrett, “Accelerated Corrosion of Copper in
Flowing Pure Water Contaminated with Oxygen
and Sulfide,” Corrosion 33(1977): 257-262; “The
Mechanism of Accelerated Corrosion of Copper-
Nickel Alloys in Sulfide Polluted Seawater,” COR-
ROSION/80, paper no. 33 (Houston, TX: NACE,
1980; “The Mechanism of Accelerated Corrosion
of Copper-Nickel Alloys in Sulphide-Polluted Sea-
water”, Corros. Sci. 21 (1981): 187-209.
20. I. Nilsson, S. Ohlson, L. Haggstrom, N. Molin,
and K. Mosbach, “Denitrification of Water Us-
i ng ImmobiIized Pseudomonas denitrificans Cel Is,”
Introduction
Europ. J. Appl. Microbiol. Biotechnol. 1O(1980):
261-274.
21. P.H. Ribbe, ed., Sulfide Mineralogy (Washington,
DC: Mineralogical Society of America, 1976).
22. B. Little and P. Wagner, “Impact of Alloying Ele-
ments on Microbiologically Influenced Corrosion,”
MP 32, 9(1993): 65-68.
23. C. Myers and K.H. Nealson, “Bacterial Manganese
Reduction and Growth with Manganese Oxide as
the Sole Electron Acceptor,” Science 240(1988):
1319-1 321.
24. (2.0. Obuekwe, D.W.S. Westlake, J.A. Plambeck,
and F.D. Cook, “Corrosion of Mild Steel in Cultures
of Ferric Iron Reducing Bacterium Isolated from
Crude Oil. I. Polarization Characteristics,” Corro-
sion 37, 8(1981):461-467.
25. Z. Lewandowski, S.A. Altobelli, and E. Fukushima,
“NMR and Microelectrode Studies of Hydrodynam-
ics and Kinetics in Biofilrns,” Biotechnol. Prog.
9(1 993): 40-45.
26. M.B. McNeil and B.J. Little, “Corrosion Mechanisms
for Copper and Silver Objects in Near-Surface En-
vironments,” J. Amer. Inst. Conserv. 31, 3(1992):
355-3 66.
27. M.B. McNeil and B.J. Little, “Mackinawite Formation
During Microbial Corrosion,” Corrosion 46,7(1990):
599-600.
28. B.J. Little, P.A. Wagner, K.R. Hart, and R.I. Ray,
“Spatial Relationships Between Bacteria and Lo-
calized Corrosion,” CORROSION/96, paper no. 278
(Houston, TX: NACE, 1996).
29. S.C. Dexter, “Role of Microfouling Organisms in Ma-
rine Corrosion,” Biofouling, 7(1993): 97-1 27.
30. M.J. Franklin, D.C. White, and H.S. Isaacs, “Pit-
ting Corrosion by Bacteria on Carbon Steel,
Determined by the Scanning Vibrating Elec-
trode Technique,” Corros. Sci. 32, 9(1991): 945-
952.
31. B. Little, P. Wagner, P. Angel, and D. White, “Cor-
relation Between Anodic Areas and Oceanospiril-
lum Biofilms on Copper,” Int. Biodet. Biodegrad. 37,
3-4( 1996): 159-1 62.
32. S.R. De Sanchez and D.J. Sciffrin, “Bacterial
Chemo-Atractant of Metal Ions from Dissolving
Electrode Surfaces,” J. Electroanal. Chem. 403
(1996): 39-45.
33. P. Angel, J.-S. Luo, and D.C. White, “Studies of the
Reproducible Pitting of 304 Stainless Steel by a
Consortium Containing Sulphate-Reducing Bacte-
ria,” Proceedings of the 1995 International Confer-
Introduction
ence on Microbially Influenced Corrosion (Houstan;
TX: NACE and American Welding Society, 1995),
pp. 1/1-1/10.
34. G.J. Licina, G. Nekoksa, and R.L. Howard, “An
Electrochemical Method for On-Line Monitoring
of Biofilm Activity in Cooling Water Using the
BloGEORGE- probe,” in Microbially Influenced
Corrosion Testing, eds. J.R. Kearns and B.J.
Little, ASTM STP 1232 (Philadelphia, PA: ASTM,
1994), pp. 118-1 27.
35. S.G. Gomez de Saravia, M.F.L. de Mele, and
H.A. Videla, “Interacciones de Biopeliculas Bacte-
rianas y Compuestos lnorganicos Sobre Aceros
Protegidos Catodicamente,” in 5th Congreso
Ibero-americano de Corrosion y Proteccion, ed.
D. Grandosa (La Laguna, Tenerife, lslas Canarias,
Spain, 1995), pp. 201-202.
1,9
36. H.A. Videla, S.G. Gornez de Saravia, and M. de
Mele, “Early Stages of Bacterial Biofilm and Ca-
thodic Protection Interactions in Marine Environ-
ments,” Proceedings of the 12th International Cor-
rosion Congress, (Houston, TX: NACE, 1993),
pp. 3687-3695.
37. S.C. Dexter and J. P. LaFontaine, “Effect of Natural
Marine Biofilrns on Galvanic Corrosion,” Corrosion,
54, ll(1998):851-861.
38. H.J. Zhang and S.C. Dexter, “Effect of Biofilms
on Crevice Corrosion of Stainless Steel in
Coastal Seawater,” Corrosion 51 1 (1995): 56-
66.
39. J.G. Stoecker, “Microbiological Influence and Elec-
trochemical Types of Corrosion: Back to Basics,”
CORROSION/94, paper no. 259 (Houston, TX:
NACE, 1994).

Fungal-Influenced Corrosion of Metals
in Humid Environments
Introduction
The availability of water influences the dis-
tribution and growth of microorganisms. Water
availability can be expressed as water activity (a,)
with values ranging from 0 to 1 .O. Microbial growth
has been documented over a range of a, from 0.60
to 0.998.’ Fungi are the most dessicant-resistant
microorganisms and can remain active down to
a, = 0.6 whereas few bacteria remain active at a,
values below 0.9.2 Fungi are nonphotosynthetic
organisms, having a vegetative structure known
as a hypha, the outgrowth of a single microscopic
reproductive cell or spore. A mass of threadlike
hyphae make up a mycelium (Figure 2.1).3 Mycelia
are capable of almost indefinite growth in the pres-
ence of adequate moisture and nutrients so that
fungi often reach macroscopic dimensions. Yeasts
are fungi that multiply by forming buds instead
of mycelia. Fungi are ubiquitous in atmospheric
and aquatic environments where they assimilate
organic material and produce organic acids
including oxalic, lactic, acetic, and citric. Spores,
the nonvegetative dormant stage, can survive
long periods of unfavorable growth conditions,
e.g., drought and starvation. When conditions for
growth are favorable, spores germinate.4
Biodeterioration due to fungi has been doc-
umented for the following: cellulosic materials
(paper, composition board, and wood); communi-
cation wire; cable splices; telephone cable; cable
sheaths; photographic film; polyvinyl chloride
2.1
CHAPTER 2
By B, Little and R, Ray
films; sonar diaphragm coatings; map coatings;
paints; metals; crude oil; fuel oil; jet fuel; kerosene;
greases; waxes; lubricants; adhesives; asphalt;
hydraulic fluids; rain repellents; textiles (cotton
and wool); vinyl jackets; leather shoes; feathers
and down; natural and synthetic rubber; optical
instruments; mechanical, electronic, and electric
equipment (radar, radio, flight instruments, wire
strain gauges, helicopter rotors); hammocks;
tape; thermal insulation; brick masonry and
concrete; medicines; and museum valuables.
Most documented cases of fungal-induced biode-
terioration involve materials other than metals or
metals exposed in aquatic or fluid environments.
For example, despite the extensive database
that has been developed on biodeterioration and
biocides, fungi remain a modern problem for
production, transportation, storage, and use of
hydrocarbon fuels contaminated with even small
amounts of water as documented by Videla5
and Stranger-Johannessen8 reported
deterioration of the epoxy resin coating of ship
holds filled with molasses, fatty oils, and other fluid
cargoes. She also confirmed fungal degradation
of polyurethane cable sheathing in the marine
e n ~ i r o n m e n t There
.~ are fewer documented case
histories of fungal-influenced corrosion of metals
in humid atmospheric conditions. Geesey’O dis-
cussed the potential corrosion problem for metal
containers selected for storage of nuclear waste
in terrestrial environments. The following are
documented case histories of fungal-influenced
corrosion of metals in humid environments.
2.2 Fungal-Influenced Corrosion of Metals in Humid Environments

FIGURE 2.1
Growth stages of filamentous fungi. (See color plates.)

FIGURE 2.2
(a) Wooden spool on which wire rope was stored. Pieces of paper are attached to rim edges. (b) Inside surface of
wooden spool. White deposits are the result of fungal growth. (See color plates.)
Funaal-InfluencedCorrosion of Metals in Humid Environments 2.3

Wire Rope

Between May 1992 and February 1993, cor-

rosion inspection statistics were compiled for 117
spools of wire rope used in military applications.”
Five of 58 highlines stored indoors showed some
sign of corrosion whereas 42 of the 59 spools
stored outdoors were unsuitable for use because
of localized corrosion. Time in storage was not
a factor. The one-inch carbon steel wire ropes
used in military applications are prepared with
six individual strands around an independent wire
core coated with a thick maintenance grease and
threaded onto wooden spools (Figure 2.2a) that
are wrapped in brown paper and black plastic prior

FIGURE 2.4
(a) Wire rope that had been in contact with wood and
PDA inoculated with Aspergillus niger. Rope rolled aside
to show localized corrosion after contact with agar or
wood (3X). (b) Light micrograph of localized corrosion
associated with fungi (40X). (See color plates.)

to storage. Wire rope may be stored for weeks

to months before being used. Any visible sign of
corrosion means that the rope cannot be used for
its intended purpose. Fungal growth was observed
on interiors of some wooden spools stored out-
doors (Figure 2.2b) and corrosion was most se-
vere on wraps of wire in direct contact with the
wooden spool flanges. There were numerous re-
ports of a musty odor associated with spools when
plastic packaging was removed. Aspergillus niger
and Penicillium sp. were isolated from wooden
spool flanges (Figure 2.3a,b). Isolates could not
FIGURE 2.3 be maintained on the protective grease (i.e., these
(a), (b) Micrographs of fungi associated with wooden fungi could not break down the maintenance
spool. coating to obtain nutrients). Instead fungi growing
2.4 Fungal-InfluencedCorrosion of Metals in Humid Environments

on wood produced copious amounts of CO2. The

FIGURE 2.5
Interior of H-53 helicopter with luxurious fungal growth
on polyurethane paint. (See color plates.)
pH of condensate monitored using a microelec-
trode with a tip diameter of 2.4 mm (Microelec-
trodes Inc., Londonderry, NH) was consistently
below 5.0. The acidic condensate dissolved the
maintenance grease and produced localized cor-
rosion (Figure 2.4a,b).
Laboratory data and field statistics implicated
the practice of storing carbon steel highlines in
humid conditions wrapped in plastic with microbi-
ologically influenced corrosion. The replacement
of plastic wrapping with paper packaging and re-
design of wooden spool flanges to include slats
one-half inch apart to promote ventilation are
currently being evaluated as control

FIGURE 2.6
( a ) Aureobasidiurn sp. colonizing polyurethane paint taken from H-53 helicopter. (bj 3 X magnification of (a). (c) ESEM
micrograph of Aureobasidiurn sp. on polyurethane paint. (dj Aureobasidiurn sp. on underside of polyurethane paint
chip (40X). (See color plates.)
Fungal-InfluencedCorrosion of Metals in Humid Environments 2,5

measures. One-hundred and forty-three new high-

lines manufactured in exactly the same way as
previously described are being monitored. Six of
seven spools wrapped in plastic and stored out-
doors showed signs of localized corrosion after
two months. There have been no reports of
localized corrosion of redesigned spools stored
outdoors where plastic wrap was eliminated.

Microfungal Degradation
of Painted Surfaces

Ship Holds
Stranger-Johannesseni2 reported that ship
holds carrying cereals, woods, and other dry
cargoes were severely corroded within months.
Heavy pitting and reduced thickness of the steel
plate were observed. Viable fungi were cultured
from the corrosion products. Originally the holds
had been coated with a chlorinated rubber paint.
Laboratory tests demonstrated that fungal isolates
grew on the coating without any additional nu-
trients. Fungal growth caused blistering and dis-
bonding within 10 days.
Military Helicopters
Numerous reports document fungal growth
in passenger compartments of in-service aircraft
coated with polyurethane paint (Figure 2.5). A
report by Lavoie and Little13 documented the
following eight fungal genera associated with
H-53 aircraft: Pestalotia, Trichoderma, Epicoc-
cum, Phoma, Stemphylium, Hormodendrum (also
known as Cladosporium), Penicillium, and Aure-
obasidium. At least one of the isolates can degrade
paint14 and other studies report that fungi of the
same class are capable of causing deterioration of
polyester-based urethane coatings currently used
on interiors of military helicopter^.^^^'^ Bacteria
and fungi were cultured from all surfaces of all plat-
forms. Representative culture plates indicated that
several fungal species were collocated. Distribu-
tion of organisms was not limited to standing water
or fluids. Organisms were cultured from virtually
FIGURE 2.7
Fungal-induced corrosion of bare 2024 T-6 aluminum
(40x1. (See color plates.)
all interior surfaces, including primer-coated and
polyurethane-coated 2024 T-6 aluminum, fiber-
glass structural members, caulking, synthetic fab-
rics, wiring, and air-conditioning ducts. Concen-
tration of organisms did depend on the availability
of nutrients and water. Fungi were more numer-
ous in low areas and occluded spaces hold-
ing water or hydraulic fluid. Fungi appear to
be able to use hydraulic fluid and lanolin as
sources of nutrients, but neither appears to be
the source of the fungi. The topcoat of a piece
of peeling paint was uniformly colonized by fungi
(Figure 2.6a-d). Environmental scanning electron
microscopy (ESEM) was used to demonstrate that
the fungus penetrated the coating and caused dis-
bonding between topcoat and primer. Glossy fin-
ish polyurethane fouled more readily than did the
same formulation with a flat finish. Aged paint
fouled more rapidly than new coatings. Labora-
tory tests demonstrated that in the presence of hy-
draulic fluid or lanolin, most of the isolates caused
localized corrosion of bare 2024 T-6 aluminum
(Figure 2.7).
Conclusions
The possibility of fungal-influenced corrosion
of metals in humid environments has enormous
2,6
economic consequences. In relative humidities of
60% or greater with adequate nutrients, fungi can
thrive and produce acidic by-products that cause
corrosion of bare metals and disbonding of coat-
ings on coated metals.
Acknowledgments
This work was supported by the Office of
Naval Research, Program Element 601 153N and
Wright Patterson U S . Air Force Base, Program
Element 631 12F. It is NRL Contribution Number
NRUBN7303-99-000 1.
References
1. D.A.A. Mossel and M. Ingram, “The Physiology of
the Microbial Spoilage of Foods,” J. Appl. Bacteriol.
18(1955): 232-268.
2. H.G. Schegel and H.W. Jannasch, “Prokaryotes
and their Habitats,” in The Prokaryotes: A Hand-
book on Habitats, Isolation, and Identification of
Bacteria, eds. M.P. Starr, H. Stolp, H.G. Truper, A.
Balows, and H.G. Schegel (New York: Springer-
Verlag, 1986), p. 52.
3. H.L. Barnett, lllustrated Genera of Imperfect Fungi,
2nd ed. (Minneapolis, MN: Burgess, 1965).
4. J.E. Smith and D.R. Berry, An Introduction to
Biochemistry of Fungal Development (New York:
Academic, 1974), p. 85.
5. H. Videla, ”The Action of Cladosporium resinae
growth on the Electrochemical Behavior of Alu-
minum,” in Proceedings of the lnternational Confer-
ence on Biologically Induced Corrosion (Houston,
TX: NACE, 1986), p. 215.
6. B.M. Rosales, A. Puebla, and D. Cabral, ”Role of
the Metal Uptake by the Mycelium of the Fungus
Hormoconis resinae in the MIC of Aluminum Al-
loys,” in Proceedings of the 12th lnternational
Fungal-InfluencedCorrosion of Metals in Humid Environments
Corrosion Congress (Houston TX: NACE, 1993),
p. 3773.
7. R.C. Salvarezza and H.A. Videla, “Microbiolog-
ical Corrosion in Fuel Storage Tanks. Part 1:
Anodic Behaviour. Acta Cien. Venezol. 35(1984):
244-247.
8. M. Stranger-Johannessen, “Microbial Deteriora-
tion of Corrosion Protective Coatings,” in Microbial
Problems in the Offshore Oil Industry (New York:
Wiley, 1986), pp. 57-61.
9. M. Stranger-Johannessen, “The Role of Microor-
ganisms in the Blistering and Debonding of Corro-
s io n Protective Organic Coatings ,” in Proceedings
of the XVIlIth FATlPEC Congress (Venezia, Italy:
1986), VOI. 3, pp. 1-13.
10. G. Geesey, ed. G. Cragnolino, “Review of the
Potential for Microbially Influenced Corrosion of
High-Level Nuclear Waste Containers, prepared for
Nuclear Regulatory Commission Contract NRC-02-
88-005 (San Antonio, TX: NRC, 1993).
11. B. Little, R. Ray, K. Hart, and I? Wagner, “Fungal
Induced Corrosion of Wire Rope in Humid Atmo-
spheric Conditions,” CORROSION/95, paper no.
190 (Houston, TX: NACE, 1995).
12. M. Stranger-Johannessen “Fungal Corrosion of the
Steel Interior of a Ship’s Holds,” in Biodeterioration
6, eds. S. Barry and D. R. Houghton (CAB Int. My-
cological Inst., 1986), pp. 218-223.
13. D. Lavoie and B. Little, “Fungal Contamination Of
H-53 Aircraft,” Naval Research Laboratory Memo-
randum Report NRL/MR/733-96-7725, 1996.
14. R. Zabel and F. Terracina, “The Role of Aureobasid-
ium pullulans in the Disfigurement of Latex Paints,”
Dev. Ind. Microbiol. 21 (1980): 179-1 90.
15. W. Cook, J. Cameron, J. Bell, and S. Huang,
“Scanning Electron Microscope Visualization of
Biodegradation of Polycaprolactones by Fungi,”
J. Polym. Sci. Lett. 19(1981): 159-165.
16. D. Wales and B. Sager, “The Mechanism of
Polyurethane Biodeterioration,” in Biodeterioration
and Biodegradation of Plastics and Polymers, ed.
K.J. Seal, Occasional Publications No. 1 (Kew, UK:
Biodeterioration Society, 1985), pp. 56-65.
 CHAPTER 3

Biodegradation of Nonmetallic
Engineering Materials
By B, Little, R.I. Ray, and P, W a g n e r

Int roduction Fungi are the most widespread and destruc-

tive group of microorganisms encountered in
biodegradation of materials. Fungi are aerobic,
All engineering materials become colonized by
nonphotosynthetic organisms with a vegetative
bacteria and fungi within hours after exposure in
structure known as a hypha that is the outgrowth
natural waters and in many atmospheric environ-
of a single microscopic reproductive cell or spore.
ments. Microorganisms grow and produce a vis-
Mycelia, masses of hyphae, are capable of al-
coelastic layer or biofilm. Most naturally occurring
most indefinite growth in the presence of adequate
biofilms contain a consortia of microorganisms
moisture and nutrients so that fungi often reach
with varied oxygen and nutritional requirements.
macroscopic dimensions. Fungi are ubiquitous
Additionally, nutritional needs of one species may
in atmospheric and aquatic environments where
be provided by other members of the community.
they assimilate organic material and produce or-
The environment at the biofilm/material interface
ganic acids including oxalic, lactic, acetic, and
is radically different from the bulk medium in terms
citric. Additionally, fungi produce carbon dioxide,
of pH, dissolved oxygen, and organic and inor-
which reacts with water to form carbonic acid.
ganic species. Biodegradation due to the activities
Fungal spores are widely distributed, and they tol-
of bacteria and fungi has been documented for
erate extreme ranges of temperature, pH, and hu-
nonmetallic materials including cellulosics (paper, midity. Fungi cause esthetic degradation via direct
wood), fabric (cotton, wool, rayon), vinyl textiles,
surface attachment in addition to loss of mechani-
leathers, greases and lubricants, rubber, coatings
cal properties due to enzymatic activities and pro-
(e.g., for electronics and structural applications),
duction of aggressive organic acid metabolites.
and architectural products including masonry and
This chapter will present recent studies and
concrete.
examples of biodegradation of nonmetallic engi-
Bacteria can tolerate a wide range of envi-
neering materials. Additional architectural materi-
ronmental conditions including extremes of pH
als are discussed elsewhere in this book.
and temperature. They vary in oxygen require-
ments from obligately aerobic to obligately anaer-
obic. Heterotrophic bacteria derive energy from a
large range of organic molecules while autotrophic Polymeric Materials
bacteria oxidize inorganic compounds as energy
sources. Bacterial production of gases, organic/ Until recently, little attention has been paid to
inorganic acids, and sulfides, as well as the for- environmental degradation of polymeric materials
mation of concentration cells, results in biodegra- because of the assumption that polymers would
dation of nonmetallic materials. not suffer the corrosion, biofouling, or deterioration

3.1
3.2
found in conventional materials. It is now recog-
nized that polymeric materials are subject to many
kinds of environmental degradation resulting in
loss of flexibility, elasticity, and strength due to frac-
ture, disbonding, or delamination. Possible mech-
anisms for microbial degradation of polymeric ma-
terials include: direct attack by acids or enzymes,
blistering due to gas evolution, enhanced cracking
due to calcareous deposits and gas evolution, and
polymer destabilization by concentrated chlorides
and sulfides. Fungal-induced black pitting (mildew)
and pink staining have been reported in the tex-
tile and paint industries.’ Enzymatic attack of poly-
meric plasticizers in flexible vinyls was related to
loss of elasticity and increased brittleness. Fungal
attack of polyester polyurethanes has also been
reported2
Organic additives including plasticizers, fillers,
and stabilizers, many of the ester type, may
provide nutrients for microbial growth and ulti-
mate d e g r a d a t i ~ n .Polymeric
~ materials are sub-
ject to degradation from moisture intrusion and
osmotic b l i ~ t e r i n g .Both
~ may be influenced by
biofilms. Weight change measurements suggest
that biofilms may act as a diffusion barrier for wa-
ter, retarding moisture ~ p t a k e . ~ , ~
Fiber-Reinforced Polymeric
Composites (FRPCs)
FRPCs are commonly used in atmospheric
and aquatic environments to replace conventional
materials in structural applications. Evaluations of
FRPCs in marine heat exchangers, condensers,
pumps, shipboard structures, and deep-sea appli-
cations are ~ n g o i n g Fiberglass-reinforced
.~ plas-
tics are in use as piping and pipe linings and
as protective claddings over metals and con-
crete. Performance advantages include increased
strength to weight ratio, hardness, wear and corro-
sion resistance, and stiffness and improved creep
behavior. Modifications during fabrication, includ-
ing the altering of thermal properties and configu-
rations, can be tailored for specific applications.
Fibers, resins, and the fiber-resin interface
have differing susceptibilities to biodegradation.
Fibers, usually glass or carbon, provide reinforce-
Biodegradationof Nonmetallic Engineering Materials
ment strength with low density. Resin matrices
provide load transmission and energy dissipation.
Fiber-resin interface bonding is essential for com-
posite integrity.
In laboratory experiments bacterial cultures
were chosen, to represent specific degrada-
tion mechanisms for worst-case exposures of
FRPC coupons (2.5 x 2.5 x 0.6 ~ m ) Cultures . ~
included Thiobacillus ferroxidans, a su Ifur/iron-
oxidizing bacter i um ; Pseudomonas fluorescens,
a calcareous-depositing bacterium originally
isolated from polIuted seawater; Lactococcus
lactis subsp. lactis, ATCC #19435, an ammonium-
producing bacterium ; Clostridium acetobutylicum,
ATCC #824, a bacterium previously shown to pro-
duce copious amounts of hydrogen from fermenta-
tion of s ~ g a r s and
; ~ a mixed facuItative/anaerobic
marine culture containing sulfate-reducing
bacteria (SRB) originally isolated from corroded
carbon steel in marine service.10 Two FRPCs-a
carbon fiber (T-300) reinforced epoxy and a
glass (S-2) and carbon (T-300) reinforced vinyl
ester-were exposed to all microbiological cul-
tures for 161 days. Additionally, carbon fibers,
glass fibers, vinyl ester, and epoxy resins were
individually exposed for 90 days to SRB and
hydrogen-producing bacteria. Glass fibers had
been treated with an organofunctional silane
surfactant to promote adhesion between the resin
and fibers and to facilitate handling.
Neither the epoxy nor the vinyl ester com-
posites were adversely affected by calcareous-
depositing or ammonium-producing bacteria.
There was no evidence of attack of resins, and
fibers remained embedded within both matrices.
Composites exposed to sulfur/iron-oxidizing bac-
teria were covered with crystalline deposits con-
taining iron and sulfur in addition to microbial cells.
All surfaces exposed to SRB were black due to the
deposition of iron sulfides. No damage to the epoxy
composite, epoxy neat resin, or carbon fibers could
be attributed to the presence and activities of SRB
and hydrogen-producing bacteria.
Glass fibers (Figure 3.la) exposed to SRB
lost all rigidity after a 90-day exposure so that the
weave pattern was no longer evident (Figure 3.1 b).
Control glass fibers remained rigid and maintained
Biodegradation of Nonmetallic Engineering Materials
FIGURE 3.1
Glass fibers (2X) (a) unexposed, (b)exposed to SRB in cul-
ture medium, and (c) exposed to sterile culture medium.
3.3
- BACTERIA
CELLS
- DlSBONDlNG
FIGURE 3.2
Hydrogen-producing bacteria at disrupted interfaces be-
tween fibers and vinyl ester resin.
the original weave pattern after exposure to sterile
culture medium (Figure 3 . 1 ~ )There
. was no direct
attack on the glass. Fibers are not usually directly
degraded by microorganisms, although Pendrys’
reported that p-55 graphite fibers were attacked
by a mixed culture of Pseudomonas aeruginosa
and Acinetobacfer calcoaceticus, common soil
isolates.
Hydrogen-producing bacteria appeared to dis-
rupt bonding between fibers and vinyl ester resin
(Figure 3.2). Disruption may have been due to gas
formation.
The impact of SRB on the tensile strength
of stressed FRPC was evaluated using acoustic
emission (AE). Flat rectangular lengths of a car-
bon fiber reinforced epoxy resin composite (6 ply,
unidirectional fiber volume 50%) were prepared
and assembled in three- and four-point bends at
controlled strains.12 After seven months bacteria
and/or sulfide crystals were preferentially concen-
trated along fiber-resin interfaces and in superfi-
cial surface scratches (Figures 3.3 and 3.4). AE
testing suggested a 10% loss in tensile strength
as the result of microbial exposures.
Gu et reported fungal degradation of
carbon-reinforced epoxy, carbon-reinforced
bismaleimide, and glass-reinforced fluorinated
polyimide composites due to hyphae penetration
into resin interiors. Electrochemical impedance
spectroscopy was used to demonstrate increas-
ing permeability over 8 months exposure to a
naturally occurring fungal culture, containing
Aspergillus versicolorand a Chaetomium species.
3.4
FIGURE 3.3
Bacteria and crystals preferentially distributed along
fiber-resin interfaces and surface anomaly.
The authors concluded that microorganisms may
derive energy from resins and fiber sizings.
Polymeric Coatings
Moisture- and chemical-resistant polymeric
coatings and linings are used to protect underly-
ing metals against corrosion. The coatings may be
based on acrylonitrile, oleoresins, polyurethane,
polyamide, vinyl, epoxy, or other resins. Coat-
ing performance is influenced by composition,
thickness, continuity, adhesion to the metal sub-
stratum, and resistance to microbial degradation.
Bacteria and fungi can produce acids and en-
zymes that cause degradation. Polyesters and
polyester polyurethane coatings can be vulnera-
ble to microbial attack by enzymatic hydrolysis of
the ester segment.14 Microbial production of acids
and enzymes may result in selective leaching of
coating components with increased ion transport
and porosity.
FIGURE 3.4
Disrupted fibers of stressed coupons colonized by
rn icroorgan ism.
Biodegradation of Nonmetallic Engineering Materials
There are numerous references to deteriora-
tion of coatings and linings in fuel tanks. Premature
failures were accompanied by heavy microbio-
logical growth.15-17 Spatial relationships between
microorganisms and blisters have received con-
siderable attention. One assumption had been
that microorganisms must penetrate the coating to
cause loss of adhesion and blistering. Stranger-
Johannessen and Norgaard18 observed that
microbial metabolites attacked the surface of coat-
ings containing zinc chromate and zinc phos-
phate exposed in humid environments, changing
chemical and physical properties without coat-
ing penetration. The degree of blistering was re-
lated to the amount of growth. In their studies,
blister-substratum interfaces were usually dry, and
when fluid was present it was often sterile or
contained microorganisms that would not induce
coating degradation.
Epoxy resin coatings have been reported to
fail after nine months of service when used to coat
ship holding tanks for molasses, fatty oils, and
other fluid cargoes. Two spore-forming bacilli iso-
lated from the failures caused blistering in newly
coated surfaces after one week.lg Similarly, ship
holds carrying cereals, wood, and other dry cargo
became severely corroded after months of service
due to the activities of unidentified fungi on the
chlorinated rubber coating, causing disbonding.20
Breaches in the coatings expose metal sub-
strata to further attack. Jones et aLiO described
breaches in nylon, epoxy, and polyurethane coat-
ings over steel exposed to mixed marine com-
munities of anaerobic and facultative bacteria, in-
cluding SRB. Additionally, epoxy, but not nylon,
coatings showed pinpoint holes, blistering, and
peeling after a one-month exposure to a non-
marine bacterial assemblage including SRB. The
authors suggested that microorganisms respon-
sible for breaching the coatings may not neces-
sarily be those that initiate localized corrosion
on the metal under the failed coating. Jones-
Meehan et aL2I demonstrated water and bacterial
intrusion under a polythioether conductive caulk
that resulted in corrosion of the underlying steel
(Figure 3.5a,b).
Mansfeld et a1.22evaluated microbial degrada-
tion of coatings in both marine and atmospheric
Biodegradation of Nonmetallic Engineering Materials
FIGURE 3.5
(a) Conductive caulk applied to 4140 steel after 15-
month exposure to a mixed, SRB-containing culture and
(b) microbial biofilm under the caulk on the steel surface.
exposures. A damage function, calculated based
on remotely collected EIS and electrochemi-
cal noise analysis, was confirmed visually. Each
damage function was directly related to an area
FIGURE 3.6
(‘1) Latex c o,ititig breach and (b) associated bacteria after exposure to SRB-containing culture.
3.5
of delamination. Damage functions were used
for qualitative assessment of coating deterio-
ration. Steel coupons coated with phosphate
primer, epoxy midcoat, and polyurethane topcoat
with an average thickness of 76 p m were ex-
posed for 405 days in Pacific Ocean seawater.
Blisters in the coating were typically associ-
ated with microorganisms (Figure 3.6a,b). After
exposures to a mixed culture containing SRB,
coating breaches in latex topcoats with zinc primer
and epoxy polyamide midcoat on steel were sur-
rounded by corrosion products and bacteria. Simi-
lar microbial preference for surface anomalies was
observed on alkyd-coated steel after exposure to
the same SRB culture. The association of bacteria
with blisters or corrosion products cannot be inter-
preted as microbiologically influenced corrosion.
Recent work by Little et al.2324 demonstrated that
marine bacteria and iron corrosion products are
collocated in corrosion products produced by abi-
ological corrosion mechanisms.
Gu et al.25studied fungal degradation of poly-
imide films used as insulators in electronic pack-
aging. Increased ionic permeability was observed
using EIS after a one-week exposure to a fungal
consortium largely identified as A. versicolor. Re-
sistance of the films dropped from 1 O8 to 1O6 ohms
cmP2,indicating significant changes in the coating
dielectric properties.
Lavoie and Little26 isolated fungi from thick
black deposits (Figures 3.7a,b) on oily, painted
aluminum surfaces of military helicopter interiors.
Fungi were growing on polyester polyurethane
coatings, underlying aluminum. fiberglass. caulk-
ing. synthetic fabrics, and electronic wiring. The
36 Biodegradation of Nonmetallic Engineering Materials

FIGURE 3.7
Fungal growth on polyester polyurethane coating at magnifications of (a) 6 X and (b) and (c) ESEM micrographs of fungal
spores associated with corrosion products in breaches in polyester polyurethane coating.

following nine genera were identified: Aureoba-
sidium, Hormodendrum, Phoma. Alternaria, Epic-
occum, Penicillium, Pestalotia. Stemphylium. and
Trichoderma. Aureobasidium is known to colonize
and discolor organic coatings.27 Fungi were physi-
cally associated with corrosion products formed in
scratches in the protective coating (Figure 3 . 7 ~ ) .
Concrete
Concrete is used in worldwide structural appli-
cations because of its strength, durability, and low
cost. It is used for large storage tanks and pipes.
interior linings and exterior ballast coatings for
steel pipe and containers, paving and many other
applications. A major construction application is
municipal wastewater collection and treatment
systems. Concrete is currently being evaluated as
one of the barriers for protection of nuclear waste
during storage. Severynz8estimates that the dete-
rioration of concrete in wastewater collection and
treatment systems is primarily due to biodegrada-
tion and that over $1 00 million are spent annually
to replace manholes, wet wells, concrete pipes,
treatment facilities, and grit chambers.
Concrete is an inert aggregate, such as rock
and gravel. surrounded by a cement binder. Hy-
drated silicates and aluminates are produced in
the reaction with water. Deterioration of concrete
will result when any environmental agent can
break the inorganic bonds of the cement binder.
Acids, sulfates, ammonium and magnesium
salts. alkalies, organic esters. and carbon dioxide
can destroy a binder over time. Perfettini et al.29
evaluated degradation of cement binder induced
by metabolic products of two fungal strains,
Aspergillus niger and Mycelia sterila. isolated
from soil samples. Portland cement was exposed
in direct contact to the two fungal strains for 1 1
months. Acids produced by A. niger (gluconic and
oxalic) dissolved the cement, increasing poro-
sity by 11.4% and reduced the bending strength
(the strength applied to three points on the
surface that causes breakage) by 78%. Increased
porosity indicates cement dissolution and permits
penetration of biological and chemical species.
M. sterila (gluconic and malic acids) caused a
Biodegradation of Nonmetallic Engineering Materials 3.7

significant 4.2% leaching of calcium original con-

tent, an 11% increase in porosity, and a 62% loss
in bending strength. Major organic acids produced
by fungi solubilize calcium, silica, aluminum, and
iron minerals. Solubilization is related more to the
nature of the acid than to concentration.
Kulpa and Baker30 and Mansfeld et aL3’ de-
scribe the complex biodegradation process in
sewage collection systems involving aerobic and
o~--i anaerobic bacterial mediation of the sulfur cycle.
J I I I I I Under anaerobic conditions SRB reduce sulfate
to sulfide in the sewage. Hydrogen sulfide (H2S)
is released into the aerobic ,environment at the
sewer pipe crown above the sewage where it is

3 100
c
/ oxidized to sulfuric acid by sulfur-oxidizing bac-
teria, commonly Thiobacilli. As acid is produced
0 the pH level may reach a value of 2.0 or lower.
3
L Dissolution of the concrete pipe occurs as the re-
sult of corrosive action of the acid. Mansfeld et
aL3’ monitored surface pH values and corrosion
rates of embedded steel sensors to evaluate con-
crete deterioration and control measures. Linear
0 polarization techniques were used to determine
0 40 80 120 160 200 polarization resistance and cumulative corrosion
DAYS loss (INT) for sewage-flushed and control sensors
FIGURE 3.8 (Figure 3.8). Most concrete structures include
Cumulative corrosion loss ClNT for mild steel sensors steel reinforcements, which will readily corrode
embedded in concrete and exposed to a sewer bypass: if exposed as a result of concrete deterioration
(a) control sample and (b) flushed sample. (Figure 3.9a,b). Moosavi et aL3* reported that the

FIGURE 3.9
(a) Corrosion of rebar in concrete and (b) bacteria associated with corrosion product. (See color plates for 3.9a.)
3.8
NON-DEGRADED
ASPHALT
-
FIGURE 3.10
Bacterial colonization and degradation of asphalt.
biogenic production of H2S by SRB could perme-
ate concrete and convert the passive iron oxide
film on steel rebars to a nonprotective iron sulfide
film.
Other Engineering Materials
Aspha/f
Asphalt is the unrefined residue of the frac-
tional distillation of petroleum crude oil and is
used extensively in road construction. Petroleum-
degrading bacteria excrete biosurfactants that
emulsify petroleum hydrocarbons by reducing
interfacial tension between the hydrocarbons
and water. pen dry^^^ exposed asphalt for
three weeks to a mixed culture (Pseudomonas,
Acinetobacter, Alcaligenes, Flavimonas, and
Flavobacterium genera) cultivated to use asphalt
as a sole carbon source. The author concluded
that resultant brittleness and flaking were limited
mainly to the asphalt surface (Figure 3.10). The
saturate and naphthalene aromatic distillation
phases supported increased bacterial growth with
concomitant emulsification.
Wood
Wood is one of the most commonly used
engineering materials. Its main components are
cellulose, polyoses (polysaccharides), and lignin.
Cellulose cell structure determines tensile
Biodegradation of Nonmetallic Engineering Materials
- COLONIZATION
BACTERIAL
7
DEGRADED
ASPHALT
strength, polyoses influence wood swelling and
shrinkage, and lignin makes the wood resistant
to pressure.34 Fungal species are the most com-
mon microorganisms in colonization/attack, espe-
cially in humid conditions. Bacterial attack of wood
is known but not as common. Fungal coloniza-
tion of coatings on painted and processed woods
may cause ingress of moisture. Basidiomycetes
(soft rot fungi) may degrade one or more of the
three main wood components leading to loss of
strength and weight in addition to disfigurement
(Figure 3.1 la,b,c).
Additional Comments
The emphasis of this chapter has been on
the negative aspects of biodegradation of non-
metallics. However, biodegradation can have pos-
itive effects. Synthetic polymeric composites of
polyactide, polyglycolide, and polyhydroxybutyric
acid are designed for use as implant screws,
pins, and plates to fix fractured bones in place.
Biodegradable plastics reduce the number of
operations a patient must undergo.35 Biodegrad-
able polymer resins compete with plastic materials
in the form of mulch films, planting containers,
hay twine, surgical stitching, medicine capsules,
and composting bags.36 Biodegradable conformal
coating for printed boards and components can
be removed by microorganisms rather than toxic
Biodegradation of Nonmetallic Engineering Materials 3.9

Conclusions

Most engineering materials are ultimately sus-

ceptible to microbial deterioration. Both sus-
ceptibility and rate of degradation vary among
materials. Laboratory and field data have been
collected that document biodegradation of fiber-
reinforced polymeric composites, polymer-coated
metals, concrete, asphalt, and wood. In excep-
tional cases it is possible to estimate the percent-
age of the total degradation of a particular mate-
rial that can be attributed to microbial processes.
For example, Severyn28estimates that biodeteri-
oration of concrete in wastewater collection and
treatment systems costs approximately $1 00 mil-
lion annually. Laboratory evidence indicates that
asphalt is biodegradable at a slow rate. However,
there are no case histories that document the prob-
lem in an engineering application. In most cases
economic data related to biodegradation are not
available.

Acknowledgments

This work was supported by the Office of Naval

Research, Program Element 0601 153, the De-
fense Research Sciences Program, and is NRL
Contribution Number NRUBN7333-98-00XX.

References

1. P. Baker, Plastics Compound. SepVOct, (1978): 35.

FIGURE 3.11
(a) Deterioration of wood due to bacteria and fungi, (b)
fungal colonization (400x1, and (c) staining to show bac-
terial penetration of wood (1 OOOX). (Courtesy of R. Lutey,
Buckman Laboratories, Memphis, TN.) (See color plates.)
solvents and detergents. Biosynthetic materials,
such as polyhydroxyalkanoates, poly-L-malate,
and polycaprolactone, are candidate materials
to replace thermoplastics because of their biode-
gradability, especially in ~eawater.~’
2. R.A. Pathirana and K.J. Seal, Biodeferiorafion 5
(London: Wiley, 1983), p. 679.
3. F.J. Upsher, “Microbial Attack on Materials,” Proc.
Roy. Austral. Chem. Inst. 43-44, 6( 1976): 173.
4. R. Davis, J.S. Ghotra, T.R. Malhi, and G. Pritchard,
“Blister Formation in RP: The Origin of the Os-
motic Process,” 38th Annual Conference, SPI Re-
inforced PlasticsComposites Institute, paper no.
17-8 (New York: Society of Plastics Industry,
1983).
5. V. Stolarski, A. Letton, W. Bradley, and L.R.
Cornwell, “Environmental Degradation of Poly-
mer Matrix Composite Exposed to Seawater,”
3.10
Proceedings of the 12th International Corrosion
Congress (Houston, TX: NACE, 1993).
6. Pu B. Little, J.S. Puh, P.A. Wagner, and W.L.
Bradley, “The Effects of Biofouling on Graphite/
Epoxy Composites,” J. Compos. Technol. Res. 20,
1(1998): 59-67.
7. A.J. Sedriks, MP 33, 2(1994): 56.
8. P.A. Wagner, R.I. Ray, B.J. Little, and W.C. Tucker,
MP 33, 4(1994): 46.
9. T.E. Ford, P.C. Searson, T. Harris, and R. Mitchell,
J. Electrochem. SOC.,137(1990): 1175.
10. J.M. Jones, M. Walch, and F.B. Mansfeld, “Micro-
bial and Electrochemical Studies of Coated Steel
Exposed to Mixed Microbial Communities,” COR-
ROSION/91, paper no. 108 (Houston, TX: NACE,
1991).
11. J.P. Pendrys, J. Electrochem. SOC., 136(1989):
113C.
12. P. Wagner, R. Ray, K. Hart, B. Little, W. Bradley,
and P.-L. Chiou, “Microbial Degradation of Stressed
Fiber Reinforced Polymeric Composites,” CORRO-
SION/95, paper no. 200 (Houston, TX: NACE,
1995).
13. J.-D. Gu, T.E. Ford, K.E.G. Thorp, and R. Mitchell,
“Microbial Deterioration of Fiber Reinforced Com-
posite Materials,” Proceedings of the International
Conference on Microbially Influenced Corrosion,
P. Angel1 et al., eds. (Houston, TX: NACE, 1995)
p. 25/1.
14. B. Mitton, T.E. Ford, E. LaPointe, and R. Mitchell,
“Biodegradation of Complex Polymeric Coatings,”
CORROSION/93, paper no. 296 (Houston, TX:
NACE, 1993).
15. J.J. Reynolds, M.G. Crum, and H.G. Hedrick, “Stud-
ies on the Microbiological Degradation of Aircraft
Fuel Tank Foatings,” Develop. Indust. Microbiol.
8(1967): 260-266.
16. H. Becker and H. Gross, “Beschadigung von Tank-
innenbeschichtungen durch Mikroorganism,” Farbe
und Lack, 77(1971): 533-539.
17. R.N. Miller, W.C. Herron, A.G. Krigrens, J.L.
Cameron, and B.M. Terry, Microorganisms Cause
Corrosion in Aircraft Fuel Tanks,” Mater. Protec.
3(1964): 60-67.
18. M. Stranger-Johannessen and E. Norgaard, Int.
Biodeterior. 27( 1991): 157.
19. M. Stranger-Johannessen, “Microbial problems in
the Offshore Oil Oli Industry,” Proceedings of an
International Conference organized by the Insti-
tute of Petroleum Microbiology Committee, held in
Aberdeen, April 1986, eds. E.C. Hill, J.L. Shennan,
Biodegradation of Nonmetallic Engineering Materials
and R.J. Watkinson (New York, NY: Wiley, 1987),
pp. 57-62.
20. M. Stranger-Johannessen, “Fungal Corrosion of
the Steel Interior of a Ship’s Holds,” in Biode-
terioration 6, eds. S. Barry and D.R. Houghton
(CAB Int. Mycological Inst., 1986), pp. 218-
223.
21. J. Jones-Meehan, K.L. Vasanth, R.K. Conrad, B.
Little, and R. Ray, “Corrosion Resistance of Sev-
eral Conductive Caulks and Sealants from Marine
Field Tests and Laboratory Studies with Marine,
Mixed Communities Containing Sulfate Reducing
Bacteria ,” Int ernat io nal Symposium on Mic robio Iog-
ically Influenced Corrosion (MIC) Testing (Miami,
FL: American Society for Testing and Materials,
1994).
22. F. Mansfeld, H. Xiao, L.T. Han, C.C. Lee, C. Chen,
J. Jones-Meehan, and B. Little, “Evaluation of Coat-
ing Degradation for Polymer Coated Steel Exposed
to Seawater,” CORROSION/96, paper no. 659
(Houston, TX: NACE, 1996).
23. B.J. Little, P.A. Wagner, K.R. Hart, and R.I. Ray,
“Spatial Relationships Between Bacteria and Lo-
calized Corrosion,” CORROSION/96, paper no. 278
(Houston, TX: NACE, 1996).
24. B. Little, R. Ray, P. Wagner, J. Jones-Meehan, C.
Lee, and F. Mansfeld Spatial Relationships Be-
tween Marine Bacteria and Localized Corrosion,”
Biofouling X(2000): X.
25. J.-D. Gu, T.E. Ford, K.E.G. Thorp, and R. Mitchell,
“Microbial Degradation of Polymeric Materials,” in
Proceedings of the Tri-Service Conference on Cor-
rosion (Orlando, FL: 1994), p. 291.
26. D.M. Lavoie and B.J. Little, “Fungal Contamina-
tion of H-53 Aircraft,” Naval Research Labora-
tory Memorandum Report NRL/MR/733-96-7725,
1996.
27. R.A. Zabel and F. Terracina, Dev. Ind. Microbiol. 21
(1980): 179.
28. G. Severyn, “Concrete Protection Systems for
Repair of Deteriorated Infrastructures from MIC,”
in Microbially Influenced Corrosion and Biodete-
rioration, eds. N.J. Dowling, M.W. Mittleman, and
J.C. Danko (Knoxville, TN: Univ. Tennessee, 1991),
pp. 6-23.
29. J.V. Perfettini, E. Revertegat, and N. Langomazino,
Experientia 47(1991): 527.
30. C.F. Kulpa and C.J. Baker, “Involvement of Sulfur-
Oxidizing Bacteria in Concrete Deterioration,” in
Microbially Influenced Corrosion and Biodeterio-
ration, eds. N.J. Dowling, M.W. Mittleman, and
Biodegradation of Nonmetallic Engineering Materials
J.C. Danko (Knoxville, TN: Univ. Tennessee, 1991),
4-7.
31. F. Mansfeld, H. Shih, A. Postyn, J. Devinny, R.
Islander, and C.L. Chin, “Corrosion Monitoring
and Control in Concrete Sewer Pipes,” CORRO-
SION/90, paper no. 113 (Houston, TX: NACE,
1990).
32. A.N. Moosavi, J.L. Dawson, and R.A. King, “The
Effect of Sulphate-Reducing Bacteria on the Cor-
rosion of Reinforced Concrete,” in Biologically In-
duced Corrosion, ed. S.C. Dexter (Houston, TX:
NACE, 1986) p. 291.
33. J.P. Pendrys, Appl. Environ. Microbiol. 55(1989):
1357.
3.1 1
34. European Federation of Corrosion, Microbiologi-
cal Degradation of Materials-and Methods of Pro-
tection (London: The Institute of Materials, 1992),
p. 37.
35. P. Tormala, “Biodegradable Plastics for Use in Im-
plants,” Biomed. Mater. Feb.(l993): 2.
36. D.E. Beach, R. Boyd, and N.D. Uri, “Expanding
Biodegradable Polymer Resin Use: Assessing the
Aggregate Impact on the US Economy,”Appl. Math.
Model. 20(1996): 388-398.
37. H.P. Molitoris, “Decomposition of Plastics in the
Sea,” in Proceedings of the 9th International
Congress on Marine Corrosion and Fouling
(Portsmouth, UK: 1995).

The Biodeteriorationof Building Materials
Introduction
Throughout history humans have used the
most beautiful and durable stone for monumental
buildings. Beginning in the sixth century B.C., mar-
ble extracted from the Pentelikon quarry became
a common building material. Abundant limestone
and marble quarries enabled the ancient Greek
architects to build the Acropolis and Roman archi-
tects to build the Forum.
Weathering starts as soon as a stone is
extracted from a quarry or a mortar is placed in a
building. Weathering of building materials is cau-
sed by natural environmental factors. Sun, frost,
wind, rain, and so forth contribute gradually to this
process in which materials are broken down into
smaller particles and ultimately into constituent
minerals.
Colonization and biodeterioration on build-
ing materials usually are linked to environmental
conditions.’ The most significant parameters af-
fecting microbial growth are represented by phys-
ical factors, mainly moisture, temperature, and
light, as well as by the chemical nature of the sub-
stratum. Only water and a minimal supply of min-
eral salts are required for colonization by pioneer-
ing organisms. It is the duration of the period of
wetness that is crucial, rather than the frequency of
wetting, in predisposing a surface to colonization.
Inoculation is more rapid where there is ad-
jacent or overhanging vegetation from which mi-
croorganisms can be brought by wind and rain,
and development is further accelerated by bird
droppings, agricultural fertilizers, and pollution-
derived nitrogen oxides, which introduce additional
4.1
CHAPTER 4
By C. Saiz-Jimenez
nitrogen and phosphorus. Rough or porous sur-
faces facilitate attachment of a,irborne propagules
and the accumulation of nutrients.
A primary colonization of chemoautotrophic
bacteria favors settling of heterotrophic bacteria
and fungi. The activity of heterotrophic bacteria
on stone is governed by the availability of suitable
organic matter. Most stones contain sufficient or-
ganic matter from deposition of airborne particles,
dust, soil, or dead autotrophic and phototrophic
organisms to maintain growth and activity of large
populations of bacteria.
Many building materials are prone to colon-
ization by organisms. Recently, biorecepfivify was
defined as the aptitude of a material to be
colonized by one or several groups of living
organisms without necessarily undergoing any
biodeterioration.* Biodeterioration implies material
degradation. Bioreceptivity tests for three different
materials-Carrara marble, Balegem calcarenite,
and mortar-have been carried out. These ma-
terials were previously subjected to different kinds
of physical treatments, including frost-thaw cycles
and thermal shock treatments, to induce physical
and chemical weathering.
After three months of incubation with the
cyanobacterium Gloeofhece sp. PCC 6909, it was
observed that bioreceptivity was different for the
three materials. Better growth and development
of the biofilm was provided by mortar, followed
by Carrara marble, and Balegem calcarenite. The
type of treatment apparently had no effect on the
bioreceptivity of mortar and Carrara marble to
cyanobacterium. In the case of the calcarenite,
growth was absent in untreated samples or sam-
ples treated with frost-thaw cycles (frost and thaw
4.2
by air). Treatments that included water as thaw-
ing or cooling agents (in frost-thaw and thermal
shock treatments, respectively) allowed the growth
of Gloeothecesp. Therefore, in these cases physi-
cal treatment changed the bioreceptivity of the ma-
terials to the organism owing to the action of water
on the mineral components and its mobilization.
Guillitte and Dreesen exposed a wider range of
materials (stones, bricks, mortars, and concrete)
to a nine-month period of intermittent sprinkling on
steeply inclined runoff surface^.^ The liquid con-
tained a mixture of pioneer organisms, from which
cyanobacteria, algae, diatoms, and mosses were
successful in colonization. They demonstrated that
the bioreceptivity of building materials is highly
variable and is controlled primarily by their sur-
face roughness, initial porosity, and mineralogical
nature.
In contrast, air pollution modifies the chem-
ical composition of building materials in urban
environments, resulting in the selection of mi-
croorganisms with specific nutrient requirements
or with a defined metabolic ~ a p a b i l i t y .In ~ this
context, the enrichment of stones in nitrogen
and sulfur compounds opens the way to sulfur-
and nitrifying-bacteria c o l ~ n i z a t i o nCyanobacte-
.~
ria needing sulfates for carbohydrate sheath pro-
duction and balanced growth find a good niche
in weathered stones with gypsum crusts6 Het-
erotrophic bacteria and fungi are selected in ur-
ban environments because of the considerable in-
put of petroleum-derived compounds, from which
n-alkanes can be readily ~ t i l i z e d . ~
In this paper, colonization, growth, and deteri-
oration of building materials by organisms are re-
viewed.
Building Materials
Some of the most frequently used building ma-
terials are based on carbonates (limestone, mar-
ble, sandstone, mortar, etc.). Carbonates are an
important reservoir of carbon on the earth’s sur-
face, accounting for 78.5% of total carbon. Car-
bonates in nature may be readily degraded as a
direct or indirect result of microbiological activity.
The Biodeteriorationof Building Materials
The chemical basis for this decomposition is the
instability of carbonates in acid solution.8 There-
fore, any organism that generates organic acids
(bacteria, fungi, lichens, etc.) or inorganic acids
(bacteria) is capable of dissolving insoluble car-
bonates. Even the mere metabolic generation of
CO2 during respiration has this effect. In addi-
tion, other building materials, such as granites and
bricks, more resistant to biodeterioration, are used
for monumental constructions.
Limestones and Marbles
The relatively easy workability of limestone
makes it the most frequently used stone for con-
struction of historic buildings and monuments.
Limestone is mainly composed of calcium (calcite)
and magnesium (dolomite) carbonates, with vary-
ing amounts of other materials, such as quartz,
clay, and bioclasts. Marble is a metamorphic rock
formed by the recrystallization of limestone under
relatively high heat and pressure. It is capable of
taking a high polish and, therefore, is used for or-
namental purposes.
Microbiological analyses of weathered stones
have shown the presence of bacteria that utilize
sulfur dioxide or sulfur-containing compounds, giv-
ing rise to sulfate as a product of m e t a b o l i ~ m . ~ ~ ’ ~
Bacteria can be involved in oxidation as well as
reduction of sulfur. Atlas et al. have reported that
the calcium ions obtained by release from gypsum
when Desulfovibrio desulfuricans reduces sulfate
react with carbon dioxide, resulting in the formation
of calcite.’’ Gypsum crusts on marble treated with
a bacterial broth showed the cleaning and neomin-
eralization carried out by the bacterium, which con-
sumed a large portion of the available gypsum in
the crust.
Heterotrophic bacteria were assumed to be re-
sponsible for a red-orange stain in Carrara marble
decorating the faGade of the Certosa of Pavia, Italy
(Figure 4.1). However, further studies showed that
the origin of the stains was due to the presence
of minium (Pb304)as lead was probably used for
anchoring the marble slabs to the walls.’*
Ortega-Calvo and Saiz-Jimenez reported the
presence of phenanthrene-degrading bacteria
The Biodeteriorationof Building Materials
FIGURE 4.1
Staining of marble on the Certosa of Pavia, Italy. (See
color plates.)
in the limestones of two European cathedrals
(Seville, Spain, and Mechelen, Belgium) as
demonstrated by conversion to 14C02 of [9-
14C]phenanthrenefreshly added to the stones and
by isolation of bacteria capable of using phenan-
threne as sole source of carbon and energy.13This
suggested that microorganisms present in build-
ing stones are able to transform deposited atmo-
spheric pollutants and to use them for growth.
It has been shown that fungi can also thrive
on building stones14-16 and their growth may in-
duce mechanical or chemical changes in miner-
als. The fungi isolated from weathered stones are
usually ubiquitous saprophytes whose conidia are
readily distributed through the atmosphere. Most
of the isolated species are commonly included in
floristic listings. Aspergillus, Penicillium, and Cla-
dosporium are among the most common airborne
fungi and, thus, have worldwide distribution. Also,
these fungi have a remarkable saprophytic and
polysaccharide-degrading potential.
The in vitro fungal corrosion of limestone was
studied by Koestler et a1.l’ After only five weeks
in culture the hyphae of a Trichotecium sp. pen-
etrated at least 1 mm into the crystals. Species
of Trichotecium are known to secrete oxalic acid,
citric acid, and gluconic acid among other prod-
ucts. These secretions can chemically attack the
dolomite or calcite, causing the observed etch-
ing. The channels created by the fungus further
4.3
provide new avenues of attack deep inside the
crystal and a vastly increased surface area sus-
ceptible to attack by water and/or dissolved acids
in the water, such as nitric and sulfuric acids from
air pollutants.
Fungi could decompose mineral matter, but
probably only in a microhabitat when there is an
accumulation of organic matter that can be metab-
olized. In a survey on fungi isolated from building
stones, the most efficient oxalic acid-producing
fungus was Aspergillus niger.16 It is well known
that in laboratory conditions organic acids are pro-
duced by many fungal cultures. These acids may
play a role in mineral weathering, owing to their
ability to form complexes with cations, promoting
the removal of the latter.18119
We must ask, “Are the organic acids produced
under natural conditions?,” because the produc-
tion of large amounts of metabolic products from
carbohydrates is a pathological behavior resulting
directly from the influence of abnormal environ-
mental conditions.20
Invariably, laboratory media for cultivation of
fungi contain carbohydrates in concentrations far
exceeding those the organism would ever en-
counter in nature, and to which the fungus is
adapted for maximum efficiency of utilization. It
appears that the enzyme mechanisms normally in-
volved in complete oxidation of the carbohydrate
become saturated, and the molecules are shunted
to secondary enzyme systems. Therefore, the pro-
duction of organic acids in many fungal cultures
could be the consequence of a metabolic overflow
and should not be extrapolated to nature.
Although cyanobacteria (formerly blue-green
algae) and algae are organisms commonly as-
sociated with aquatic ecosystems, they also are
widespread over terrestrial substrata. Their occur-
rence at the surface of soils, stones, and trees, par-
ticularly in moist areas, is well known. In building
materials they grow in humid places, on cornices,
in holes and crevices, or beneath crusts, where
water is retained and evaporation is slow owing to
protection against winds or direct sunshine. Fur-
thermore, growth also may be due, for example,
to leaking or badly sited roof guttering, to inade-
quate drainage of flat areas, or to frequent wetting
4.4
FIGURE 4.2
Phototrophic microorganisms on the fagade of the cathe-
dral of Salamanca, Spain. (See color plates.)
by wind-blown rain or from adjacent watercourses
(Figure 4.2). Their growth is rarely uniform,
frequently forming streaks that follow the areas of
dampness. Their presence is more apparent on
the north faCades of buildings than on the south,
because the latter dry out more readily.
Dupuy et al. differentiated, from an ecologi-
cal point of view, two main groups of cyanobac-
teria inhabiting monuments.21The first group con-
tains species living under dim light and constant
humidity conditions. They develop sheaths and
form heavy, colored growths on interior walls in-
side the buildings. The second group is composed
of species that can stand extreme conditions, such
as high light intensity and drought periods. They
The Biodeteriorationof Building Materials
are the major agent of soiling in exterior building
surfaces.
An unfavorable microclimate in the stone may
induce the formation of resistant algal forms, as
was observed by Pietrini et al. in marble remains
in Rome.22 This is a common mechanism in sur-
vival strategy. The reddish-orange colored patina
present on the marble was produced mainly by the
presence of cysts of Haernatoccus pluvialis. Their
formation is accompanied by a change in color
from green to red-orange owing to the production
of large quantities of cytoplasmatic carotenoids,
responsible for the color alteration.
Endolithic growth also could be considered as
a survival strategy. Saiz-Jimenez et al. found a
cryptoendolithic microbial community developed
as a green layer 1 mm below the surface of a lime-
stone from the Basilica of Tongeren, Belgium.23
This community was dominated by unicellular
cyanobacteria. Giaccone et al. found the endolithic
active borer Hyella fontana in marble statues in
Rome and attributed a role in the decay of the
stone to this c y a n o b a ~ t e r i u m . ~ ~
The aggressive action of phototrophic mi-
croorganisms in relation to the substratum where
they develop has been considered negligible by
some authors. However, apart from the unaes-
thetic appearance, evident in most of the reports
on cyanobacteria and algae on historic buildings,
there are few references in the literature that point
to direct decay mechanisms. The Cestia pyra-
mid in Rome presented pronounced pitting and
black stains in its walls, which were identified as
the effect of cyanobacterial g r o ~ t h .Hyvert~ ~ , ~re-~
ported that algae also caused the cavities of the
reliefs in Borobudur temple, Indonesia, to become
more p r o n ~ u n c e d .Danin
~ ~ reported weathering
of limestone walls and monolithic tombs up to
2,600 years old in Jerusalem, Israel, induced by
coccoid cyanobacteria.28 By decreasing the co-
herence of stone crystals around their colonies,
the cyanobacteria accelerate detachment of stone
particles, leading to weathering at the rate of
5 pm/y. The same stone without cyanobacteria
does not weather even after hundreds of years.
Phototrophic microorganisms also may have a
role in the mechanical biodegradation of the stone,
exerting considerable force through repeated
The Biodeterioration of Building Materials 4,5

FIGURE 4.3
Scanning electron micrograph of Gloeothece sp. cells
involved in the sheath.

shrinking and relaxation when they undergo cy-

cles of drying and moistening. This is mainly
attributed to the mucilage formed by the sheaths of
the cyanobacteria and algae, which adheres them
to the substratum and suffers deep changes in vol-
ume because of its water retention proper tie^.^^
The sheath allows the establishment of a self-
contained aquatic environment within which the
cells can attain adequate irradiation and gaseous
exchange. In addition, the presence of this wa-
ter reservoir with a high water potential ensures
that the cells remain essentially aquatic, thus per-
mitting the cyanobacteria and algae to overcome
drought periods. Through sheath contraction and
expansion, they can loosen stone grains, contribut-
ing to the gradual destruction of the ~ t o n e (Fig-
~ ~ ~ ~ ’
ure 4.3). In addition, the formation of cyanobacte-
rial and algal patinas results in a longer moisture FIGURE 4.4
retention at the surface of the stone, increasing the Limestone tessera from a mosaic of the Roman town of
mechanical damage produced by the freezing and Italica, Spain, covered by epilithic lichens. Before (a) and
thawing of water present in the pores of the stone. after (b) removal of the lichen thalli with hydrogen per-
Deterioration of limestones, marbles, and oxide. Extensive pitting was observed beneath the thalli.
sandstones by lichens was investigated by Saiz- (See color plates.)
Jimenez and coworker^.^^-^^ Petrographic studies
of several types of deteriorated limestones from damages (pitting) at the thallus-stone interface
the Roman mosaics of ltalica due to the action (Figure 4.4a, b). Endolithic lichens occur below the
of lichens were also reported.36 Epilithic and en- stone surface38 (Figure 4.5). It is well established
dolithic lichens colonize, penetrate, and etch the that lichens are able to withstand prolonged peri-
limestones. Epilithic lichens cover the surface of ods of desiccation, reabsorbing water and swelling
the limestone, causing mechanical and chemical quickly once it becomes available again. This is
4.6
FIGURE 4.5
Fruiting bodies of an endolithic lichen (Caloplaca sp.)
emerging between calcite crystals. (See color plates.)
particularly true in xerophytic species. The process
can result in deterioration of the stone, particularly
by successive expansion and contraction of the
lichen during wetting and drying, as simple field
observation suggests that absorption of water by
dry thalli in most lichens is a rapid process and
takes 1-2 minutes to achieve full saturation.
Lichens produce a wide range of secondary
metabolites often referred to as lichen acids. Most
of these are aromatic with orsellinic acid and its
homologues as the principal structural unit, con-
densed as di-, tri-, and tetracyclic compounds.
Syers and lskandar demonstrated that orcinol and
p-orcinol depsides and depsidones are sufficiently
soluble in water to function as metal-complexing
agents in stone eat he ring.^^ Lecanoric acid
formed a reddish-yellow complex when it was al-
lowed to react with biotite, and significant amounts
of Ca, Mg, Fe, and Al were released from silicates
by solution of lichen acids. In addition, oxalic acid
is recognized as an active lichen metabolite in the
weathering of carbonate rocks in nature. Calcium
oxalate was encountered as patinas on limestone
and marble statues as a consequence of the pres-
ence of lichens, which provided the acid required
to form o x a I a t e ~ . ~ ~ ~ ~ ~
The growth of bryophytes on marbles is rare
and usually confined to crevices or holes where
accumulation of dust, sand, water, dead organic
The Biodeteriorationof Building Materials
matter, etc. allows the formation of a protosoil.
In some limestone cathedrals, the most com-
mon species were Tortula muralis, Didymodon fal-
lax, and Gymnostomum calcareum, although most
bryophytes appeared on bricks and mortar^.^^>^'
In contrast, in a tropical forest area where the
Mayan Great Jaguar Pyramid and its quarry are
located, the limestone is covered by a carpet of
mosses, up to 3 mm thick, formed by the accumu-
lation of biomass, that is green at the surface and
brown in the interior. The mosses are anchored
to the stone by rhizoids, which penetrate in depth,
forming a network. As a result, the stone, very dis-
integrated, shows holes from which a dense mat
of rhizoids emerge, and the area penetrated by the
rhizoids is completely di~aggregated.~~
Vascular plants represent the later invasion in
a plant succession. The roots cause important de-
terioration in the structure of the buildings (e.g.,
in roofings, tiles, gutters, drains, etc.), ultimately
causing their ruin.
Suncistones
The workability of some sandstones, as well
as limestone, makes it one of the most frequently
used stone for construction. Sandstones are com-
posed of consolidated sand in which the grains of
quartz and feldspar are cemented by four common
cements: silica, calcite, limonite, and clay min-
erals. Silica-cemented sandstones may resem-
ble quartzites (metamorphosed sandstones) in its
high hardness, strength, and resistance to decay.
Sandstone cemented by limonite is soft to work.
Tiano et al. studied 50 samples of deteriorated
sandstones from buildings of the historic center
of F l ~ r e n c eMicrobiological
.~ analysis showed the
presence of autotrophic bacteria of the genus
Thiobacillus, which utilize sulfur and thiosulfates
as sources of energy and which give rise to sul-
fate as a product of metabolism. The facultative
chemolithotrophs species Thiobacillus novellus
and Th. intermedius were isolated by Gugliandolo
and Maugeri from gypsum and concrete sub-
strata in the church of s. Maria degli Alemanni, in
Messina, Italy.1° Sulfur and nitrifying bacteria have
been linked to deterioration of concrete and are
The Biodeteriorationof Building Materials
thus capable, by their biological activity, of generat-
ing the same acids that may be present in acid rain.
Meincke et al. isolated nitrifying bacteria from
German sandstone monument^.^ The popula-
tion analysis indicated that the most abundant
ammonia-oxidizing bacteria in the sandstones
belongs to the genus Nifrosovibrio, although
other ammonia-oxidizing bacteria of the genera
Nifrosomonas and Nitrosospira we re detectable.
Nifrobacter was the only detectable genus of the
nitrite-oxidizers. Both groups of nitrifying bacteria
live endolithically in the sandstone of different
monuments. The pH tolerance of Nifrosovibrio
and its resistance to high concentrations of salts
might contribute substantially to the selective
enrichment of Nifrosovibrio in the sandstone of
the monuments. The bacteria of this genus acidify
their environment by excretion of nitrous acid and
thus participate in the acidic attack on calcitic
sandstone. Bock et al. identified a new species,
Nitrobacfer vulgaris, isolated from stone from the
Cologne cathedral .43
Baumgartner et al. demonstrated that stone
materials from the surface of buildings generally
release significant quantities of NO into the
~ ~ production of NO must be
a t m ~ s p h e r e .The
due to the chemolithotrophic nitrifiers present in
large numbers at the surface of building stones.
The ammonium-oxidizing as well as the nitrite-
oxidizing nitrifiers have been shown to produce
NO and N20. The nitrifiers need ammonium,
which most likely is supplied by wet and dry
deposition of atmospheric NH:, a major pollutant
in the urban atmosphere, rapidly deposited onto
stone surfaces.
Warscheid et al. identified chemoorgan-
otrophic bacteria from the uppermost layers
of sandstones of German monuments.’ It was
shown that most of the isolated bacteria used
a wide range of different carbohydrates, amino
acids, fatty acids, and hydrocarbons. About
40% of the strains analyzed were shown to be
potential acid producers, whereas the capability
of manganese and iron oxidation was only spo-
radically found in the bacteria living on the stone.
Kerosene, as a representative mixture of different
hydrocarbons detectable in polluted atmospheres,
4.7
was well metabolized by 70% of the analyzed
bacteria.
Most heterotrophic bacteria are able to use
various organic compounds as a source of carbon
and energy for growth. Tayler and May reported
that the quantitative and qualitative nature of the
heterotrophic bacterial population on sandstone
varies seasonally and can be related to moisture
and temperature changes associated with a tem-
perate climate.45 The potential of these popula-
tions to cause damage to sandstone also varies
with season. In this respect, Lewis et al. suggested
that bacteria on stone can be extremely versa-
tile and could maintain their activity during nutri-
ent perturbations, operating at low nutrient levels
and utilizing what the environment has to offer.46
As a consequence, bacterial populations may be
able to maintain their involvement in the process of
stone deterioration during periods of nutrient flux.
Petersen et al. found that Penicillium, Phoma,
and Exophiala species colonized most examined
German sandstone monuments.47 Furthermore,
they stressed the biodeteriorating activities of
the genera Cladosporium, Penicillium, and Tricho-
derma, which were the most abundant on the mon-
uments investigated. The principal genera isolated
from weathered sandstone from the cathedral of
Salamanca, Spain, were Penicillium, Phoma, Cla-
dosporium, Trichoderma, and Fusarium and an
association between fungi and algae was also
found.
An endol it hic filamentous cyanobacterium
(Phormidium sp.) was found growing under black
sulfated crusts developed on calcarenite in the
cathedral of Seville, Spain.48 Ortega-Calvo et al.
proved that under laboratory conditions, the gyp-
sum present in black crusts covering calcaren-
ites from the cathedral of Seville, Spain, can be
used as a source of sulfur by the cyanobac-
terium Gloeofhecesp.6The sulfate released to the
medium due to gypsum dissolution was progres-
sively incorporated into the carbohydrate sheath
and used for balanced growth. Black crusts de-
posited in Petri dishes with only the addition of
distilled water doubled the biomass in four weeks
when inoculated with Gloeofhece sp., showing
that growth can be produced in natural conditions
4.8 The Biodeteriorationof Building Materials

and that the mineral content of the crusts is

enough to support cyanobacterial development.
Observations of a wide range of monuments
in different enviromental conditions indicate
that black crust covering building stones sup-
ports considerable colonization of phototrophic
microorganism^,^^ which suggests that gypsum
might play a role in the cyanobacterial colonization
of blackened monuments in urban enviroments.
Cathedrals present a rich variety of lichen com-
munities that form continuous white to dark patinas
on the stones. The communities vary according to
the type of stone, the orientation, or the climato-
logical conditions. Colonization of sandstones by
lichens is helped by the contribution of the organic
matter from bird droppings, giving rise to char-
acteristic ornithocoprophilous communities. Saiz-
Jimenez described the production of cracks and
detachment of a thin layer of about 1-2 mm of cal-
carenite from the belfry (the Giralda) of the cathe-
dral of Seville by the lichen Lecania e r y ~ i b eTo .~~
this layer was anchored the lichen thallus.
Gorgoni et al. studied the deterioration induced
by lichens in the biocalcarenite of the Greek Si-
cilian colony of Selinunte, Italy.50The most com-
mon species were Dirina massiliensis, Verrucaria
nigrescens, Lecanora pruinosa, and Caloplaca au-
ranfia. The main effects produced were a strong
corrosion, sometimes with the production of cal- FIGURE 4.6
cium oxalates and, after the lichens have died, the Walls of the cathedral of Salamanca, Spain, with disperse
disintegration of surfaces. lichen thalli. (See color plates.)
The sandstones of the cathedral of Sala-
manca usually are weathered by atmospheric
agents, an effect more visible in the pinnacles probably suffered longer periods of dessication by
and balustrades of the high naves. They normally sunlight, showed the presence of cyanobacteria.
are stained by stork droppings and, consequently, The higher humidity of the sandstone allowed
colonized by ornithocoprophilous lichens, from the development of more complex microbial
which Ramalina capitafa and R. digifellata, with communities, including bacteria and fungi.
fruticose thalli, are a b ~ n d a n t . ~In’ vertical areas Warscheid et al. investigated the biodeteri-
free of droppings the absence of lichens is oration of Brazilian churches constructed with
significant, and only occasional small, disperse quartzites and soapstone and the Aachen cathe-
lichen thalli are found (Figure 4.6). Proliferation of dral, in Germany, constructed with sandstone^.^'
algae is so heavy in these areas that continuous Extremely biocorrosive heterotrophic bacteria
green patinas, visible even from ground level, were isolated from Brazilian stones, but on
are formed. A detailed species distribution was German sandstones fungi and nitrifying bacteria
reported.49 Sandstone, at the ground level, predominated. The extent of biodeterioration was
showed a complete absence of cyanobacteria influenced by the physical and chemical properties
while sandstone situated 50 meters up, which of the stone, where alkaline soapstone was more
The Biodeteriorationof Buildinq Materials 4.9

affected by biogenic attack than quartzite and

quartzitic sandstones. The climatic conditions in
Brazil (high humidity and temperature) favored the
metabolic activity of heterotrophic bacteria while
German sandstones were more affected by air pol-
lution. Mainly lichens were found on soapstone,
and bryophytes were common in the quartzites.

Granites
These rocks consist of feldspars and quartz
with varying amounts of other minerals, such as
micas, and with all mineral constituents visible to
the naked eye. They are dense and range in grain
size from fine to granular. Porosity and permeabil-
ity are usually low, and granite has high resistance FIGURE 4.7
to weathering and corrosion. Feldspar crystal with bacterial colonization.
Biodeterioration of granite is relatively insignif-
icant compared with limestones and sandstones. not only of the hyphae but often of associated
This results from its lower pH and its low solubility. communities of bacteria and algae, also could
Bell et al. stated that attack on minerals in granite be observed (Figure 4.7). Scanning electron mi-
by microorganisms mainly includes uptake of min- croscopy showed a clear discontinuity between
eral elements by absorption, production of acids, thallus and granite (Figure 4.8),but several evenly
physical disruption of minerals, and mineral alter- distributed pits of some 4-5 pm, corresponding to
ation through increased time of wetness.52 hyphae penetration, served as attachment mech-
Weed et al. reported that bacteria and fungi anism through an active penetration process.
are able to concentrate and incorporate P, Ca, The granites from the cathedral of Toledo,
Fe, and K into the cell walls; these are needed Spain, usually do not show extensive colonization
for their mineral nutrition, thus transforming micas
into vermic~lite.’~ Duff et al. showed that bacte-
ria inhabiting granite produced ketoglutaric acid,
which is capable of solubilizing silicates and phos-
phate minerals quite successfully, and that micro-
bial reduction of iron can transform biotite into
ver micuI ite.53
Ortega-Calvo et al. identified three cyanobac-
teria: Plectonema boryanum, Plectonema sp., and
Phormidium tenue, and four chlorophyta: Chlorella
homosphaera, Klebsormidium flaccidum, Muriella
terrestris, and Stichococcus bacillaris in the gran-
ites from the cathedral of Toledo, Spain.49 How-
ever, they found a higher number of species in the
adjacent mortars, which allow a higher degree of
water retention.
Arifio and Saiz-Jimenez studied the interac-
tion between the lichen Rhizocarpon geograph- FIGURE 4.8
icum and granite.54In some pores or microfissures Thallus of Rhizocarpon geographicurn on granite sur-
beneath the lichen thallus, important proliferation, face.

4.10
by bryophytes or vascular plants, except in very
specific places as the result of microclimate con-
ditions. The greater part of the supporting lichen
flora is formed by species having crustose thalli,
including some with endolithic thalli, so that the
deterioration (seen as mechanical disintegration
of the particles) is greater than in the case of tiles
and flagstones from the same building. The most
common species belong to the genera Aspicilia,
Candelariella, and Lecanora with crustose thalli.
Physcia, with foliose thalli, appear only rarely.37
Ascaso et al. observed the generation of new
minerals by the action of lichens.55 Rhizocar-
pon geographicurn was able to generate hal-
loysite from feldspars and goethite from granite.
The lichen also attacked the edges of biotite.
Parmelia conspersa produced halloysite, kaolinite,
and amorphous silica from granite and feldspars.
It also was shown that lichenic acids were able to
complex with metalic cations from granite and with
their primary minerals.
Bricks and Terracotta
Fired bricks and terracotta are manufactured
from mixtures of clay (mainly montmorillonite and
illite types) and sand (quartz type). The vitrifica-
tion and strengh of the brick depend on the tem-
perature reached during firing and the composi-
tion of the mixture. The higher the temperature is,
the stronger is the Bricks have an excel-
lent resistance to the elements and are practically
insensitive to the action of atmospheric pollution.
Although bricks usually are a very resistant ma-
terial (deterioration of bricks results from freez-
ing and salt crystallization) most of the problems
are caused by soluble salts whose action is more
marked when the material is defe~tive.~’
Biodeterioration processes of bricks have
barely been studied. Palmer cites the example
of the Schleswig Cathedral, built with alternat-
ing rows of glazed and unglazed bricks, a typi-
cal architectural style in northern Germany.58 In
the past century, the glaze has been almost com-
pletely lost from many bricks while others near
and beneath the windows are undecayed. This
deterioration was related to the high microbial
biomass of phototrophic microorganisms, from
Next Page
The Biodeteriorationof Building Materials
FIGURE 4.9
Terracotta colonized by cyanobacteria and algae o n
the Pardon Gate, cathedral of Seville, Spain. (See color
plates.)
which Synechococcus sp. and Pseudoanabaena
sp. were isolated. Scanning electron microscopy
of the underside of glaze pieces revealed heavy
colonization of Synechococcus sp.
The terracottas of the Pardon Gate of the
cathedral of Seville, Spain, showed an important
colonization by microalgae, including 10 cyano-
bacteria, 12 chlorophyta, 1 xanthophyta, and 2
bacillariophyta. The species most abundant and
frequently isolated were Nosfoc puncfiforrne,
Phormidiurn fenue, Plecfonerna boryanum,
Klebsorrnidium flaccidurn, and Muriella ferresfris.
These communities are responsible for the green
color of the terracotta statues and develop as
epilithic-forming biofilms (Figure 4.9) or are chas-
molithic in cracks or fissures. In some cases the
communities were mixed with mosses, lichens,
and fungi. All cyanobacteria except one and K.
flaccidurn developed mucilaginous sheaths that
retained dust, terracotta particles, and some
seeds. The seeds were able to germinate, and
a considerable growth of vascular plants was
observed (Figure 4.10).
Mortars
By definition, a mortar is a mixture of sand
grains joined together by a binder (lime, cement,
etc.) of plastic consistency, traditionally used as
Previous Page
The Biodeterioration of Buildina Materials
FIGURE 4.10
Vascular plants emerging from terracotta crevices on
the Pardon Gate, cathedral of Seville, Spain. (See color
p Iates .)
a building material. Ancient mortars are mainly
made of lime and sand; on some occasions other
materials, such as clay or pozzolana, were added
to improve its properties. Lime mortars are char-
acterized by high porosity with distribution of pore
size in the range of a mesopore, and they possess
low mechanical strength and a relatively high de-
formation capacity, together with excellent perme-
ability to water.59Mortars are used in construction
to bind bricks or for coating stone surfaces, carved
rocks, etc. Fresco, a technique of wall painting on
wet lime plaster, is based on carbonation of the
lime hydroxide of the rendering.
Deterioration of mortars has been studied in
recent years.42~59~60 In laboratory tests, mortar
proved to be the most bioreceptive material.
This also can be observed in buildings and
monuments made with mortar and stone or brick
or on frescoes.
Saiz-Jimenez and Samson studied the de-
terioration of the frescoes at the monastery of
Santa Maria de la Rabida, Huelva, Spain.6i The
monastery is located in a very polluted area with
sulfur dioxide concentrations reaching up to 974
pg/m3 (maximum 24-hr mean concentration). It
has been reported that 300 pg/m3 of sulfur diox-
ide can produce about 10 pg/m3 of sulfuric acid
at 50% relative humidity and twice as much in
fog with 100% relative humidity.62Therefore, it is
not surprising that the surface of the frescoes is
4.1 1
covered by gypsum crystals. Sulfur-oxidizing and
sulfur-reducing bacteria far exceeded the number
considered as a sign of biological attack and could
be the first supply of organic matter to the fres-
coes. Numerous heterotrophic bacteria (including
Micrococcus, Bacillus, Pseudomonas, Nocardia-
like, and Streptomyces) were also isolated. An-
other possible explanation for the growth of mi-
croorganisms on the frescoes was the existence
of hydrocarbons and volatile organic compounds
in the atmosphere, emitted by the neighboring oil
refineries and cellulose pulp plants.63 It has been
reported that the surface of condensing films tends
to entrain and dissolve volatiles. Substances dis-
solved in water become concentrated as water
evaporates, leaving a layer of organic contamina-
tion thick enough to provide a substrate for growth
of microorganism^.^^
Giacobini et al. observed that actinomycetes
grow on frescoes, producing a whitish powdery
mycelium or colorless patinas.65They isolated 200
strains from which only 60 were identified. The
actinomycetes thrive preferentially in caves and
mural paintings, although they also have been
recorded in limestone monument^.^^
In recent years considerable research was car-
ried out on the flora present in the 14th century
mural paintings from the chapel of Castle
Herberstein.66-68 The frescoes were restored
around 1950 and at present show serious damage
by fungi and other microorganism^.^^^^^ An area
showing a rosy color was sampled by Rolleke et al.
and used for isolation of aerobic, heterotrophic
bacteria as well as for extraction of DNA66(Figure
4.1 1). Isolated bacteria were related to Arthrobac-
ter globiformis, Streptomyces griseus, Acineto-
bacter lwoffi, and members of the Pseudonocar-
diaceae and actinomycete lineage. Total DNA was
extracted from the sample and 194-bp fragments
of the 16s rDNA were amplified with eubacte-
rial primers. The 16s rDNA fragments of uniform
length obtained from the different bacterial species
were separated according to their sequence differ-
ences by denaturing gradient gel electrophoresis
(DGGE). By sequencing excised and reamplified
individual DNA bands, members or closed rela-
tives of the genera Halomonas, Clostridium and
Frankia were identified.66
4.12
FIGURE 4.11
Deteriorated mural painting from the chapel of Castle
Herberstein, Austria. (See color plates.)
The finding of members of the genus Halo-
monas was interesting as it contains moderately
halophilic strains that grow over a wide range of
salt concentrations (0.5-30%) but have an opti-
mum of circa 8% halite for
In a further study, Rolleke et al. detected and
identified an archaeal community within these mu-
ral paintings.68Total DNA was extracted from the
mural painting material and the fragments were
amplified with archaeal specific primers. Six out
of ten analyzed samples showed the presence of
archaeal 16s rDNA fragments, identified as mem-
bers or close relatives of the genus Halobacterium.
This has important implications for the general
ecological significance of archaea in deteriorated
monuments, as it has been reported that halobac-
teria have a rigid, salt-requiring metabolism and
lyse the moment the salt concentration in their
environment drops below 10 to 15°/0.70
Competition between halophilic bacteria
(Halomonas) and archaea (Halobacterium) has
been studied by Oren, who concluded that the two
groups occupy different niches7’ The first one
forms versatile group, adapted to life at low salini-
ties, whereas archaea are found at high salinities,
which are required for the maintenance of
structural cell components. Because neutrophilic
halophilic archaea (Halobacterium, Ha/ococcus,
etc.) are unable to grow at the high pH values
The Biodeterioration of Building Materials
(-9.8) found in frescoes, mortar walls, etc. it could
be concluded that these environments are more
suitable for alkaliphilic archaea of the genera
Natronobacterium and Natrococcus. However,
in deteriorated mural paintings high variations in
salinity and pH can be found locally and this
would explain the overlapping of microorganisms
with apparent distinct growth requirements,
as sampling could mix different microniches.
Saiz-Jimenez and Laiz stated that the use of
traditional microbiological methods allows the iso-
lation of a large number of ‘heterotrophic bacte-
ria on deteriorated monuments, but the spectrum
of isolated bacteria changes when the protocols
used in studies of halophilic bacteria were ap-
plied to mural paintings, efflorescences, or min-
eral deposits.72 In fact, enumeration of the het-
erotrophic viable bacteria indicates that the higher
counts were, generally, obtained in media with
10% salt concentration. Media with epsomite al-
ways yielded higher counts than halite, particu-
larly in environments where magnesium salts were
abundant. Therefore, in studies on microbial com-
munities in deteriorated monuments, it was pro-
posed that protocols involving the use of media
with high concentrations of sodium chloride (up
to 25%) and 2% magnesium sulfate for environ-
ments in which the predominant cation is sodium
and media with high concentrations of epsomite for
environments in which the predominant cation is
magnesium should be applied. In addition, atten-
tion was drawn to the pH of the media and the mag-
nesium concentration in the design of the appro-
priate culture media to cope with both neutrophilic
and alkaliphilic halobacteria.
Saiz-Jimenez and Samson isolated the fungi
Cladosporium sphaerospermum, Engyodontium
album, and Aspergillus versicolor from the fres-
coes of Santa Maria de la Rabida monastery,
which accounted for 90% of total isolates.61 Cla-
dosporium attack was considered to be the most
serious form of deterioration of fresco painting in
modern times.73All three species found in the fres-
coes also have been related to the utilization of
hydrocarbon^.^^^^^
Lichens also colonize frescoes, as proved
by Seaward and Edwards.75 In fact, Dirina
The Biodeteriorationof Building Materials 4.13

FIGURE 4.12
Wall of the cloister of the Jeronimos monastery, Lisbon,
Portugal, colonized by lichens. (See color plates.)

massiliensis forma sorediafa, an ecologically in-

teresting lichen now profoundly affecting a wide
range of ecological niches because of its ability
to exploit man-made substrata, causes physico-
chemical deterioration of the Renaissance fres-
coes at Palazzo Farnese, in Caprarola, Italy. This
is exemplified in the production of oxalates to a
depth of 20 mm and in the mechanical damage
to the substratum when naturally detached. The
same lichen has a similar effect on the walls of
the cloister of the Jeronimos monastery in Lisbon,
Portugal (Figure 4.12), and in tomb walls of the FIGURE 4.13
Wall of the Quadrangular Mausoleum, Necropolis of
Necropolis of Carmona, Spain.
Carmona, Spain, colonized by calcifying cyanobacteria.
Although cyanobacteria and algae are pho-
(See color plates.)
totrophic organisms, deriving their energy for
growth from light, they also can be found in
very poorly illuminated places inside buildings of calcarenite-carved tombs from the Roman
and caves. Recently, Scyfonema julianum was Necropolis of Carmona, Spain, indicating that
found on the frescoes of a rock church in Matera, these cyanobacteria are not only restricted to
Italy. The cyanobacterium precipitates calcium caves but to any other niches in which dim light
carbonate to form extracellular encrustations on and more or less constant humidity conditions are
the sheath and was the first record in Italy on prevalent79 (Figures 4.13 and 4.14).
substrata of historic and artistic interest.76 This Two case studies-the mortars of the outdoor-
cyanobacterium, together with Geifleria calcarea, exposed mosaics of the Roman town of Italica,
are common inhabitants of caves.77 Coute con- Seville, Spain, and the mortars covering columns,
sidered that G. calcarea is a case of adaptation capitals, and walls of temples and buildings in the
to an extreme (strict cavernicole) environ- Roman town of Baelo Claudia, Cadiz, Spain-
ment.78 Scyfonema julianum and G. calcarea were thoroughly described.60,80It was found that
have been found in the mortar-coated walls the epilithic communities of cyanobacteria and
4.14 The Biodeteriorationof Building Materials

FIGURE 4.14 FIGURE 4.15

Encrusting calcite in the sheath of the calcifying Scanning electron micrograph of a mortar wall from the
cy anobacter iu m Geitleria ca Icarea . Roman town of Baelo Claudia, Spain, showing detail of
pitting.

algae had a strong chemical influence on the

mortar resulting from mechanical alterations were
alteration of the mortars by the formation of small
found adhering to the hyphae as well as to crys-
cavities in the colonized surfaces, suggesting
tals, mainly of calcium oxalate, resulting from the
their active participation in the dissolution of
chemical activity of lichens.
carbonate. Therefore, the surface of the colonized
The effect of mosses on mortars is also im-
areas showed small cavities in which cells had
portant. Optic and electron microscopy reveal a
become installed. The endolithic communities
profuse network of rhizoids that penetrate the mor-
develop profusely to depths of several millimeters.
tar down to the base allowing easy access of wa-
The surfaces of the mortars colonized by lichens
ter to deep levels. Penetration through the mor-
were also strongly altered, mainly reflected in
tar makes it disintegrate, with various small pieces
an intense pitting, evident after the death and
appearing joined together by the rhizoids like a
disappearance of the thalli. The pits were basically
string of beads or rosary.81The disintegration of
of two types: mesopitting, visible with the naked
mortars is strongly accelerated by the annual ac-
eye, with a diameter of about 0.1 to 0.5 mm, and
tion of mosses, contributing to organic enrichment
micropitting, present in the interface between
of the substratum, which provides a good input
the mortar and the lichen thalli, with an average
for heterotrophic microorganisms, finally leading to
diameter of 5-10 pm, distributed over the whole
the formation of humus needed for vascular plant
surface (Figure 4.15). These pits mainly affected
invasion.
the carbonated matrix, although occasionally they
perforated the quartz crystals.
The thalli of lichens penetrated a consider- Treatment and Restoration
able distance into the mortar and hyphae were
found at depths of up to 4.5 mm or sometimes of BuiIding Materials
even deeper (in fissures or fractures they pen-
etrated as far down as 1-1.5 cm). The intense Building materials have been protected
activity of the network of hyphae gave rise to con- against weathering since Greek and Roman
siderable alterations in the first millimeter of mor- civilizations. For the protection of stone and brick
tar below the thalli. Frequently, small particles of surfaces, a sacrificial layer of plaster or stucco was
The Biodeteriorationof Building Materials
used. Statuary was treated with organic acids,
waxes, and the like. The use of traditional methods
and products, however, was replaced by the use of
synthetic and polymeric materials with the advent
of modern chemistry. Several monographs and
reviews have been published on topics including
the cleaning of stone, consolidation, and the use
of water-repelling treatment^.^^-^^
Polymers and resins (acrylic and polyvinyl
resins, silicones, etc.) have often been used as
consolidants or water repellents. However, these
materials were also deteriorated by microorgan-
isms. Koestler assessed the ability of fungi to
degrade 16 different formulations. Some of the
products that are degraded the most are quite
prevalent in field use today.86Pinna and Salvadori
indicated the capability of fungi, lichens, and, to a
lesser extent, algae to grow on substrates treated
with organic resins.87Lichens produced chemical
and mechanical degradation of a polyester resin
used for consolidating stuccoed capitals.88
Methods to prevent biodeterioration includes
the control of environmental conditions (humidity,
temperature, and light), as well as nutrient supply.
Often this kind of control inhibits or slows down
biological growth and is considered as a natu-
ral or preventive conservation method. However,
whereas it is feasible to modify the environmen-
tal parameters inside museums, churches, or for
works of art in a confined area, these methods
cannot be adopted for outdoor monuments or ar-
chaeological sites.89
In outdoor environments, the most relevant
treatment for protecting stone from biodeterio-
ration is the use of biocides. A comprehensive
monography including a detailed description of
the different types of biocides (bactericides, fungi-
cides, algicides, lichenicides, and herbicides), a
literature review, and a technical sheet on 31 bio-
cides with data on their chemical structure, effi-
ciency, toxicity, environmental fate, and so on was
published recently by Caneva et aLgO
Classical biocide treatments included the use
of hydrogen peroxide and sodium hypochlorite
(against algae and lichens on stones), phenol
derivatives such as pentachlorophenol (whose
use is now severely restricted), or dichlorophene
(used as bactericide, fungicide, and algicide).
4.15
Quaternary ammonium compounds have similar
effects.89
An alternative to biocides is the use of ultra-
violet radiation. A good level of efficacy against
cyanobacteria and algae was obtained after 3 cy-
cles of 10 hours each of exposure to UV-C (100-
280 nm).91
Recently, an innovative water-compatible for-
mulation of the biocide 2,3,5,6-tetrachloro-4-
(methylsulfony1)-pyridine was developed.92 This
biocide is known to give medium-long-term pro-
tection on stone surfaces against a wide range
of fungi, algae, and lichens. The biocide is also
compatible with an experimental water repellent,
in such a way that both silicone and biocide treat-
ments can be done in a single application. A sur-
vey, 6 years after treatment, of a sandstone treated
with separate applications of both products (old
formulations) proved that they were effective in
preventing the colonization and recolonization of
the stone by phototrophic organismsg3 Similar re-
sults were reported for silicone-treated mortars in
a German castle restored in 1977.94
Summary
Building materials are subjected to deteriora-
tion as soon as they are exposed to open air. Sun,
frost, wind, rain, and so on contribute to the grad-
ual process of weathering accelerated by atmo-
spheric pollutants, which attack the materials and
provide the organisms with a variety of organic
and inorganic nutrients. Biological activity plays an
important role in the overall process. This results
in deterioration of building materials, exemplified
in staining, patina formation, pitting, etching, dis-
aggregation, exfoliation, etc. Biodeterioration pre-
vention includes the control of environmental con-
ditions or the application of biocides and/or novel
formulations based on silicones and biocides.
Acknowledgment
This work has been supported by the Euro-
pean Commission, project ENV4-CT98-0707.
4,16
References
1. J.J. Ortega-Calvo, X. AriAo, M. Hernandez-Marine,
and C. Saiz-Jimenez, “Factors Affecting the Weath-
ering and Colonization of Monuments by Pho-
totrophic Microorganisms,” Sci. Total Environ. 167
(1995): 329-341.
2. 0. Guillitte, “Bioreceptivity: A New Concept for
Building Ecology Studies,” Sci. Total Environ. 167
(1995): 215-220.
3. 0. Guillitte and R. Dreesen, “Laboratory Chamber
Studies and Petrographic Analysis as Bioreceptivity
Assessment Tools of Building Materials,” Sci. Total
Environ. 167(1995): 365-374.
4. C. Saiz-Jimenez, “Deposition of Anthropogenic
Compounds on Monuments and Their Effect on
Airborne Microorganisms,” Aerobiologia 11(1995):
161-175.
5. M. Meincke, E. Krieg, and E. Bock, “Nitrosovibrio
spp., the Dominant Ammonia-Oxidizing Bacteria in
Building Sandstone,” Appl. Environ. Microbiol. 55
(1989): 2108-21 10.
6. J.J. Ortega-Calvo, X. AriAo, L.J. Stal, and C.
Saiz-Jimenez, “Cyanobacterial Sulfate Accumula-
tion from Black Crust of a Historic Building,” Ge-
omicrobiol. J. 12(1994): 15-22.
7. T. Warscheid, M. Oelting, and W.E.K. Krum-
bein, “Physico-Chemical Aspects of Biodeteriora-
tion Processes on Rocks with Special Regard to
Organic Pollutants,” Int. Biodeterior. 28( 1991): 37-
48.
8. H.L. Ehrlich, Geomicrobiology (New York, NY:
Marcel Dekker, 1981).
9. P. Tiano, R. Bianchi, G. Gargani, and S. Vanucci,
“Research on the Presence of Sulphur-Cycle Bac-
teria in the Stone of Some Historical Buildings in
Florence,” Plant Soil 43(1975): 21 1-21 7.
10. C. Gugliandolo and T.L. Maugeri, “Biodeterioration
of Stone by Sulphur Bacteria,” in La Conservazione
dei Monumenti nel Bacino del Mediterraneo, ed.
F. Zezza (Brescia, Italy: Grafo, 1988), pp. 221-
224.
11. R.M. Atlas, A.N. Chowdhury, and K.L. Gauri, “Mi-
crobial Calcification of Gypsum-Rock and Sulfated
Marble,” Stud. Conserv. 33(1988): 149-1 53.
12. E. Zanardini, S. Bruni, F. Cariati, G. Ranalli, and
C. Sorlini, “Investigations on the Red Present on
the Carrara Marble FaGade of Orvieto Cathedral,”
in The Conservation of Monuments in the Mediter-
The Biodeteriorationof Building Materials
ranean Basin, eds. F. Fassina, H. Ott, and F. Zezza
(Venezia, Italy: Soprintendenza ai Beni Artistici e
Storici, 1994), pp. 349-352.
13. J.J. Ortega-Calvo and C. Saiz-Jimenez, “Micro-
bial Degradation of Phenanthrene in two European
Cathedrals,” FEMS Microbiol. Ecol. 22(1997): 95-
101.
14. C. Saiz-Jimenez, “Weathering and Colonization of
Limestones in an Urban Environment,” in Soil Bi-
ology and Conservation of the Biosphere, Vol. 2,
ed. J. Szegi (Budapest, Hungary: Akademiai Kiado,
1984), pp. 757-767.
15. C. Saiz-Jimenez, “Deposition of Airborne Organic
Pollutants on Historic Buildings,” Atmos. Environ.
27B(1993): 77-85.
16. M.A. de la Torre, G. Gomez-Alarcon, P. Melgarejo,
and C. Saiz-Jimenez, “Fungi in Weathered Sand-
stone from Salamanca Cathedral, Spain,” Sci. Total
Environ. 107(1991): 159-1 68.
17. R.J. Koestler, A.E. Charola, M. Wypyski, and J.J.
Lee, “Microbiologically Induced Deterioration of
Dolomitic and Calcitic Stone as Viewed by Scan-
ning Electron Microscopy,” in V e Congres lnterna-
tional sur I’Alterationet la Conservation de la Pierre,
ed. G. Felix, (Lausanne, Switzerland: Presses Poly-
techniques Romandes,l985), pp. 617-626.
18. M.E.K. Henderson and R.B. Duff, “The Release of
Metallic and Silicate Ions from Minerals, Rocks, and
Soils by Fungal Activity,” J. Soil Sci. 14(1963): 236-
246.
19. S.B. Weed, C.B. Davey, and M.G. Cook, “Weath-
ering of Mica by Fungi,” Soil Sci. SOC.Amer. Proc.
33( 1969): 702-706.
20. J.W. Foster, Chemical Activities of Fungi(New York,
NY: Academic Press, 1949).
21. P. Dupuy, G. Trotet, and F. Grossin, “Protection
des Monuments contre les Cyanophycees en Milieu
Abrite et Humide,” in The Conservation of Stone I,
ed. R. Rossi-Manaresi (Bologna, Italy: Centro per
la Conservazione dele Sculture all’Aperto, 1976),
pp. 205-219.
22. A.M. Pietrini, S. Ricci, M. Bartolini, and M.R. Giu-
liani, “A Reddish Colour Alteration Caused by Al-
gae on Stoneworks. Preliminary Studies,” in Ve
Congres lnternational sur I’Alteration et la Conser-
vation de la Pierre, ed. G. Felix (Lausanne, Switzer-
land: Presses Polytechniques Romandes,l985),
pp. 653-662.
23. C. Saiz-Jimenez, J. Garcia-Rowe, M.A. Garcia del
Cura, J.J. Ortega-Calvo, E. Roekens, and R. Van
The Biodeteriorationof Building Materials
Grieken, “Endolithic Cyanobacteria in Maastricht
Limestone,” Sci. Total Environ. 94(1990): 209-220.
24. G. Giaccone, M.L.V. Rinaldi, and C. Giacobini,
“Forme Biologiche dele Alghe Esistenti sulle Scul-
ture AII’Aperto,” in The Conservation of Stone I,
ed. R. Rossi-Manaressi (Bologna, Italy: Centro per
la Conservazione dele Sculture all’Aperto, 1976),
pp. 245-256.
25. G. Caneva, M.P. Nugari, S. Ricci, and 0. Salvadori,
“Pitting of Marble Roman Monuments and the
Related Microflora,” in 7th International Congress
on Deterioration and Conservation of Stone,
Vol. 1, eds. J.D. Rodrigues, F. Henriques, and F.T.
Jeremias (Lisbon, Portugal: LNEC, 1992), pp. 521-
530.
26. C. Saiz-Jimenez, “Microbial Melanins in Stone
Monuments,” Sci. Total Environ. 167(1995): 273-
286.
27. G. Hyvert, “Borobudur, Les Bas-Reliefs Materi-
aux, Facteurs Responsables des Degradations,
Programme de Conservation,” Stud. Conserv.
18(1973): 131-1 55.
28. A. Danin, “Weathering of Limestone in Jerusalem
by Cyanobacteria,” Z. Geomorphol. 27( 1983): 413-
421.
29. B. de Winder, H.C.P. Matthijs, and L.R. Mur, “The
Role of Water Retaining Substrata on the Pho-
tosynthetic Response of Three Drought Tolerant
Phototrophic Micro-Organisms Isolated from a Ter-
restrial Habitat,” Arch. Microbiol. 152( 1989): 458-
462.
30. J.J. Ortega-Calvo, M. Hernandez-Marine, and C.
Saiz-Jimenez, “Mechanical Deterioration of Build-
ing Stones by Cyanobacteria and Algae,” in Biode-
terioration and Biodegradation 8, ed. H.W. Ross-
moore (London, UK: Elsevier Applied Science,
1991), pp. 392-394.
31. J.J. Ortega-Calvo, M. Hernandez-Marine, and C.
Saiz-Jimenez, “Biodeterioration of Buildings Mate-
rials by Cyanobacteria and Algae,” Int. Biodeterior,
28(1991): 167-187.
32. J. Garcia-Rowe and C. Saiz-Jimenez, “Coloniza-
tion of Mosaics by Lichens: the Case Study of Ital-
ica,” in Lichens and Monuments, eds. P.L. Nimis and
M. Monte. Stud. Geobot. 8(1988): 65-71.
33. C. Saiz-Jimenez, “Weathering of Building Materials
of the Giralda (Seville, Spain) by Lichens,” 6th Tri-
ennial Meeting, ICOM Committee for Conservation,
paper no. 81/10/4 (Ottawa, Canada: ICOM, 1981).
34. C. Casas Sicart and CSaiz-Jimenez, “Los Briofitos
4.17
de la Catedral de Sevilla,” Collect. Botan. 13(1982):
163-1 75.
35. C. Saiz-Jimenez, J. Garcia-Rowe, and J.M.
Rodriguez-Hidalgo, “Biodeterioration of Poly-
chrome Roman Mosaics,” Int. Biodeterior.
28(1991): 65-79.
36. M.A. Garcia del Cura, M. Hoyos, and C.
Saiz-Jimenez, “Petrographic Characterization and
Weathering of Limestone Tesserae from Mosaics of
ltalica (Spain),” in The Conservation of Monuments
in the Mediterranean Basin, eds. D. Decrouez, J.
Chamay, and F. Zezza (Geneva, Switzerland: Mu-
seum d’Histoire Naturelle, 1992), pp. 469-475.
37. J. Garcia-Rowe and C. Saiz-Jimenez, “Lichens and
Bryophytes as Agents of Deterioration of Building
Materials in Spanish Cathedrals,” Int. Biodeterior.
28( 1991): 151-1 63.
38. J. Garcia-Rowe and C. Saiz-Jimenez, “A Case
Study of the Corrosion of Stone by Lichens: the
Mosaics of the Roman Remains of Italica,” in Mi-
crobial Corrosion, eds. C.A.C. Sequeira and A.K.
Tiller (London, UK: The Institute of Materials, 1992),
pp. 275-281.
39. J.K. Syers and I.K. Iskandar, “Pedogenetic Signifi-
cance of Lichens,” in The Lichens, eds. V. Ahmad-
jian and M.E. Hale (New York, NY: Academic Press,
1973), pp. 225-248.
40. M. del Monte, C. Sabbioni, and G. Zappia, “The
Origin of Calcium Oxalates on Historical Buildings,
Monuments and Natural Outcrops,” Sci. Total Env-
iron. 67(1987): 17-39.
41, C. Sabbioni and G. Zappia, “Oxalate Patinas on
Ancient Monument s : The Biological Hyphot es is”
Aerobiologia 7(1991): 31-37.
42. J.M. Garcia de Miguel, L. Sanchez-Castillo, J.J.
Ortega-Calvo, J.A. Gil, and C. Saiz-Jimenez, “Dete-
rioration of Building Materials from the Great Jaguar
Pyramid at Tikal, Guatemala,” Building Environ.
30(1995): 591-598.
43. E. Bock, H.P. Koops, U.C. Moller, and M. Rud-
ert, “A New Facultatively Nitrite Oxidizing Bac-
terium, Nitrobacter vulgaris sp. nov.,” Arch. Micro-
biol. 153(1990): 105-1 10.
44. M. Baumgartner, A. Remde, E. Bock, and R. Con-
rad, “Release of Nitric Oxide from Building Stones
into the Atmosphere,” Atmos. Environ. 24B( 1990):
87-92.
45. S. Tayler and E. May, “The Seasonality of Hetero-
trophic Bacteria on Sandstones from Ancient Mon-
uments,” in Biodeterioration and Biodegradation 8,
4.18
ed. H.W. Rossmoore (London, UK: Elsevier Applied
Science, 1991), pp. 390-392.
46. F.J. Lewis, E. May, and A.F. Bravery, “Metabolic
Activities of Bacteria Isolated from Building Stone
and their Relationship to Stone Decay,” in Biode-
terioration 7, eds. D.R. Houghton, R.N. Smith and
H.O.W. Eggins (London, UK: Elsevier Applied Sci-
ence, 1988), pp. 107-1 12.
47. K. Petersen, J. Kuroczkin, A.B. Strzelczyk, and W.E.
Krumbein, “Distribution and Effects of Fungi on
and in Sandstones,” in Biodeterioration 7, eds. D.R.
Houghton, R.N. Smith and H.O.W. Eggins (London,
UK: Elsevier Applied Science. 1988), pp. 455-460.
48. C. Saiz-Jimenez, B. Hermosin, J.J. Ortega-Calvo,
and G. Gomez-Alarcon, “Applications of Analyti-
cal Pyrolysis to the Study of Cultural Properties,”
J. Anal. Appl. Pyrol. 20(1991): 239-251.
49. J.J. Ortega-Calvo, P.M. Sanchez-Castillo, M.
Hernandez-Marine, and C. Saiz-Jimenez, “lsola-
tion and Characterization of Epilithic Chlorophyta
and Cyanobacteria from two Spanish Cathedrals
(Salamanca and Toledo), Nova Hedwigia 57( 1993):
239-253.
50. C. Gorgoni, L. Lazzarini, and 0. Salvadori, “Minero-
Geochemical Transformations Induced by Lichens
in the Biocalcarenite of the Selinuntine Monu-
ments,” in 7th International Congress on Deterio-
ration and Conservation of Stone, Vol. 1, eds. J.D.
Rodrigues, F. Henriques, and F.T. Jeremias (Lisbon,
Portugal: LNEC, 1992), pp. 531-539.
51 T. Warscheid, D. Barros, T.W. Becker, J. Braams,
S. Eliasaro, G. Grote, D. Janssen, L. Jung, S.P.B.
Mascarenhas, M.L. Mazzoni, K. Petersen, E.S. Si-
monoes, Y.K. Moreira, and W.E. Krumbein, “Biode-
terioration Studies on Soapstone, Quarzite and
Sandstones of Historical Monuments in Brazil
and Germany. Preliminary Results and Evalua-
tion for Restoration Practices,” in 7th International
Congress on Deterioration and Conservation of
Stone, Vol. 1, eds. J.D. Rodrigues, F. Henriques,
and F.T. Jeremias (Lisbon, Portugal: LNEC, 1992),
pp. 491-500.
52. E. Bell, P. Dowding, and T.P. Cooper, “The Biode-
terioration of Granite,” in Granite Weathering and
Conservation, eds. E. Bell and T.P. Cooper (Dublin,
Ireland: Trinity College, 1994), pp. 28-32.
53. R.B. Duff, D.W. Webely, and R.O. Scott, “Solubiliza-
tion of Minerals and Related Materials by Ketoglu-
conic Acid-Producing Bacteria,” Soil Sci. 95(1963):
105-1 14.
The Biodeteriorationof Building Materials
54. X. AriAo and C. Saiz-Jimenez, “Granite Weather-
ing by the Lichen Rhizocarpon Geographicum,” in
Granite Weathering and Conservation, eds. E. Bell
and T.P. Cooper (Dublin, Ireland: Trinity College,
1994), pp. 33-35.
55. C. Ascaso, J. Galvan, and C. Ortega, “The Pedo-
genic Action of Parmelia Conspersa, Rhizocarpon
geographicum and Umbilicaria pustulata,” Liche-
nologist 8(1976): 151-1 71.
56. V. Furlan, “Causes, Mechanisms and Measurement
of Damage to Mortars, Bricks and Renderings,” in
Science, Technology and European Cultural Her-
itage, eds. N.S. Baer, C. Sabbioni, and A.I. Sors
(Oxford, UK: Butterworth-Heinemann, 1991),
pp. 149-159.
57. M.T. Blanco Varela, “Deterioro de Materiales Ar-
tificiales. 11,’ in La Humedad como Patologla Fre-
cuente en la Edificacion (Madrid, Spain: Colegio
Oficial de Aparejadores,l993), pp. 171-181.
58. R.J. Palmer, “Microbial Communities in the Weath-
ering of Three Historic Buildings in Northern Ger-
many,” in Science, Technology and European Cul-
tural Heritage, eds. N.S. Baer, C. Sabbioni, and A.I.
Sors (Oxford, UK: Butterworth-Heinemann, 1991),
pp. 478-480.
59. F. Puertas, M.T. Blanco-Varela, A. Palomo, J.J.
Ortega-Calvo, X. Ari Ao, and C. Saiz-Jimenez, “De-
cay of Roman and Repair Mortars in Mosaics from
Italica, Spain,” Sci. Total Environ. 153(1994): 123-
131.
60. C. Saiz-Jimenez and X. Aritio, “Biological Coloniza-
tion and Deterioration of Mortars by Phototrophic
Organisms,” Mater. Constr. 45( 1995): 5-1 6.
61. C. Saiz-Jimenez and R.A. Samson, “Microorgan-
isms and Environmental Pollution as Deteriorating
Agents of the Frescoes of Santa Mariade la Rabida,
Huelva, Spain,” 6th Triennial Meeting ICOM Com-
mitee for Conservation, Ottawa, paper no. 81/15/5
(Ottawa, Canada: ICOM, 1981).
62. E.M. Winkler, “Weathering Rates of Stones in Ur-
ban Atmospheres,” in The Conservation of Stone I,
ed. R. Rossi-Manaresi (Bologna, Italy: Centro per
la Conservazione delle Sculture all’Aperto, 1976),
pp. 27-36.
63. C. Saiz-Jimenez, “Causas del Deterioro de 10s Mu-
rales de Daniel Vazquez D/az, Monasterio de Santa
Maria de la Rabida, Huelva,” Mundo Cientifico
18(1981): 1007-1 01 1.
64. R.A. Rasmussen, R.S. Hutton, and R.J. Garner,
“Factors in Establishing Microbial Populations on
The Biodeteriorationof Building Materials
Biologically Inert Surfaces,” in Biodeterioration of
Materials, Vol. 1, eds. A.H. Walters and A.J.
Elphick (New York, NY: Elsevier, 1968), pp. 79-98.
65. C. Giacobini, M.A. de Cicco, I. Tiglie, and G.
Accardo, “Actinomycetes and Biodeterioration in
the Field of Fine Art,” in Biodeterioration 7, eds.
D.R. Houghton, R.N. Smith, and H.O.W. Eggins
(London, UK: Elsevier Applied Science, 1988),
pp. 418-423.
66. S. Rolleke, G. Muyzer, C. Wawer, G. Wanner, and
W. Lubitz, “Identification of Bacteria in the Biode-
graded Wall Painting by Denaturing Gradient Gel
Electrophoresis of PCR-AmplifiedGene Fragments
Coding for 16s rRNA,” Appl. Environ. Microbiol.
62(1996): 2059-2065.
67. M. Berner, G. Wanner, and W. Lubitz, “A Compara-
tive Study of the Fungal Flora Present in Medieval
Wall Paintings in the Chapel of the Castle Herber-
stein and in the Parish Church of St. Georgen in
Styria, Austria,” Int. Biodeterior. Biodegr. 40( 1997):
53-61.
68. S. Rolleke, A. Witte, G. Wanner, and W. Lubitz, “Me-
dieval Wall Paintings-a Habitat for Archaea: Iden-
tification of Archaea by Denaturing Gradient Gel
Electrophoresis (DGGE) of PCR-Amplified Gene
Fragments coding for 16s rRNA in a Medieval Wall
Painting,” Int. Biodeterior Biodeg. 41 (1998): 85-92.
69. P.D. Franzmann and B.J. Tindall, “A Chemotaxo-
nomic Study of Members of the Family Halomon-
adaceae,” System. Appl. Microbiol. 13(1990): 142-
147.
70. D.J. Kushner, “Life in High Salt and Solute Concen-
trations: Halophilic Bacteria,” in Microbial Life in Ex-
treme Environments, ed. D.J. Kushner (New York,
NY: Academic Press, 1978), pp. 317-368.
71. A. Oren, “The Ecology of the Extremely Halophilic
Archaea,” FEMS Microbiol. Rev. 13(1994):p. 415-
440.
72. C. Saiz-Jimenez and L. Laiz, “Occurrence of Halo-
toleranVHalophilic Bacterial Communities in Dete-
riorated Monuments,” Int. Biodeterior. Biodeg. (in
press).
73. C. Giacobini and R. Lacerna, “Problemi di Microbi-
ologia nel Settore Degli Affreschi,” Boll. 1st. Cent.
Restauro (1965): 83-1 08.
74. E.J. Nyns, J.P. Auquiere, and A.L. Wiaux, “Taxo-
nomic Value of the Property of Fungi to Assimilate
Hydrocarbons,” Anton. Leeuw. 34(1968): 441-457.
75. M.R.D. Seaward and H.G.M. Edwards, “Lichen-
Substratum Interface Studies, with Particular Ref-
4.19
erence to Raman Microscopic Analysis. 1. Deterio-
ration of Works of Art by Dirina massiliensis forma
sorediata,” Crypt. Bot. 5(1995): 282-287.
76. A.M. Pietrini and S. Ricci, “Occurrence of a Calcare-
ous Blue-Green Alga, Scytonema julianum (Kutz.)
Meneghini, on the Frescoes of a Church Carved
from the Rock in Matera, Italy,” Cryptogam. Bot.
3(1993): 290-295.
77. A. Coute, “Essai Preliminaire de Comparai-
son de Deux Cyanophycees Cavernicoles Cal-
cifiees: Geitleria calcarea Friedmann et Scy-
tonema julianum Meneghini,” Arch Hydrobiol.
SUPPI.71(1985): 91-98.
78. A. Coute, “Geitleria calcarea Friedmann (Cyano-
phyceae, Hormogonophycidae, Stigonematales,
Stigonemataceae): un Cas d’Adaptation a un Milieu
ExtrQme,” Bull. SOC.Bot. Fr. 136(1989): 113-1 30.
79. X. Aritio, M. Hernandez-Marine, and C. Saiz-
Jimenez, “Colonization of Roman Tombs by Cal-
cifying Cyanobacteria,” Phycologia 36( 1997): 366-
373.
80. X. Aritio and C. Saiz-Jimenez, “Colonization and
Deterioration Processes in Roman Mortars by
Cyanobacteria, Algae and Lichens,” Aerobiologia
12( 1996): 9-1 8.
81. J.A. Gil and C. Saiz-Jimenez, “Biodeterioration of
Roman Mosaics by Bryophytes,” in 7th lnterna-
tional Congress on Deterioration and Conservation
ofstone, Vol. 1, eds. J.D. Rodrigues, F. Henriques,
and F.T. Jeremias (Lisbon, Portugal: LNEC, 1992),
pp. 51 1-519.
82. G.G. Amoroso and V. Fassina, Stone Decay
and Conservation (Amsterdam, The Netherlands:
Elsevier, 1983).
83. L. Lazzarini and M.L. Tabasso, /I Restauro della
Pietra (Padova, Italy: CEDAM, 1986).
84. M. Matteini and A. Moles, La Chimica nel Restauro
(Firenze, Italy: Nardini Editore, 1989).
85. J. Delgado Rodrigues and A.E. Charola, “General
Report on Water Repellents,” Sci. Technol. Cultural
Heritage 5(1996): 93-1 03.
86. R.J. Koestler, “Polymers and Resins as Food for
Microbes” in Of Microbes and Art, eds. 0. Ciferri,
P. Tiano, and G. Mastromei (New York, NY: Kluwer
Academic/Plenum, 2000), pp. 153-1 67.
87. D. Pinna and 0. Salvadori, “Biological Growth
on Italian Monuments Restored with Organic or
Carbonatic Compounds,” in Of Microbes and Art
(Florence, Italy: Abstracts ICMC’99, 1999),
pp. 149-1 54.
4.20
88 X. Ariiio and C. Saiz-Jimenez, “Lichen Deteri-
I 92. R. Balzarotti-Kammlein, M. Sansoni, and A.
oration of Consolidants Used in the Conserva-
tion of Stone Monuments,” Lichenologist 28( 1996):
391-394.
89. C. Caneva, M.P. Nugari, and 0. Salvadori, Biology
in the Conservation of Works of Art (Rome, Italy:
ICCROM, 1991).
90. C. Caneva, M.P. Nugari, D.Pinna, and 0. Salvadori,
I/ Controlo del Degrado Biologico (Fiesole, Italy:
Nardini Editore, 1996).
91, M. Bartolini, A.M. Pietrini, and S. Ricci, “Use of
UV-C Irradiation on Artistic Stoneworks for Con-
trol of Algae and Cyanobacteria,” in Of Microbes
and Art (Florence, Italy: Abstracts ICMC’99, 1999),
pp. 221-227.
The Biodeteriorationof Building Materials
Castronovo, “An Innovative Water-Compatible
Formulationof Algophase for Treatmentof Mortars,”
in Of Microbes and Art (Florence, Italy: Abstracts
ICMC’99, 1999), pp. 217-220.
93. A. Gomez-Bolea, X. Ariiio, R. Balzarotti, and C.
Saiz-Jimenez, “Surface Treatment of Stones: Con-
sequences on Lichenic Colonisation,” in Of Mi-
crobes and Art (Florence, Italy: Abstracts ICMC’99,
1999), pp. 233-237.
94. R. Mansch, C. Pinck, C. Urzi, F. De Leo, and P. Sala-
mone, “Microbial Colonisation of Silicone Treated
Mortar at Schloss Weissenstein in Pommersfelden,
Germany,” in Of Microbes and Art (Florence, Italy:
Abstracts ICMC’99, 1999), pp. 200-205.

Microbiologically Influenced Corrosion
in Fire Protection Sprinkler Systems
Abstract
Microbiologically influenced corrosion (MIC)
has emerged in the past several years as a
major cause of problems in fire protection sprin-
kler systems (FPS). These problems include fail-
ures of FPS components due to corrosion (usually
pinhole leaks), plugging of system components
(including sprinkler heads) by biological growths
and corrosion products, and reduced flow capac-
ity due to the presence of deposits on the interior
diameter of the FPS piping. In this paper, a sum-
mary of the cases that have been seen thus far
is presented. These cases have involved various
types of FPS, materials, and geographic locations.
Methods for diagnosis, treatment, and monitoring
of MIC in FPS are discussed.
Definition of MIC
Microbiologically influenced corrosion (MIC) is
corrosion affected by the presence or activities
of microorganism^.(^-^) MIC almost always occurs
concurrently with, and is virtually impossible to
separate from, other corrosion mechanisrns.(l3)
This is due, in large part, to the fact that microbes
help create conditions under which other corro-
sion mechanisms (e.g., crevice corrosion, oxygen
concentration cell corrosion, underdeposit corro-
sion, and acid attack corrosion) can occur.(13) MIC
can change the form, appearance, and rate of cor-
rosion from that normally associated with other
corrosion mechanisms. These characteristics can,
5.1
CHAPTER 5
By D.H, Pope and R.M. Pope
and most often do, differ in various locations in a
FPS, in various geographic areas, and in different
phases of the MIC process.
Examples of MIC in FPS
Figure 5.1 presents examples of MIC in wet,
dry, steel, and copper FPS from different locations
in the United States.
MIC and MIC Control in FPS Is
Different in Many Respects from
MIC in Other Facilities
MIC in FPS is similar in many respects to MIC
in other facilities in that it can occur in aerobic
and anaerobic regions, can involve almost any
alloy (except titanium), involves communities of mi-
crobes, and is most often seen as underdeposit pit-
ting corrosion. However, MIC in FPS differs from
MIC in other systems in several critical aspects.
Many of the differences are explained, in
part, by how FPS are constructed and operated.
Figure 5.2 is a generic diagram showing the com-
ponents in a typical FPS. It is important to note that
the piping at the inlet to the FPS is larger in diam-
eter than the cross-mains. The internal diameters
of the branch lines and pipes directly coupled to
sprinkler heads are even smaller. This makes me-
chanical cleaning of the pipe very difficult.
A FPS can be operated as a wet system, which
contains water most of the time, but through which
5.2 MicrobiologicallyInfluenced Corrosion in Fire Protection Sprinkler Systems

FIGURE 5.1
Examples of MIC in FPS. (a) Discrete deposits (nodules) and deposits in steel wet FPS pipe. (b) Galvanized wet steel
FPS pipe showing heavier deposition and pitting on bottom of pipe. (c) Pit in copper wet FPS pipe. (d) Deposits in
galvanized steel dry FPS pipe. (e) Pinhole leak in galvanized steel dry FPS pipe. (See color plates.)
Microbiologically Influenced Corrosion in Fire Protection Sprinkler Systems
FIGURE 5.2
Diagram of an automatic sprinkler system.
water is not normally circulated. This creates prob-
lems for controlling corrosion, scale, and microbes
since it is virtually impossible to regularly deliver
treatment chemicals to all parts of the FPS. Alter-
natively, a FPS can be operated as a dry system. In
theory, a dry FPS contains water only when pur-
posefully introduced during hydrotesting, inspec-
tor’s tests, or in case of a fire. The dry system
has several problems. First, water-based treat-
ment chemicals cannot be maintained in the FPS
most of the time since most of the FPS is “dry.”
Second, these systems never actually operate in
a totally dry state because water is introduced
during inspector’s tests. Finally, dry FPS are al-
most never thoroughly dried, leaving some resid-
ual water, dirt, etc. in portions (most often low
points) of the piping.
While most FPS are made of carbon steel,
a significant number utilize galvanized or copper
pipe. Fittings are often cast materials, and sprin-
kler heads are often nickel coated or made of
brass. Problems in diagnosis and treatment of FPS
are created by the presence of a variety of these
materials, including iron or steel, cast iron, brass,
copper, plastics, rubber seals, etc., making selec-
tion of treatment chemicals compatible with FPS
5.3
components more difficult. Also, most FPS are lo-
cated in areas where leaks could expose person-
nel to waters containing treatment chemicals. Fur-
thermore, many FPS receive water directly from
potable water systems, the suppliers of which
are understandably reluctant to approve treatment
chemicals in the FPS that might leak back into the
potable water systems. These characteristics of
FPS make traditional approaches to treatment of
MIC and other forms of corrosion very difficult.
Summary of Information from MIC
Cases Studied Thus Far
The information obtained from the investiga-
tion of over 200 cases of MIC in FPS supports the
following conclusions:
1. MIC in FPS is almost always associ-
ated with discrete deposits (tubercles
or nodules). Failures are most often
due to pinhole leaks.
2. Deposit formation and MIC can occur
in all parts of the FPS (underground
5.4 MicrobioloaicallvInfluenced Corrosion in Fire Protection Sprinkler Systems
supply, storage tanks, risers, mains,
branch lines, couplings, and sprinkler
heads). It is probable that most parts
of the FPS are colonized by bac-
teria and that some deposition oc-
curs in these areas. However, in dead
legs (smaller cross-mains and branch
lines) the microbiological, deposition,
and corrosion processes often slow
down because of the lack of nutri-
ents and reactants. Water, oxygen, and
dissolved organic and inorganic ma-
terials are critical to these processes
since the major source of materials
for continued deposit formation is the
water, not the metal being corroded.
This is supported by the finding that
the most severe deposition and cor-
rosion is almost always seen in areas
, in periodic contact with water contain-
ing some oxygen (i.e., the risers and
mains). These areas receive untreated
make-up water containing microbes,
nutrients, and oxygen when inspector’s
tests of the system are performed (this
may be done bi-weekly, monthly, or
quarterly). Even in those cases where
the damage is seen in the smaller
branch lines, corrosion has usually
been greatly accelerated after the sys-
tem has been emptied and refilled as
the result of repairs or renovation of the
system.
3. Metal loss is confined to the area under
the deposits and is usually in the form
of pits. In some cases (especially those
with larger deposits), the MIC corrosion
sites may appear grossly as relatively
shallow areas of metal loss. However,
closer inspection usually reveals that
these areas are composed of multiple
corrosion pits.
4. MIC is usually most severe or ad-
vanced where the most and largest
deposits accumulate (generally along
the bottom of the pipe). For this rea-
son, it is recommended that when FPS
piping is installed, the weld be placed
on the top.
5. There seems to be no preferential at-
tack of MIC at the weld region or other
worked areas such as grooves. How-
ever, some of these areas may have
less wall thickness than other regions,
often causing leaks to appear in these
areas first.
6. Thinner schedule pipe may show signs
(Len,leaks) of MIC earlier than thicker
schedule piping; however, neither are
immune to MIC.
7. The smelly, black “sulfurous” material
recovered with many samples from
branch lines and sprinkler heads is
composed primarily of residual cutting
oils, iron hydroxides, iron oxides, and
other materials. These materials are, in
fact, almost always low in sulfide con-
tent and are not, in most cases, formed
by sulfate-reducing bacteria (SRB) ac-
tivity.
8 . MIC involves communities of bacteria
and is not caused by just one type (e.g.,
SRB) of bacteria. MIC in FPS has usu-
ally been found to be more extensive
and severe in portions that routinely
come into contact with new water and
oxygen (i.e., riser and mains). MIC is
caused by communities of microorgan-
isms working together to produce con-
ditions under which biofilms and de-
posits can be formed and corrosion can
occur. These microbes include:
Aerobic bacteria that require
oxygen to live. Aerobes are very
important in forming biofilms and
discrete deposits (nodules and
tubercles).
Low-nutrient bacteria (LNB) that
grow in conditions of low organic
foodstuffs (e.g., potable water).
MicrobiologicallyInfluenced Corrosion in Fire Protection Sprinkler Systems
LNB are generally aerobic bac-
teria and are very important in
the processes of biofouling, de-
posit formation, and corrosion. In
FPS, they are generally found in
larger numbers than other micro-
bial groups.
lron-related bacteria (IRB) that
precipitate iron compounds
through a variety of metabolic
processes. These bacteria are
largely responsible for forming
discrete deposits (nodules and
tubercles) on surfaces.
Acid-producing bacteria (APB)
that produce organic acids. Or-
ganic acids are very important
factors in the initiation of MIC.
Sulfate-reducing bacteria (SRB)
that produce sulfides. Sulfides
and SRB can be important in
MIC, but they should not be used
as the sole indication of MIC.
9. Microbes capable of causing MIC are
present in virtually all ground and sur-
face waters, soils, dust, etc. There-
fore, they can enter the FPS during
construction. They will also be in wa-
ters used to hydrotest, fill, or make-up
to the FPS, unless these waters are
treated sufficiently to kill all MIC mi-
crobes. These microbes are, in many
cases, not killed by the disinfection pro-
cess applied by the water supplier.
10. MIC can occur in any geographic
area in North America and probably
throughout the world.
11. MIC can affect most, if not all, materials
found in FPS.
12. MIC deposits can cause reduced flow
capacity in the FPS and, therefore, pre-
vent the FPS from performing its func-
tion of containing or putting out a fire.
5.5
13. MIC can plug sprinkler heads, leading
to failure of the heads to activate and
deliver water to control a fire.
14. MIC can possibly “glue” sprinkler head
components together to the extent that
they may not operate properly.
15. MIC may cause changes in rubber
components such as gaskets and 0-
rings, causing them to weep small
amounts of water to the outside of the
piping, often resulting iri severe corro-
sion on the outside of the pipe.
16. Each FPS must be studied and treated
individually, as each has its own unique
features.
In the process of investigating and treating cases
of MIC in FPS, we have studied and tested nu-
merous methods for diagnosis and treatment. The
following guidelines and methods have proven to
be the most practical for dealing with MIC in FPS
and attempt to accommodate the differences be-
tween the different systems.
Diagnosis of MIC in FPS
Test samples from the FPS for viable bacteria
of the types most often involved in MIC of FPS (see
item 8 , above). Also determine pH, dissolved oxy-
gen, total iron, hardness, and free residual chlo-
rine. Tests should be done on water samples from
the make-up to the system (riser or main) and at
the end of a branch line or inspector’s test valve.
Since each FPS is unique, each system must be
tested for MIC. If the tests show the presence of
any type of MIC bacteria, it is probable that the
FPS has MIC. Greater numbers and variety of
microbes increase likelihood of MIC.
If a diagnosis of probable MIC is made visu-
ally inspect the interior of the riser(s) cross mains
and branch lines for deposits (nodules and tuber-
cles) and underdeposit pitting corrosion, which are
strong indicators of MIC. Also determine chemical
nature of deposits.
5.6 Microbiologicallyinfluenced Corrosion in Fire Protection Sprinkler Systems
Treatment of MIC in FPS
~~ ~ _ _ ~ ~
If deposits and/or corrosion are present, the
FPS should be rehabilitated by flushing with dis-
infectant or other cleaning chemicals, it should be
chemically cleaned to remove the deposits, or the
pipe should be replaced. The rehabilitation method
chosen should depend upon an analysis of the
extent to which MIC is present and on risk-benefit
analysis.
After rehabilitation, the FPS should be disin-
fected and a device installed on the make-up to
disinfect all water entering the FPS (during fill,
inspector’s tests, or flow tests, or due to pres-
sure fluctuations or jockey pump operations). This
prevents MIC from recurring. The choice of dis-
infectants and use of other treatment chemicals
will depend on the type of FPS, water chemistry,
materials contained in the FPS, and regulations
pertaining to FPS in your area.
If deposits and corrosion are absent in both
the riser and branch lines, the FPS should be dis-
infected and a device installed on the make-up
to disinfect all water entering the FPS (during fill,
inspector’s tests, or flow tests, or due to pressure
fluctuations or jockey pump operations). This pre-
vents MIC from developing in the FPS. Again, the
choice of disinfectants and use of other treatment
chemicals will depend on the type of FPS, water
chemistry, materials contained in the FPS, and
regulations pertaining to FPS in your area.
All new FPS should be cleaned and treated
with effective biocides and oxygen consuming
chemicals to prevent occurrence of MIC.
We have developed the FPS Questionnaire,
located on the following page, as an aid in gather-
ing data necessary to diagnose and treat MIC in
FPS. A detailed mitigation plan should be prepared
before any work is started.
Monitoring MIC in FPS
The FPS should be tested immediately af-
ter the treatment device is installed and regu-
larly thereafter for viable bacteria and chemical
parameters, including levels of treatment chemi-
cals, to confirm that disinfection is being achieved.
FPS operations, treatments, and treatment levels
should be reviewed at least once a year and when-
ever changes to the FPS are contemplated. This
will ensure that treatment continues to be ade-
quate to prevent MIC in the FPS.
References
1. D.H. Pope, D.J. Duquette, D.C. Wayner, Jr., and
A. H. Johannes, Microbiologically Influenced Corro-
sion: A State of the Art Review (Columbus, OH: Ma-
terials Technology Institute of the Chemical Process
Industries, 1984).
2. D.H. Pope, “State-of-the-Art Report on Monitoring,
Prevention and Mitigation of Microbiologically Influ-
enced Corrosion in the Natural Gas Industry,” Topical
Report GRI-92/0382 (Chicago, IL: Gas Research In-
stitute, 1992).
3. G. Kobrin, ed., A Practical Manual on Microbiolog-
ically Influenced Corrosion (Houston, TX: NACE,
1993).
MicrobiologicallyInfluenced Corrosion in Fire Protection Sprinkler Systems 5,7

FPS QUESTIONNAIRE
This FPS QUESTIONNAIRE is a tool for assembling information necessary to recommend proper treatment for your FPS. Provide
as much information as possible. Fill out a separate questionnalre for each FPS.

It is assumed that you followed the directions in BTl’s “GUIDE TO DIAGNOSIS AND TREATMENT OF MIC IN FPS” to obtain data
allowing a diagnosis of MIC in your FPS. It is also assumed that you used MICkitTMFPS test kits to determine bacteria and chemical
parameters and that you or BTI inspected pipe from your FPS to confirm that it has MIC.

1. Client name
2. Namellocation of FPS
3. Type of facility or facilities served by FPS
4. Size of facility or facilities served by FPS
5. Number of buildings served by FPS
6. Number of years since FPS installed
7. Pipe material (e.g., black iron, steel (stainless,
galvanized, etc.), copper, etc.)
8. Pipe schedule
9. Valve materials (e.g., brass, cast iron, etc.)
10. Sprinkler head materials (e.g., brass)
11. Other metallic components
12. Rubber components (types and materials)
13. Plastic components (types and materials)
14. System construction (e.g., welded, screwed,
grooved, slip, socket, or others)
15. Type system (wet, dry, deluge, or others)
16. Volume of water storage tank (gal) feeding FPS
17. Volume of underground (gal) feeding FPS
18. Number of FPS “systems” fed by underground
19. Backflow preventor present (yesho)
20. Volume of each FPS (gal) to be treated
21. Roof design density
22. Sprinkler coverage (square feet)
23. Maximum flow rate (gpm) and pressure (psi)
of water into FPS from fire pump or city supply
24. Jockey pump rating (gpmlpsi)
25. Source of water (e.g., potable from supplier,
treated well water, untreated water, etc.) used
to fill and make up to the FPS
26. Water treatment performed prior to entering
FPS, other than that done by water supplier
27. Chemical composition of deposits in FPS
28. Chemical compostion of cleaning solution(s)
andlor flushing solutions, if any, used or to be
used in FPS

A diagram of the entire FPS is very useful in deciding where to apply treatment.

Results obtalned using MICkitTMFPS-SCREEN :

26. Locations in FPS where samples taken

27. Type of bacteria (LNB, APB, IRB, SRB) found
28. pH
29. Dissolved oxygen
30. Hardness level
31. Total iron
32. Free residual chlorine

Please include any additional information that you think would be useful

MIC in Underground Environments:
External Corrosion in the Gas
Pipeline Industry
Introduction
Gas transmission systems developed over
the past half century now carry much of the
world’s energy conveniently and cheaply from
source to market over great distances. These
systems consist of buried large-diameter carbon
steel pipe transporting clean, dry gas at high
pressures. The line pipe is typically protected with
a surface coating, which prevents direct contact
of the external soil environment with the steel
surface, and by cathodic protection (CP) systems,
which maintain a negative charge on the steel
and prevent its dissolution in corrosion processes
wherever the steel is exposed.
External corrosion is a key threat to the on-
going integrity of gas transmission lines. Con-
sequences of a major pipeline rupture include
issues of public safety and environmental dam-
age as well as the economic losses associated
with system failure. To manage the risks posed,
a proactive approach to integrity management is
desirable. Overall, any proactive integrity manage-
ment plan is based on a sequence of steps carried
out in a more or less formal way. While details vary
depending on the unique featires of each system
the general process involves:
1. understanding the nature of the threat
posed,
2. assigning priority based on risk to parts
of the system,
6.1
CHAPTER 6
By T.R. Jack
3. using effective tools to identify locations
of immediate concern,
4. selectively rehabilitating affected sec-
tions or taking mitigative action to re-
duce risk, and
5. setting a schedule for future actions
as part of an ongoing maintenance
scheme.
This article focuses on the role played by micro-
organisms in initiating external corrosion and on
the management of microbiologically influenced
corrosion (MIC) on gas pipeline systems. This
article will not detail ways to recognize and
characterize MIC sites. A major research pro-
gram sponsored by the Gas Research Institute
(GRI) has provided a state-of-the-art review of
monitoring methods along with practical field
guides for this p ~ r p o s e Commercial
. ~ ~ ~ ~ ~ assay
kits suitable for field use are readily available for
some of the more important bacteria involved in
MIC,2~3~4 and ongoing research is looking at ways
to characterize mixed populations by new deoxyri-
bonucleic acid (DNA) probe technique^.^^^
Setting the Stage
Pipeline coatings bonded to the steel surface
of the pipe provide an impermeable barrier of high
electrical resistance. This effectively isolates the
6.2 MIC in Underground Environments: External Corrosion in the Gas Pipeline Industry

(A) Degraded Coating: (B) Shielding Disbondment:

CP Penetrates Coating CP Limited Access
SOIL SOIL

FIGURE 6.1
Principal Modes of Coating Failure: (a) Degraded coating: The coating loses integrity, becomes permeable, hardens, and
cracks to allow CP access to steel surface. (b)Shielding disbondment: The coating remains impermeable and electrically
insulating. CP penetration into disbondment is limited by conductivity of water trapped under disbondment.

steel from the surrounding environment. Where
the coating is properly applied and remains in-
tact, external corrosion is effectively prevented;
however, application problems and subsequent
degradation during service can compromise coat-
ing performance. Microorganisms play a role in the
in-service degradation of coatings.
Microorganisms are naturally present in soil
environments. Conditions in the backfilled ditch
around pipelines can promote microbial activity. In
cold and temperate climates, the warm gas flow-
ing through the system elevates the temperature
around the pipe, promoting biological activity. Mi-
crobial populations depend on a number of factors,
including soil moisture levels and nutrient avail-
ability. The backfill around the pipe is often more
permeable to air and water and this provides en-
hanced levels of nutrients to microbial colonies in
the soil next to the pipe. In the past, before top soil
and surface debris were segregated and handled
separately during construction, organic material
was often interred with the backfill, and its decay
promoted microbial activity around the pipe.’ Fi-
nally, coating components and other construction
materials can themselves be a source of nutrients
for a microbial community.
As early as 1939, Bunker8 emphasized the
undesirability of employing coatings containing
materials that foster microbial growth. Despite this
warning most of the early coating systems did
support microbial growth and suffered damage in
consequence as susceptible coating components
were biodegraded. From the point of view of in-
tegrity management, two basic failure modes can
be distinguished (Figure 6.1). In one mode the
coating degrades in place, losing its ability to in-
sulate the pipe from its external environment. In
this failure mode, cathodic protection can reach the
underlying steel surface and protect the pipe from
corrosion (Figure 6.la). Early asphalt and coal tar
coating systems typically failed in this way. The
second mode of coating failure occurs where an
inert, durable coating retaining its insulating prop-
erties pulls away from the pipe surface to create
a disbondment capable of shielding the underly-
ing steel surface from cathodic protection (Figure
6.lb). This is a more serious failure mode. Al-
though many kinds of coatings have been used
in pipeline protection, asphalt enamel and tape
wrap coatings are discussed here to illustrate the
characteristics of the two basic kinds of coating
failure. These coatings have been chosen to pro-
vide examples because of their widespread ap-
plication in the pipeline industry and because a
great deal of information is available on their per-
formance.
MIC in UndergroundEnvironments: External Corrosion in the Gas Pipeline Industry
1.4 - retained a high level of electrical resistance, 10
"E
si
!
w 1.0
Z
0.8.
w
' degraded coating in which fine cracks had devel-
1
3
0.6.
0.4
u 0.2.
1965 1970 1975 1980 1985 1990 1995
YEAR
FIGURE 6.2
Increase in current density required to sustain cathodic
protection on an asphalt enamel pipeline over time.
Coating Degradation
The petroleum asphalt and coal tar based coat-
ing systems used in the 1940s and 1950s degrade
in place, losing their insulating qualities and their
adherence to the steel surface. Microorganisms
can be involved in this degradation, especially in
the case of asphalt coatings. Phenols in coal tar
coatings tend to discourage microbial growth.'
Excavations carried out on a 30-year-old
NPS16 pipeline with an asphalt enamel coating
provide examples of what to expect for this mode
of coating failure. Figure 6.2 illustrates the ongo-
ing loss of coating integrity on this line. In the fig-
ure, the progressive failure of the coating is evident
from the ever-increasing current density needed
to maintain an acceptable level of cathodic protec-
tion in the associated impressed current CP sys-
tem. As the coating failed, more and more steel
surface became accessible to cathodic protection.
Over time the number of anode beds needed to
support the CP system had to be substantially in-
creased to maintain adequate levels of protection.
Samples of asphalt enamel taken from exca-
vations on this line reflect this change in insulat-
ing ability. For example, a sample from a strongly
bonded area of intact coating on this pipeline
6.3
megaohms, while an uncracked specimen from an
adjacent area of coating, which had degraded and
separated from the steel surface, showed less than
10% of this resistance for the same size speci-
men measured in the same way. An even more
oped as the coating hardened and became brit-
tle showed a resistance of only 1 kiloohm. Pre-
sumably, continued cracking would ultimately have
led to a complete loss of insulating ability. These
changes in electrical properties reflect changes in
the composition of the coating, as water leaching
and biodegradation remove susceptible hydrocar-
bon components over time.
The involvement of various microorganisms in
coating degradation or MIC can be documented
in a variety of ways. An effective traditional ap-
proach is to use the Most Probable Number tech-
nique based on simple growth tests in which a
selective growth medium is inoculated with var-
ious dilutions of a field sample. The extent of
growth in the dilution series reflects the num-
ber of viable bacteria in the original sample that
were able to grow in the specific test medium
used. Samples of degraded asphalt coating from
the line described above were found to host a
mixed population of hydrocarbon-degrading bac-
teria, acid-producing bacteria (APB), and sulfate-
reducing bacteria (SRB). In contrast, in samples
of adjacent ditch soil, hydrocarbon-degradingbac-
teria and APB were not detected at all while
SRB counts were a thousand-fold less than those
associated with the degraded coating. The loss
of coating components can be seen by compar-
ing the infrared spectra of intact and degraded
material.
Degradation of the coating does not necessar-
ily represent a threat to pipeline integrity. The loss
of electrical resistance and increased permeability
of the coating allows cathodic protection to reach
the underlying steel surface, especially where
the salinity of local groundwater provides an
electrolyte of good conductivity. Effective cathodic
protection reduces protons in aqueous solution
to cathodic hydrogen on the steel surface. This
process increases the pH of the aqueous phase
6.4 MIC in Underground Environments: External Corrosion in the Gas Pipeline Industry
next to the pipe and can coincidentally concen-
trate bicarbonate and carbonate salts under the
coating. One site excavated in a sodium sulfate
salt seep showed trapped waters of pH 10 or
more and extensive deposits of crystalline ther-
monatrite (Na2C03-HZO) in dried-out areas under
nonadherent degraded asphalt coating. In these
conditions, microbial growth is discouraged and
corrosion cannot proceed. Thus, MIC is not a
threat. Historically, the relatively good perfor-
mance of asphalt coated lines confirms that loss
of coating integrity need not result in corrosion
where adequate CP levels are maintained.
Where effective cathodic protection is not
maintained, MIC can occur. One such situation is
found where soil dries out locally around the pipe
to give a high resistance barrier to CP while leaving
sufficient water trapped in and under the degraded
coating to support corrosion. These sites occur in
relatively well drained areas exposed to periodic
water fluxes.
This kind of coating failure can be monitored
generally for a facility by tracking the current de-
mand in the associated impressed current CP sys-
tem as shown in Figure 6.2. Affected spots can be
identified by holiday detection methods and short-
interval pipe to soil potential surveys. Locations
showing bad coating and poor CP potentials are
candidates for MIC failures.
Shielding Disbondments
Plastic tape coating systems, which appeared
in the 1960s, provided a durable coating with high
electrical resistance and excellent insulating abil-
ities. Unfortunately, where these tapes separate
from the pipe surface, a shielding disbondment can
result (Figure 6.1 b).
In this scenario, penetration of protective ca-
thodic protection potentials under the disbonded
coating depends strongly on the conductivity of
the water trapped in the pocket under the sepa-
rated coating. Algorithms have been developed to
determine the degree of CP penetrati~n.~ Where
groundwater is very fresh and has low conductivity
(1 mS/cm), protective potentials are limited to a few
centimeters from the opening of the disbondment
by the potential (IR) drop through the electrolyte.
For long disbondments, much of the steel surface
exposed by separation of the coating remains at
a freely corroding potential. Because CP cannot
penetrate these disbondments, they fail to show
up as potential dips in normal pipe to soil poten-
tial surveys or in other holiday detection methods
normally used to find missing coating without ex-
cavation. Often the first indication of a problem is
a leak or rupture. The most susceptible locations
are those in which a low conductivity groundwater
is present.
While the polymers used to form tape coat-
ings (polyethylene, polypropylene, polyvinyl chlo-
ride) remain inert to microbial attack by virtue of the
large size of the polyolefin molecules,10other coat-
ing components are susceptible to loss and alter-
ation. Adhesives and primers that fix the tape to the
pipe surface are particular targets for biodegrada-
tion. Table 6.1 shows that these components rather
than the tape itself provide the nutrients for micro-
bial activity (in this case the reduction of sulfate to
sulfide by anaerobic sulfate-reducing bacteria).' '
A mixed microbial community is involved in break-
ing down the complex organics in the adhesive
to feed the SRB. In Figure 6.3, a piece of coat-
ing from the field is exposed to a pure culture of
SRB previously obtained from a pipeline corrosion
site. A burst of sulfide production results but then
the process stops as suitable nutrients already
present in the degraded adhesive and primer are
TABLE 6.1
35S-SulfateReduction to Sulfide(A)
35S-Sulfide
Incubation Time (counts per
Medium (days) minute)
Mineral Salts Medium 7 1275
(MSM) 15 1445
Polyolefin Tape in MSM 7 4704
(adhesive removed) 15 3264
Adhesives from Tape in 7 501,535
MSM 15 1,593,310
(A) By seven-day-old cultures of sulfate-reducing bacteria (Desulfovibrio vulgaris var.
vulgaris NClB 8303) grown anaerobically on tape coating components from a field
corrosion site."
MIC In Underground Environments: External Corrosion in the Gas Pipeline Industry 6.5

2.8 with an increased current demand.' 1913 Where the

? current density available is not sufficient to meet

-6
rn
2.4

I
I
I this increased current demand, protective CP po-
tentials will be lost.
There is evidence that biodegradation of the
@t3 I
adhesive promotes disbondment of tape coating
from the pipe surface. Lab studies15 have shown
T-d 2.0
5 that tape wrap systems are especially susceptible
W I to loss of adhesion on exposure to wet biologically
z
0 I active soil. Figure 6.4 shows the loss of adhesion
p 1.6 of a polyethylene tape coating around a holiday
I
exposed to various environments for 20 weeks.
n I After exposure the specimens were subjected to
O 1.2 I a cathodic disbondment test16 to assess changes
E I in the tenacity of bonding of the coating to the
a steel surface. Exposure to a wet biologically active
E 0.8 clay soil had more impact on coating adhesion
5
v)
than exposure to a water control treated with
antibiotic. This suggests that soil organisms play
a role in reducing the adhesion of such coating
0.4 systems in service. Field observations indicate
that microbial effects can occur in the adhe-
sive layer even where the surrounding coating
appears well bonded and intact. Pressurized
20 40 60 80 100 bubbles of gas (Figure 6.5) found between layers
DAYS of tape wrap as well as under the coating in
FIGURE 6.3 a field excavation were obviously of microbial
Microbial reduction of groundwater sulfate to sulfide on origin. The composition of the trapped gas was
disbonded tape coating samples incubated anaerobically that expected for a mixed anaerobic population
with a pure culture of sulfate-reducing bacteria (SRB) and including methanogens: methane, 64-8970;
with a mixed culture containing SRB. carbon dioxide, 11-34%; nitrogen, 9-1 9%; and

1
Polyethylene Tape
exhausted (Figure 6.3). The SRB are not able to 40 r
attack complex organics present in the adhesive. 335
Repeating the experiment with a mixed popula- 30
tion of bacteria maintained in the lab on field coat- c
25
-a
l
1
ing samples gives a different result (Figure 6.3). In g 2o
this case sulfide production is sustained as other 4 15 Extruded Polyethylene
organisms continue to break down the coating ad- 4 10
E

hesive and feed the SRB the nutrients needed to Li5

sustain sulfide production. 0
The iron (11) sulfides ultimately produced by WATER CLAY WATER CLAY WATER CLAY

this microbial community are a family of unusual FIGURE 6.4

materials,12 many of which display interesting
electrical properties. These become involved in
corrosion cells (as will be described presently) but
can also challenge the cathodic protection system
Cathodic disbondment of coatings16 around holidays
after exposure to microbially active clay soil for 20
+
weeks compared to exposure to water antibiotic as the
control.
6.6 MIC in Underground Environments: External Corrosion in the Gas Pipeline Industry

FIGURE 6.5
Pressurized bubbles of gas in the adhesive between coating layers on a tape-wrapped pipeline. (See color plates.)

hydrogen, 0.2-1.2%. Such observations clearly
demonstrate that microbial growth can occur in
the adhesive layer of a tape coating system with
evident damage to coating adhesion (Figure 6.5).
While polyethylene or polypropylene tapes
remain intact indefinitely in an underground envi-
ronment even when disbonded from the pipe sur-
face, polyvinyl chloride (PVC) may lose its integrity
over time through biodegradation. The proper-
ties of PVC are adjusted to meet the needs of
coating applications by inclusion of plasticizers.
These are typically phthalates, which constitute
50% or more of a pipeline tape coating. Although
the polymer itself remains inert to degradation
in an underground application, the plasticizers
may be lost by a variety of mechanisms, includ-
ing bi0degradation.l’ This results in embrittlement
and cracking. Where this occurs over time, the
coating loses its ability to form a shielding disbond-
ment; however, field observations18 indicate that
this degradation is not sufficiently rapid to avoid
corrosion problems.
Shielding disbondments are not confined to
tape coating systems. In priniciple, any coating that
separates from the pipe surface to allow access of
a low conductivity groundwater to the steel surface
can create a shielding disbondment. For example,
shielding disbondments can be found under as-
phalt coatings where coating degradation has not
proceeded to the point where CP can penetrate the
coating to reach steel surface prior to separation of
the coating from the pipe. Shielding disbondments
provide the opportunity for MIC, especially where
the coating components feed microbial growth.
Understanding the
Corrosion Threat
Unprotected Steel
The corrosion of unprotected steel in soil is
relatively well understood as a combination of
chemical and microbiological processes. Simple
chemical corrosion depends on the presence of
an aggressive agent, which provides the oxidizing
power needed to convert iron in the steel to ionic
MIC in Underground Environments: External Corrosion in the Gas Pipeline Industry 6.7

form, and on the presence of an electrolyte, which OALVANlC BACTERIAL

supports the electrochemical processes leading COUPLE ENHANCEMENT
to metal loss. In general piping exposed to oxy-
gen and groundwater under conditions of neutral
pH will corrode to form iron (Ill) oxides at a mod-
est rate. Decreasing pH below 4 leads to rapidly
accelerated corrosion as acid becomes the ag-
gressive agent and corrosion products dissolve
readily to expose fresh steel surface to attack.lg
Increasing the salinity of the water in contact with
the steel surface increases corrosion rates by
improving the efficiency of the corrosion cell.
Overall Reaction:
These simple chemical considerations suggest
that corrosion under anaerobic conditions at near 8H' + 4Fe +S042- + "FeS" + We2++ 4H20
neutral pH should be modest, but this is not the
case. FIGURE 6.6
In the 193Os, severe corrosion rates were Schematic diagram of the mechanism of corrosion in
found in such circumstance^.^^^^ Water mains in a steel/FeS/SRB corrosion cell. The galvanic couple be-
black water logged soils in Holland had to be re- tween steel and iron sulfide is created and probably sus-
tained by SRB removing electrons from the iron sulfide
placed every two or three years. These biologi-
matrix as a source of reducing power.
cally active soils were found to contain SRB, a
group of anaerobic organisms that reduce ground-
water sulfate to sulfide as part of their essential
metabolism. Microbially generated black iron sul- predicting corrosion risk for unprotected steel in
fide precipitates are very aggressive toward steel. soil. These are shown in Table 6.2.
The mechanism involved is now usually described In this scheme, aerobic soils with low conduc-
as a galvanic couple formed between iron sulfide tivity groundwater are deemed relatively benign
and steel,21which is created and sustained by mi- while anaerobic soils are considered more aggres-
crobial action14 as shown in Figure 6.6. Corrosion sive presumably due to the potential for anaerobic
rates of 0.2 mm/year and penetration rates greater SRB to set up corrosion cells (Figure 6.6). Re-
than 0.7 mm/year have been reported in field18 duced soil resistivity is taken as more aggressive.
and lab14studies, but the actual corrosion rate is
a function of the iron sulfide content of the matrix in
contact with the steel s ~ r f a c e . ' ~Soils
~ ' ~with high TABLE 6.2
clay content, which retain water saturation and pro- Soil Aggressivity Model(A)
mote anaerobic conditions at pipe depth, are es-
pecially conducive to this scenario. Criterion Aggressive Nonaggressive
In general the relative importance assigned Resistivity (ohms-cm) t2000 >2000
to these simple chemical and microbial corrosion and/or
mechanisms is supported by early schemes for de- Oxidation Reduction ~0.400 >0.400
Potential (at pH 7, or ~0.430if clay or >0.430 if clay
termining soil aggressivity. These schemes used
measurable soil parameters taken at pipe depth to v WE))
Borderline Cases to >20 <20
assess the threat of corrosion damage in various Be Resolved by
locations. One such scheme developed by Booth Water Content ("A)
et al. in the 1970s was based on the extensive
(A) Based on average values of soil resistivity, redox potential, and water content
collection of soil information over dozens of field of the soil at pipe depth.22,23Because soil readings varied in some sites over
time, predictions in this model were based on the average of as many readings as
Correlations of observations to actual possible for each site.
corrosion damage established a set of criteria for
6.8 MIC in Underground Environments: External Corrosion in the Gas Pipeline Industry
Increased conductivity of both soil and ground-
water makes conditions more aggressive as this
provides a better electrolyte to support a more
efficient corrosion cell. The degree of soil wa-
ter saturation is taken as a secondary parameter
for prioritizing locations, with other factors being
equal.
Such schemes are in principle useful for as-
signing the likelihood of unprotected steel in
a given location suffering significant corrosion
damage. Appropriate soil probes have been
designed for the convenient collection of the
needed data.24 The information gained can be
used for risk assessment and for identification
of locations needing high-priority attention in an
integrity management plan. Unfortunately, the
simple model shown in Table 6.2 breaks down
when applied to operating pipeline systems with
protective coatings and under cathodic protection.
Protected Steel
For pipelines under cathodic protection, the
dependence of aggressivity on the soil resistivity
factor as shown in Table 6.2 is reversed. The sim-
ple model predicts that more corrosion will occur
with lower soil resistivity but the opposite is true for
cathodically protected pipelines. Here better elec-
trical conductivity in the groundwater leads to more
effective CP for steel exposed by:
missing coating in “holidays” or “jeeps,”
degraded coating that has lost its insu-
lating ability, or
shielding disbondments.
Even MIC involving the steeI/iron sulfide/SRB
corrosion cell shown in Figure 6.6 is arrested
by cathodic protection potentials of -950 mV
(CU/CUSO4). ’ than the mackinawite precipitated in the simple
In the real world, swings between aerobic
and anaerobic conditions at a single location
lead to mixed corrosion scenarios, some of which
give surprisingly severe corrosion rates. Table 6.3
summarizes the six common corrosion scenarios
found in almost 200 corrosion excavations on
protected pipeline systems in western Canada.
The primary corrosion scenarios correspond to
mechanisms that underlie simple soil aggressivity
models. The secondary transformations represent
cases where transitions occur between aerobic
and anaerobic conditions in the field. These are
not adequately represented in the schemes such
as the one shown in Table 6.2.
The various scenarios shown in Table 6.3 can
be identified by analysis of corrosion products
taken from field site^.^^^^^ In general, X-ray diffrac-
tion (XRD) can be used to identify crystalline prod-
ucts that are diagnostic for the various scenarios
shown. In some situations, microbially produced
iron sulfides are amorphous and cannot be seen
by XRD. In this case simple qualitative chemi-
cal analysis3 or energy dispersive X-ray analysis
(EDXA) can be used to detect telltale sulfides. Us-
ing corrosion products to assign the mechanism of
attack is convenient, and it has the advantage that
organisms do not have to be numerous and active
at the time of excavation for one to recognize an
MIC scenario.
The most severe corrosion scenarios found
to date (Table 6.3) all involve sulfides produced
by microbial action.14 The steelhron sulfide/SRB
corrosion cell is a feature of anaerobic conditions
but can be considerably worsened by the occa-
sional incursion of oxygen as shown in laboratory
studies (Figure 6.7). These corrosion cells are
extremely difficult to oxidize thoroughly and they
revert readily to the original corrosion rate when
anaerobic conditions return.26 Conversion of an
aerobic corrosion cell that has produced iron (Ill)
oxides as its corrosion products to an anaerobic
scheme with active SRB leads to the production of
unique iron (11) sulfides in the microbially sustained
corrosion mechanism. These sulfides are more
aggressive in nonbiological studies of the galvanic
couple formed between steel and iron sulfides
primary SRB scenario.21 This suggests that the
secondary transformation of an aerobic corrosion
site to an anaerobic SRB one may be a more
severe corrosion scenario than shown in the table.
The importance of at least two secondary
transformations as severe corrosion scenarios
MIC in Underground Environments: External Corrosion in the Gas Pipeline Industry 6.9

TABLE 6.3
Corrosion ScenariodA)

Frequency Diagnostic Corrosion Rates

Scenario (W Corrosion Products (mm/year)
PrimarycB)
Aerobic 3 iron oxides: lepidocrosite, 0.03 to 0.2
maghemite, magnetite,
hematite, goethite
Anaerobic 29 iron carbonate: siderite 0.01
Anaerobic + SRB 27 iron sulfides: 0.2 (general)
amorphous "FeS:' 0.7 (pitting)
mackinawite, greigite
Secondary(c)
Anaerobic becomes aerobic 21 +
iron oxides siderite 0.03to 0.2
underneath
Aerobic becomes anaerobic + SRB 3 marcasite, pyrite 0.2 (general)
0.7 (pitting)
or more?
Anaerobic + SRB becomes aerobic 17 elemental sulfur, iron 1 to 5(D)
oxides, siderite

(A) Deduced from corrosion product analysis based on excavation of corrosion sites on pipelines in western Canada.'4,25
(B) A primary scenario is one that occurs under one set of conditions.
(c) A secondary scenario is one in which the original scenario changes to a second scenario.
(D) Extreme rates may be related to very aggressive short-lived intermediates (such as sulfur) and may not be sustained.

suggests that the simple criterion for soil oxi- locations showing either a sustained anaerobic na-
dation reduction potentials (ORP) shown in the ture (consistent with Table 6.2) or showing periodic
soil aggressivity model, Table 6.2 is inade- swings between anaerobic and aerobic conditions.
quate. Worst-case scenarios can be expected for

Other MIC Scenarios

0.07
2 0.06
v Although SRB are important agents for MIC,
2 0.05
3 0.04 they are not found at all external corrosion sites
5 0.03t
.* cornsion Rate = o 11 mm/yr I \ on pipeline systems. An extensive survey of field
0 0.02 sites carried out in a Gas Research Institute project
0.01
0
on MIC found that many sites did not contain
0 50 100 150 zoo these organisms.' Other mechanisms for MIC
p2

Time (Days) have been suggested. Notable observations were

FIGURE 6.7
Weight-loss experiment under anaerobic conditions with
steel exposed to wet clay soil rich in SRB and iron sul-
fide/iron carbonate corrosion products. A period of air
exposure in the middle of the experiment greatly en-
hances corrosion rates. Return to anaerobic conditions
restores the original scenario.
made with respect to the concentration of organic
acid anions found in corrosion deposits' and an
assay was developed to enumerate the sort of mi-
croorganisms involved. A fingerprint for the micro-
scopic metal damage in the bottoms of corrosion
pits associated with microbial involvement was de-
scribed as diagnostic for MIC sites. Techniques for
6.10 MIC in Underaround Environments: External Corrosion in t h e Gas Pipeline Industry
generally assessing field sites for MIC along with
tools to do so, which came out of this program,
have been described e l ~ e w h e r e In
. ~the
~ ~ context
of this discussion, these other MIC scenarios rep-
resent situations where external pipeline corrosion
is aggravated by involvement of bacteria other than
SRB. In terms of integrity management, the possi-
bility of MIC in sites without iron sulfide suggests
that corrosion scenarios may be more severe than
expected on the basis of simple chemical stud-
ies of corrosion rates for scenarios without SRB in
Table 6.3. More needs to be known of these other
scenarios and where they occur before further
implications can be drawn.
MIC may be aggravated by the presence of
chloride anions. Laboratory studies show that a
synergy exists between pitting of stainless steels
and corrosion by SRB.27 In the field a general
correlation is seen between the chloride content
of corrosion products and the severity of damage
seen in corrosion pits on pipelines.’I2 This sug-
gests that chloride levels in a groundwater may ul-
timately be linked to enhanced corrosion damage
in future predictive models for soil site aggressiv-
ity. Preliminary lab experiments and available liter-
ature suggest that chloride concentrations above
about 150 ppm merit attention.
Newer Coatings
The two basic types of coating failure de-
scribed here have been illustrated using avail-
able information on asphalt and tape coated lines.
Newer coating systems employing a wide range of
materials and application technologies have been
in service less time and their modes of failure are
yet to be understood fully. In general, newer coat-
ings such as factory applied fusion bond epoxy
powder technologies, extruded polyethylenes,
and combination coatings involving intimately
bonded layers of fusion bond epoxy (FBE) and
polyolefins promise superior performance and
potentially lower life-cycle costs. Certainly, initial
evaluations suggest that they will be less sus-
ceptible to disbondment (Figure 6.4),and field
performance to date has been very good in terms
of the frequency of corrosion failures.
Integrity Management
Microorganisms are important to consider in
pipeline integrity management as agents of coat-
ing degradation and disbondment as well as MIC.
For MIC or any other external corrosion mecha-
nism to proceed, both the mating and CP system
have to be rendered ineffective.
For steel surfaces exposed by missing or de-
graded coatings, adequate cathodic protection can
forestall and mitigate corrosion damage. Monitor-
ing the current density required to maintain ade-
quate CP potentials in pipe to soil potential sur-
veys along the right of way can identify degraded
coating problems. Installation of new anode beds
or increasing current output for existing ones can
maintain the integrity of the system where the coat-
ing ultimately degrades to lose its electrical resis-
tance. Close interval surveys and holiday detec-
tion techniques are useful to help pinpoint potential
trouble spots.
Shielding disbondments offer an insidious op-
portunity for MIC and other external corrosion
problems. These do not show up in pipe to soil po-
tential surveys where groundwater salinities are
too low to allow penetration of CP under the
disbonded coating. Low-conductivity groundwater
(<4 mS/cm) combined with very anaerobic condi-
tions (-300 mV Cu/CuSO4 or less) or conditions
that vary between anaerobic and aerobic provide
worst-case conditions for corrosion damage. For
tape coatings that tend to form shielding disbond-
ments, wet soils with a high clay content (>20%)
in freshwater locations have proven particularly
prone to MIC involving SRB and iron sulfide.
At present, shielding disbondments cannot be
identified by any kind of surface survey. Moni-
toring is confined to the use of intelligent tools
for In Line Inspection (ILI). Identification of ex-
ternal metal loss allows excavation and repair of
specific locations representing high risk. Analy-
sis of corrosion products in excavated sites and
MIC in Underground Environments: External Corrosion in the Gas Pipeline Industry
a knowledge of the external environmental fac-
tors that foster various corrosion scenarios along
the right of way can be used to assign the worst-
case corrosion rates for locations not excavated.
These predicted corrosion rates can be used to
set an interval for future ILI runs. As subse-
quent ILI data become available, the progress
of corrosion damage at specific sites can be
tracked and the ongoing maintenance program
refined.
Future Needs
Use of newer coating systems offers the
promise of improved performance, but past history
suggests that careful analysis of failure modes in-
cluding testing for susceptibility to microbial degra-
dation be carried out as part of coating qualification
tests.
For existing systems, complete rehabilitation
by extensive excavation and recoating is extremely
costly. Improved integrity management methods
must be developed to locate and repair specific
locations of special susceptibility, high risk, or im-
pending failure. Ideally, ways must be found to ex-
tend this approach by soil probe measurements
and surface survey techniques to lines not acces-
sible to ILI.
The outstanding needs to achieve this aim
include:
a way to locate shielding disbondments
without ILI or excavation,
a better understanding of the mecha-
nisms of MIC not involving SRB,
reliable correlations between measur-
able environmental parameters in the soil
around a pipe and the likelihood of cor-
rosion under adjacent degraded and dis-
bonded coatings, and
tools to make the necessary measure-
ments by surface survey without excava-
tion.
6.11
References
1. D.H. Pope, “Microbiologically Influenced Corrosion
in the Natural Gas Industry,” Gas Research Insti-
tute, Topical Report GRI-92/0469 (Chicago, IL: Gas
Research Institute [GRI], 1992).
2. D.H. Pope, “State-of-the-Art Report on Monitoring,
Prevention and Mitigation of Microbiologically Influ-
enced Corrosion in the Natural Gas Industry,” Gas
Research Institute, Topical Report GRI-92/0382
(Chicago, IL: GRI, 1992).
3. “Microbiologically Influenced Corrosion (MIC):
Methods of Detection in the Field,” Gas Research
Institute, GRI Report no. 88/0113 (Chicago,lL: GRI,
1991).
4. P.J.B. Scott and M. Davies, MP 28, 5(1992): 64.
5. G.A. Voordouw, Y Shen, C.S. Harrington, C.S.
Telang, T.R. Jack, and D.W.S. Westlake, Appl. En-
viron. Microbiol. 59(1993): 4104.
6. G.A. Voordouw, A.J. Telang, T.R. Jack, J. Fought,
P.M. Fedorak, and D.W.S. Westlake, “ldentifica-
tion of Sulfate-Reducing Bacteria by Hydrogenase
Gene Probes and Reverse Sample Genome Prob-
ing,” in Applications of Molecular Biology in Envi-
ronmental Chemistry, eds. R.A. Minear, A.M. Ford,
L.L. Needham, and N.J. Karch (Boca Raton, FL:
Lewis Publishers, 1995).
7. B. Davis, Petroleum Microbiology (New York, NY:
Elsevier, 1967), pp. 403-439.
8. J. Bunker, J. SOC.Chem. Ind. 58(1939): 93.
9. T.R. Jack, G.Van Boven, M.J. Wilmott, R.L.
Sutherby, and R.G. Worthingham, MP 33,8(1994):
17.
10. J.E. Potts, R.A. Clendinning, W.B. Ackart, and W.D.
Niegisch, “The Biodegradability of Synthetic Poly-
mers,” in Polymers and Ecological Problems, ed. J.
Guillet (New York, Plenum, 1973), pa71,
11. T.R. Jack and R.G. Worthingham, in Biologically
Induced Corrosion, ed. S.C. Dexter (Houston, TX:
NACE, 1986), p. 339.
12. J.S. Smith and J.D.A. Miller, Brit. Corros. J. 10, 3
(1975): 136.
13. T.R. Jack, R.G. Worthingham, and F.G. Ferris, in
Microbially Influenced Corrosion and Biodeteriora-
tion, eds. N.J. Dowling, M.W. Mittelman, and J.C.
Danko (Houston, TX: NACE, 1990), pp. 4-19.
14. T.R. Jack, M.J. Wilmott, R.L. Sutherby, and R.G.
Worthingham, “External Corrosion of Line Pipe-A
Summary of Research Activities Performed Since
6.12 MIC in Underground Environments: External Corrosion in the Gas Pipeline Industry
1983,”CORROSION/95, paper no. 354 (Houston,
TX: NACE, 1995).
15.T.R. Jack, G. Van Boven, M. Wilmott, and R.G.
Worthingham, “Evaluation of Coating Performance
After Exposure to Biologically Active Soils,” COR-
ROSION/95, paper no. 353 (Houston, TX: NACE,
1 995).
16.Canadian Standards Association, CSA 2 245.20-
M92,clause 12.9.
17. E.S. Pankhurst, J. Oil Colour Chem. Assoc. 56
(1973):373.
18. R.G. Worthingham, T.R. Jack, and V. Ward, in
Biologically Induced Corrosion, ed. S.C. Dexter
(Houston, TX: NACE, 1986),p. 330.
19. W. Whitman, R. Russell, and V. Altieri, Ind. Eng.
Chem. 16(1924):665.
20. C.A.H. Von Wohlzogen Kuhr and L.S. Van der Vlugt,
Water (The Hague), 18(1934):147.
21. R.A. King and J.D.A. Miller, Anti Corrosion August
(1 977):9.
22. G.H. Booth, A.W. Cooper, and P.M. Cooper, Brit.
Corros. J. 2,May (1 967):109.
23. G.H. Booth, A.W. Cooper, and A.K. Tiller, Brit. Cor-
ros. J. 2,May (1 967):1 16.
24. M. Wilmott, T.R. Jack, J. Geerligs, J. Sutherby, R.L.
Diakow, and B. Dupuis, Oil Gas J. 93, 14(1995):
54*
25. T.R. Jack, M.J. Wilmott, and R.L. Sutherby, MP 31,
ll(1995):19.
26. T.R. Jack, M. Wilmott, J. Stockdale, G. Van Boven,
R.G. Worthingham, and R.L. Sutherby, “Corrosion
Consequences of Secondary Oxidation of Micro-
bial Corrosion Scenarios” in Proceedings of the
1995 InternationalConference on Microbially Influ-
enced Corrosion, held May 8-1 0, 1995 (Houston,
TX: NACE, 1995),p. 28/1.
27. T.S. Gendron, R.D. Cleland, and P.A. Lavoie, in
Microbially Influenced Corrosion and Biodeteriora-
tion, eds. N.J. Dowling, M.W. Mittelman, and J.C.
Danko (Houston, TX: NACE, 1990),p. 2-1.

Microbiologically Influenced Corrosion of
Internal Aspects of Natural Gas Industry
Pipelines and Associated Equipment:
Mechanisms, Diagnosis, and Mitigation
Introduction
Microbiologically influenced corrosion (MIC)
processes are those forms of corrosion that are
influenced by the presence and activities of mi-
croorganisms. Microbiologically influenced corro-
sion usually acts in concert with other corrosion
mechanisms and may, at times, appear to be un-
der deposit acid attack, crevice corrosion, oxygen-
concentration-cell corrosion, ion-concentration-
cell corrosion, or carbon-dioxide corrosion. In its
most severe form MIC can lead to highly local-
ized metal loss and premature system failure. The
problem-causing microbes may be present, di-
rectly influencing the local corrosion rates, for only
a portion of the overall corrosion process, a fact
that led to the current terminology microbiology in-
fluenced corrosion, as opposed to the older refer-
ences to microbiologically inducedcorrosion, bac-
terialcorrosion, or biocorrosion. It is very important
to realize that the presence of active microbes in a
system does not dictate that MIC is occurring, but
it does indicate the potential for its occurrence.
MIC has been documented in a wide variety of
pipelines, including, but not limited to, those trans-
porting potable water, sewage, natural gas, liquid
hydrocarbons, production chemicals (e.g., soaps,
acids), and cooling waters. Several reviews are
6.13
CHAPTER 6 (PARTII)
By D.H. Pope
available that will give the reader an introduction
to these topics and provide specific references to
particular situations that are beyond the scope of
this chapter.(l-lO)
MIC has been described for almost all pipeline
metals and alloys, except t i t a n i ~ m . ( ~ l ~Mi-
-~~~)
crobiologically influenced deterioration of other
pipeline materials such as cement, concrete, and
linings and coatings, although not strictly speaking
corrosion events, represent serious problems to
pipeline operator^(^^^^^^' l) (see also Chapter 6,
Part I, this volume).
MIC-related failures can be diagnosed by test-
ing for microbiological and chemical constituents
at the corrosion site and evaluating these data
with the results of metallurgical tests and opera-
tional information. In the opinion of the author there
is no single biological, chemical, or metallurgical
factor upon which a diagnosis should be made
(e.g., presence, absence, or numbers of sulfate-
reducing bacteria or the biochemical activity levels
of these organisms, or presence of certain forms of
iron sulfide (mackinawite). Rather, all of the avail-
able information should be taken together to form
an opinion and to determine whether the influence
of the microbes was principally in the past or is
continuing at the time of the investigation. Early
detection of MIC and continued monitoring of cor-
rosion rates, including maximum pitting rates, are
6.14
necessary if MIC is to be brought and kept under
control.
Treatment of MIC can be accomplished using
a wide variety of methods. These should be ap-
plied to a given system only after careful testing
of effectiveness in that particular location, consid-
eration of compatibility with system materials and
other treatment chemicals, safety, environmental
issues, and cost.
These various aspects of MIC diagnosis, mon-
itoring, and treatment are discussed in further de-
tail in the following sections of this chapter, with
examples given to illustrate the main points. Since
this chapter deals primarily with internal MIC of gas
pipelines, the reader is referred to other sources
(e.g., References 2 and 3) for comprehensive in-
formation on MIC and its occurrence on a wide
variety of industrial metals and alloys. References
2 through 11 provide case histories and more de-
tailed information on MIC mechanisms, detection
methods, and mitigation strategies than can be
provided in this chapter.
Microbes Involved in MIC
Most types of microbes occurring naturally in
waters or soils have the potential to participate in
MIC of some type of metal or alloy.(1~3~4~10~1
Micro-
biologically influenced corrosion of pipelines has
been documented as involving aerobic, anaerobic,
slime-forming, acid-producing, sulfate-reducing,
nitrate-reducing, iron-oxidizing, and iron-reducing
bacteria. Within each of these general physiolog-
ical groups are hundreds of individual species of
bacteria. It is important to recognize that MIC is
almost always due to the presence and action of
microbial communities containing many different
types of microbes. The composition of the com-
munity may change with each stage in the devel-
opment of the MIC site and from one specific lo-
cation to another. Contrary to popular belief, MIC
is rarely due to the activities of any single group
of organisms such as sulfate-reducing bacteria
(SRB).
Microbiologically Influenced Corrosion of Internal Aspects
Mechanisms of MIC
The classic mechanism for MIC of steel and
iron was proposed by von Wolzgen Kuhr in 1934.
The mechanism was based on the idea that
the rate-limiting step in corrosion is the dissoci-
ation of hydrogen from the cathodic site. Some
(hydrogenase-positive) strains of SRB consume
hydrogen and thus “depolarize” the cathode and
accelerate the corrosion process. Although the
cathodic-depolarization mechanism may be a con-
tributing factor in MIC, it is rarely seen as the sole
mechanism for corrosion in laboratory-controlled
and industrial environments.
Figures 6.8 through 6.13 illustrate a model in
which microbial colonization can lead to a corro-
sion site and examples from field sites of each ma-
jor phase in the development of a MIC site. The
concept is based on the formation of an occluded
spot on the surface of the metal, which, in the pres-
ence of an electrolyte, creates anodidcathodic re-
lationships between the occluded area and sur-
rounding metal. Phase 1 (Figure 6.8), the initial
attachment of microbes to the surface, may be
related to preexisting corrosion, metallurgical fac-
tors (welds, inclusions, etc.), or other local con-
ditions. The local chemical-electrochemical envi-
ronment is also an important factor for microbial
attachment and colony development. Figure 6.9
shows the surface of carbon steel exposed to
tap water for 3 days and demonstrates Phase I
< J
C Bacteria
Adsorbed Nutrients
-
Metallurgical Feature Desirable to Bacteria
FIGURE 6.8
Phase 1. Microbial attachment.
Microbiologically Influenced Corrosion of Internal Aspects
FIGURE 6.9
FITC-stained MIC community on carbon steel exposed
to city water for 8 days. (See color plates.)
colonization. Note the patchy nature of the colo-
nization.
Phase 2 (Figure 6.10) shows the development
of a discrete and well-developed microbial commu-
nity, fixed to the metal, which creates an occluded
area that may be relatively anodic to the surround-
ing area. The communities often produce sticky
polymers that retain organic and inorganic mat-
ter and aid in the occlusion process. The contin-
ued buildup of material in and over the community
allows the conditions inside and under the com-
munity (i.e., oxygen level, ion concentration, pH)
Microbial Community (Calls, Polymer and Corrosion products)
Crevice Anode
It is suspected that the pH in the crevice
region is above 4 during this phase
FIGURE 6.10
Phase 2. Microbial community development and initia-
tion of crevice corrosion under fixed anode.
6,15
to become chemically dissimilar to the surround-
ing surface. As the community matures, interde-
pendencies continue to develop between the in-
dividual community members. For example, the
organic acids produced by acid-producing bac-
teria (APB) provide nutrients for other microbes
including SRB. Most microbes use only the an-
ionic part of the organic acids; thus their con-
sumption results in a buildup of protons, leading to
lower pH in the corrosion site developing under the
community. The lower pH tends to attract anions
(CI- >> SO, > OH-) into the occluded area, which
can add to the corrosivity of the environment and
stimulate the biochemical actidties of certain types
of microbes. These conditions under the commu-
nity lead to occluded corrosion. Thus, character-
istically, Phase 2 involves a fixed community over
an area of occluded corrosion, acidic conditions in
the occluded region, accumulation of chloride and
other anions, and aggregation of these materials
with corrosion products into the beginnings of what
will eventually be recognized as discrete deposits
(also called nodules or tubercles). Figure 6.1 1 is a
picture of a well-developed, Phase 2 MIC site.
Phase 3 (Figure 6.12) involves the formation of
a mature nodule, or tubercle, over a well-defined
pit. At this stage, the pH in the active pit region is
often less than 4. Owing to the low pH, most of
FIGURE 6.11
Internal diameter of gas pipeline showing Phase 2 of a
MIC site. (See color plates.)
6.16
Anlona (CL ,SO ,,
It is thought that most of the nodule is corrosion product
live bacteria are present in crust of nodule
FIGURE 6.1 2
Phase 3. Nodule formed over well-defined pit.
the viable microbes are now in the crust of the
tubercle, rather than in the pit. The corrosion
process now takes the form of underdeposit acid
attack and is driven (rate controlled) chemically
rather than as a direct result of microbial coloniza-
tion. Thus, the corrosion process would continue
even in the absence of the microbes. Therefore,
when the problem is in the advanced stages,
simple chemical treatment to kill microbes will not
solve the corrosion problem, but rather, mechan-
ical and/or chemical cleaning and treatment are
required. Figure 6.13 is a composite of Phase
FIGURE 6.1 3(a)
Phase 3. MIC nodule on a sucker rod from an oil well,
showing layers of corrosion product. Layer at bottom of
pit is very rich in chloride. (See color plates.)
Microbiologically Influenced Corrosion of Internal Aspects
-
FIGURE 6.1 3(b)
Copper-nickel (90/10) tubing showing mature discrete
deposits. Severe pitting was seen under most deposits.
(See color plates.)
3 nodules on various metals and alloys. All of
these showed severe, localized pitting under the
nodules.
Detection of MIC
A variety of methods have been used or pro-
posed for use in detection and diagnosis of MIC
and for on-line monitoring of MIC. A review of
FIGURE 6.1 3(c)
304 Stainless steel piping showing mature nodules es-
pecially at weld and heat-affected zone. Goblet-shaped
pits were observed under the nodules. (See color plates.)
Microbiologically Influenced Corrosion of Internal Aspects
I
I
Liquid S s m p l e
Collect in Sterile
Container
Analysis Kit
Imolrtion of
Spociflc Micro-
Anorobic Bacteria Orgrni8mr
Aoid-produoing B sotaria
I
Sulfate-roducing B acteria
I
I Iron-related Bacteria I
I Low Nutrient Bacteria I
NitribdNitrato
Motabolizing Bacteria
Liquid and solid samples.
these methods, specific to the pipeline industry,
was done in which the advantages and disadvan-
tages of each were d i s c ~ s s e dThe
. ~ following is a
discussion of the methods that have proven use-
ful to the author and co-workers in research and
consulting work on pipelines, including those used
in several research programs performed for the
Materials Technology Institute, the Gas Research
Institute (GRI), the Electric Power Research Insti-
tute (EPRI), water distribution systems, fire protec-
tion systems, oil pipelines, and a variety of private
industries.
Viable culture of microbes in samples can be
done to determine the types and numbers of mi-
crobes present in samples. These tests are simple
and quantitative, and can be used to detect very
low levels (1 cell) of bacteria, if performed using
quality media and done according to the appro-
priate procedures. Viable culture tests should be
done immediately after collection of the sample.
6.17
Solid Samples (Soil.
Corrosion Productrr.
Place i n Sterile
D e i o n i z e d W star
and Makc Slurry
Fixativr Bottl0
c ~ . ~ formalin
.. or Analyses
glutorrldohydo)
-
A n r l y om
for soluble
Cb-m foal
S P E O f i c M
FIGURE 6.14
The samples must also be processed carefully to
avoid killing microbes of importance to a proper
diagnosis. A generalized scheme for sample col-
lection and processing for a variety of samples (liq-
uids, soils, corrosion products) is shown in Figure
6.14. A more detailed discussion of each proce-
dure is given in Reference 8.
Microscopic examination of samples can be
done on site or on samples properly preserved at
the time of collection. The sample can be observed
using a light microscope or an epifluorescence mi-
croscope after staining with a fluorescent dye that
will attach specifically to biological materials. Spe-
cific types of microbes in samples can be detected
using fluorescently labeled antibody probes. A
generalized diagram for such procedures is given
in Figure 6.15.These microscopic techniques re-
quire the use of a relatively expensive microscope
and a trained observer. However, such an observer
can gain considerable useful information regarding
6.18 Microbiologically Influenced Corrosion of Internal Aspects

1;kks
I
n

prepared on-site in PBS-Formalin

with MIC. If the chemical results indicate MIC, it
should be confirmed by microbial culture along
’ c , m

1 Small volume spotted onto slide

Heat fixed
Stained with FlTC or
fluorescent antibody
Viewed using epifluorescence
FIGURE 6.15(a)
Procedure for total microscopic count using fluorescent
stain for biological material and epifluorescent micro-
scope. (See color plates.)
the numbers and types of microbes in the sample,
their physiological status, and their relationship to
the corrosion site or products.
Chemical characterization of corrosion prod-
ucts and bulk fluids is also important in the diag-
nosis of MIC. The presence of metals in the ap-
proximate ratio of the degraded alloy indicates a
corrosion product as opposed to a product of de-
position. However, in MIC of stainless steels, the
nickel content in the corrosion product is normally
lower than in the alloy (“denickelfication”). The
presence of ferrous iron and sulfide in pitted re-
gions, in conjunction with lower pH, is consistent
- SRB
0 - non-SRB
Cells from PBS-forrnalin heat
fixed to microscopic slide
Rabbit anti-SRB antibody
added to slide & allowed to
react
Goat anti-rabbit second
antibody labeled with FlTC
allowed to react with rabbit
anti-SRB
Viewed using epifluorescence
imicroscopy
FIGURE 6.15(b)
Procedure for enumeration of specific bacteria using flu-
orescently labeled antibodies. (See color plates.)
with consideration of the conditions at the site.
Tests for chemical species such as sulfide and
ferrous iron and for pH should be done immedi-
ately after sample collection; otherwise significant
changes may occur in these materials, leading to
false results.
The physical characteristics of the corrosion
site can also be of use in diagnosing MIC. In car-
bon steel, the degradation often takes the form of
hemispherical, cup-like pits within pits or scooped-
out pits. Also, microbial colonization may follow
manganese-sulfide inclusions that are “strung out”
in the process of rolling carbon steel, which re-
sults in a type of material loss that resembles tun-
neling. In stainless steels the pits are usually as-
sociated with the weld, heat affected zone, or an
area where the material has been deformed. Sub-
surface, goblet-shaped pits are usually observed
in stainless steels. Other patterns are characteris-
tic of MIC in aluminum alloys, copper alloys, and
nickel alloys. The metallurgical characterization of
the suspect MIC site should be done in the field,
if possible. Guidelines for metallurgical examina-
tion have been published in field guides for the
investigation of MIC in pipelines for a variety of
industries 7-9)
Finally, the physical and chemical characteris-
tics of the affected system should be considered in
the diagnosis. For example, microbial activity, and
the previously described electrochemical mecha-
nisms, require water to be present in the corrosion
site at least periodically; therefore, MIC historically
occurs in places within systems where water can
accumulate. Other factors, such as system tem-
perature, should be considered to determine if MIC
is feasible.
Monitoring for MIC
Monitoring for MIC is a topic discussed by
several authors with various points of view and
with different experiences. It should be pointed
out that monitoring in laboratory settings and in
actual pipelines is quite different. The author and

Microbiologically Influenced Corrosion of Internal Aspects
colleagues involved in research and testing for MIC
in a wide variety of industrial settings have con-
cluded that a monitoring program for internal cor-
rosion should include consideration of as many of
the following factors as possible.
System conditions including the presence of
water, nutrients, and other chemical constituents
(e.g., pH, akalinity, chloride, sulfate, sulfide), vi-
able microbes (in liquids and on metal surfaces),
and operational conditions should be determined
as precisely as possible. It is critical that some di-
rect measurement of general and localized (pitting)
corrosion also be used. The most reliable results
in the author’s studies have come from the use of
coupons that are analyzed for colonization, gener-
alized corrosion rates, and maximum pitting rates
(by performing microscopic pit analyses). It is ab-
solutely critical that coupons used in monitoring be
of the same metallurgy and surface condition as
the pipe. Polished coupons, in our experience, will
rarely be colonized or corroded in the same way
or to the extent as mill-finished coupons. It is also
crucial that the coupons be located in areas that
have conditions conducive to the development of
MIC (i.e., the worst-case conditions for the pipeline
under consideration). Coupons used for MIC mon-
itoring should be removed and processed imme-
diately using culture and microscopic examination
for microbes and corrosion (details can be found
in Reference 8). An attempt must be made to cor-
relate the presence and activities of microbes to
corrosion, since the simple presence of microbes
in a sample is rarely suff icient to prove MIC involve-
ment in the corrosion events at the site.
Mitigation of MIC
~ ~~~
Mitigation of internal MIC must be done af-
ter careful monitoring and consideration of the
local situation; otherwise considerable time and
money can be spent performing unnecessary or
ineffective treatment of the pipeline. A much more
detailed discussion of mitigation methods, their
application, and monitoring of treatment success
is contained in Reference 8.
Next Page
6.19
Physical Methods
Pigging, which physically cleans the internal
surfaces of the pipeline, is very effective for mit-
igating MIC when performed regularly and may
be enhanced with a cleaning agent (e.g., alcohol),
corrosion inhibitor, and/or biocide. Pigging disturbs
the corrosion sites and removes water, microbes,
corrosion products, and food for microbes. It also
allows treatment chemicals access to the area of
active corrosion in the pits, where the corrosion
process and/or bacterial activity may be more ef-
fectively integrated.
Chemical Methods
Corrosion inhibitors and biocides can be of use
in mitigating MIC as well as in preventing MIC from
becoming established. However, it is imperative
that treatments be tested on actual samples from
the sites to be treated to determine whether the
treatment regime will work and to avoid over- or
undertreating. Details of field tests and methods
of testing mitigation measures are contained in
References 8 and 10. Significant incompatibilities
can exist between corrosion and scale inhibitors
and some biocides (see Table 6.4 for examples).
These must be checked before chemical treat-
ment is implemented in the actual facility. Chem-
ical treatments can be used with great success,
economy, and minimal risk to the environment and
personnel if the principles of targeted treatment
and optimization are followed. This requires find-
ing the location of the microbes, water, etc. and
eliminating them as close to the source as possi-
ble with the minimum amount of biocide or corro-
sion inhibitor necessary to do the job. This must
be accompanied by aggressive follow-up monitor-
ing to make sure that the treatment is continuing
to work.
Some Examples
An example of targeted treatment is shown in
Figures 6.16-6.18. An offshore production, gath-
ering, and transmission system had suffered from
MIC. After performing system-wide microbiological
Previous Page

6.20 Microbiologically Influenced Corrosion of Internal Aspects

TABLE 6.4
Compatibility Tests of Biocides and Corrosion and Scale Inhibitors

Corrosion Scale Liquid Phase Coupon

Biocide Inhibitor@) APB SRB APB SRB
(100 PPm) (50 PPm) (20 PPm) Sample Time Loglo/mL Log1o/mL Loglo/mL Loglo/mL
None None None 0 4 4 4 4
None None None 0 4 4 4 4
None None None 4 hours 4 4 4 4
None None None 30 days 4 4 4 4
Biocide-1 None None 4 hours 0 0 0 0
Biocide-1 None None 30 days 0 0 0 0
Biocide-2 None None 4 hours 4 4 4 4
Biocide-2 None None 30 days 4 4 4 4
None c.1.-1 None 4 hours 4 4 4 4
None (3.1.-1 None 30 days ND@) ND ND ND
None C.I.-2 None 4 hours 4 4 4 4
None C.I.-2 None 30 days 4 4 4 4
Biocide-1 c.1.-1 None 4 hours 0 0 2 0
Biocide-1 (2.1.-1 None 30 days 0 0 4 4
Biocide-1 C.I.-2 None 4 hours 0 0 1 0
Biocide-1 C.I.-2 None 30 days 0 0 0 0
Biocide-2 c.1.-1 None 4 hours 4 4 4 4
Biocide-2 c.1.-1 None 30 days 4 4 4 4
Biocide-2 C.I.-2 None 4 hours 4 4 4 4
Biocide-2 C.I.-2 None 30 days 4 4 4 4
Biocide-1 c.1.-1 s.1.-1 4 hours 0 0 2 0
Biocide-1 c.1.-1 s.1.-1 30 days 4 4 4 4
Biocide-1 c.1.-1 S.I.-2 4 hours 1 0 2 0
Biocide-1 c.1.-1 S.I.-2 30 days 0 0 4 4
Biocide-1 C.I.-2 s.1.-1 4 hours 0 0 1 0
Biocide-1 C.I.-2 s.1.-1 30 days 0 0 2 0
Biocide-1 C.I.-2 s.1.-2 4 hours 0 0 2 0
Biocide-1 C.I.-2 S.I.-2 30 days 1 1 3 3
Biocide-2 (2.1.-1 s.1.-1 4 hours 4 4 4 4
Biocide-2 c.1.-1 s.1.-1 30 days 4 4 4 4
Biocide-2 c.1.-1 S.I.-2 4 hours 4 4 4 4
Biocide-2 c.1.-1 S.I.-2 30 days 4 4 4 4
Biocide-2 c.1.-2 s.1.-1 4 hours 4 4 4 4
Biocide-2 c.1.-2 s.1.-1 30 days 4 4 4 4
Biocide-2 C.I.-2 S.I.-2 4 hours 4 4 4 4
Biocide-2 c.1.-2 S.I.-2 30 days 4 4 4 4
Biocide-2 None s.1.-1 4 hours 4 4 4 4
Biocide-2 None s.1.-1 30 days 4 4 4 4
Biocide-2 None S.I.-2 4 hours 4 4 4 4
Biocide-2 None S.I.-2 30 days 4 4 4 4

(A) C.1.-1 =corrosion inhibitor #1: C.I.-2 =corrosion inhibitor #2

(B) S.1.-1 = scale inhibitor #1; S.I.-2 =scale inhibitor #2
ND = no data
Microbiologically Influenced Corrosion of Internal Aspects 6.21

AVERAGE BACTERIA LEVELS IN LINE D

(AFTER TREATMENT)

c\\ Gathering Platform

LlNE
APB 1-
SEPARATOR SRB 1-
APB - 1
SRB 1- U
Production Platform

FIGURE 6.18
FIGURE 6.16 Line D after treatment.
Offshore production, gathering, and transmission system.

frequent treatment with biocides, which disappear

testing, liquidsas separators of two production
platforms were identified as the contributors of
most of the microbial contamination. Focusing the
treatment on these producer’s separators, rather
than the entire system, mitigated the problem with
minimal expense and use of chemical.
Figure 6.19 shows the results of treatment of
a gas storage well with an effective biocide, in this
case glutaraldehyde. Note that the bacteria were
controlled very well in the fluids and that the iron
levels dropped during treatment. However, discon-
tinuing glutaraldehyde treatment, an event that oc-
curred during a shut-in resulted in very quick return
of the microbes and higher iron levels, indicating a
return to higher corrosion rates. This demonstrates
the utility of continued monitoring to optimize treat-
ment and the necessity for continual or at least very
AVERAGE BACTERIA LEVELS IN LINE D
(BEFORE TREATMENT)
Gathering Platform
LINE
APB - 3
APE
. .. -
WELLS SEPARATOR SRB 2
APB
SRB
-2
- 1
APB - 4
0-m
SRB -3 - Production Platform
FIGURE 6.1 7
Line D before treatment.
from the treatment sites in a short period of time.
Figure 6.20 shows that another biocide, a qua-
ternary amine (QA), used at the same field as that
shown in Figure 6.19, failed to control microbes in
the fluid phase. However, on fresh metal coupons
the QA formed a film that discouraged microbial
colonization of the metal surface. The treatment
resulted in reduced iron levels in the produced flu-
ids and lower general corrosion rates and pitting
rates on coupons in the wells and in the gathering
system pipelines. The reasons for this are under
study, as are attempts to optimize the use of such
chemicals to prevent MIC. This has important in-
dustrial implications as the Q A biocides may also
provide inhibition of other corrosion mechanisms.
The QAs are also more environmentally benign
than some other biocides.
Table 6.5 shows the results of a one-time
treatment of a drip on a natural gas transmission
pipeline with 500 gal of isopropyl alcohol (approx-
imately 25% of the volume of the drip). The net
result was long-term cleanup of the drip, dehydra-
tion, and control over microbes in the drip with the
use of a chemical commonly employed in pipelines
for freeze protection, with no added environmental
or safety issues and at very low cost. This treat-
-
ment has replaced a much more expensive biocide
treatment program.
Figure 6.21 shows the results of treating gath-
ering system pipelines by soaking with 30% iso-
propyl alcohol for a period of seven days and then
6.22 Microbiologically Influenced Corrosion of Internal Aspects

m S R B WAPB mlron -Effe*ive Biocids

FIGURE 6.19 FIGURE 6.20

Well at a gas storage field after treatment with an effec- Well at the same gas storage field as in Figure 6.19,
tive biocide. Note the effects of discontinuing treatment treated with a quaternary-amine-based biocide.
during a shut-in.

withdrawal season. This treatment has replaced a

blowing out the liquids, corrosion products, and
other debris. The result was complete cleaning
of the piping at little cost and with no added en-
vironmental or safety issues. The microbe levels
in the gathering system piping gradually returned
to higher levels during the withdrawal season
(Figure 6.22); however, it was determined that this
period of three to four months was not sufficient
to cause high corrosion rates, if alcohol treatment
was repeated immediately after withdrawal had
ended and the pipelines left clean until the next
much more expensive biocide treatment program
at this gas storage field.
Figure 6.22 shows the internal diameter of a
gas pipeline just downstream of a low point that
contained produced liquids of pH 4.0. A failure oc-
curred at this low point. It was recognized that the
damage was due principally to MIC, with APB hav-
ing a major role in the corrosion events. It was
shown that the corrosion inhibitor being used in
this pipeline actually helped to support the growth
of MIC-related bacteria. The strategy was to pig

TABLE 6.5
Results of lsopropyl Alcohol Treatment of Drip, East Texas Site

Time after IPA Log,, Number Bacteria per ml lsopropyl

Site Date Sampled Treatment AER ANA APB SRB Alcohol Level
Lacy 4118/94 0 3 4 3 1 None
Lacy 4118/94 2.5 hours 3 3 2 0 High
Lacy 4119/94 15 hours 2 2 1 1 High
Lacy 412 1194 3 days 2 2 2 1 ND(A)
Lacy 6110194 2 months 0 0 0 0 ND
Lacy 912ai94 5 months 0 0 0 0 ND

(A) ND = no data
Microbiologically Influenced Corrosion of Internal Aspects 6.23

# bottles turned +AP0 NSR0

....................

................................

............. .......................

.......... ....................

ma
12/21 1/9/94 to/* 1/04

Sampling Date

FIGURE 6.21
Natural gas storage field gathering system pipelines.

FIGURE 6.22
Internal diameter of a natural gas pipeline showing corrosion at 6 o’clock position, immediately downstream of low
point in pipeline. (See color plates.)
6.24 Microbiologically Influenced Corrosion of Internal Aspects

FIGURE 6.23
Internal diameter of a liquid hydrocarbon pipeline at low point where water and debris accumulated. Note severe
pitting principally at 5-7 o’clock portions of pipe. (See color plates.)

fluids from the pipeline, eliminate treatment with
that particular corrosion inhibitor, and treat with an
effective biocide.
Figure 6.23 shows the internal diameter of a
pipeline carrying liquid hydrocarbons. Several fail-
ures occurred at low points where debris and wa-
ter accumulated. Biocide and corrosion inhibitors,
which were being used in the pipelines at “suffi-
cient” levels, were shown not to reach these loca-
tions in amounts necessary to control microbes or
corrosion. Rather, these chemicals appeared to be
suspended in water droplets in the hydrocarbons.
It was concluded that pigging to remove solids and
water (brines) from low points, followed by treat-
ment with an effective biocide-corrosion inhibitor
combination that partitions into the water phase
would likely give the best control over corrosion.
Acknowledgments
Much of this work was funded by the Gas
Research Institute (GRI), Chicago, Illinois, the
Southern California Gas Company (SOCAL),
Montebello, California, and The Department of
Energy under a Cooperative Research and De-
velopment Agreement (CRADA) between Argonne
National Laboratory (ANL), Argonne, Illinois, and
SOCAL. The authors express their appreciation
to Mr. Steve Foh of the GRI, Ms. Laurie Perry of
SOCAL, and Dr. James Frank of ANL for their con-
tinuing support of these programs.
References
1. D.H. Pope, D.J. Duquette, D.C. Wayner, Jr., and
A.H. Johannes, Microbiologically Influenced Cor-
rosion: A State of the Art Review (Columbus,
OH: Materials Technology Institute of the Chemi-
cal Process Industries, 1984), 76 pp.
2. D.H. Pope, D.J. Duquette, A.H. Johannes, and P.C.
Wayner, “Microbiologically Influenced Corrosion of
Industrial Alloys,” MP 23(1984): 14-1 8.
3. D.H. Pope, “A Study of Microbiologically Influenced
Corrosion in Nuclear Power Plants and a Practical
Guide for Countermeasures,” Final Report, EPRl
Microbiologically Influenced Corrosion of Internal Aspects
NP-4582 (Palo Alto, CA: Electric Power Research
Institute, 1984).
4. D.H. Pope, “A Study of Microbiologically Influenced
Corrosion and a Practical Guide for Its Treat-
ment and Prevention,” Final Report, EPRl CS-5495
(Palo Alto, CA: Electric Power Research Institute,
1986).
5. D.H. Pope, H.D. Aldrich, D.C. White, and D.R.
Jackson, “Microbiologically Influenced Corrosion in
the Natural Gas Industry,” Annual Report (Chicago,
IL: Gas Research Institute, 1990).
6. D.H. Pope, “Microbiologically Influenced Corro-
sion in the Natural Gas Industry,” Annual Report
(Chicago, IL: Gas Research Institute, 1991).
7. D.H. Pope, “State-of-the-Art Report on Monitor-
ing, Prevention and Mitigation of Microbiologically
6.25
Influenced Corrosion in the Natural Gas Industry,”
Topical Report (Chicago, IL: Gas Research Insti-
tute, 1992).
8. “Microbiologically Influenced Corrosion (MIC):
Methods of Detection in the Field,” Field Guide
(Chicago, IL: Gas Research Institute, 1990).
9. “Microbiologically Influenced Corrosion (MIC) II: In-
vestigation of Internal MIC and Testing Mitigation
Measures,” Field Guide (Chicago, IL: Gas Research
Institute, 1992).
10. G. Kobrin, ed., A Practical Manual on Microbiolog-
ically Influenced Corrosion (Houston, TX: NACE,
1993).
11. D.D. Mara and D.J.A. Williams, “Corrosion of Mild
Steel by Nitrate Reducing Bacteria,” Chem. Indus.
May (1971): 566.

A Case Study-Microbially Induced
Organic Acid Attack in a Natural
Gas Gathering System
Abstract
Microbially produced organic acids, in contact
with mild steel pipelines, can cause an accelerated
form of corrosion similar in appearance to a C02
type of attack.lP2 While the two types of corrosion
may appear to be similar, identification of the cor-
rosion mechanism(s) is essential in developing an
effective corrosion mitigation strategy. Microbially
induced organic acid attack was identified as a cor-
rosion mechanism in a sweet natural gas pipeline
through trace organic acid analysis and microbio-
logical testing for acid-producing bacteria (APB).
This case study deals with the application of APB
and organic acid monitoring techniques in the eval-
uation of a MIC mitigation program that has been
implemented in a sweet natural gas gathering
system.
Introduction
AEC East, a business unit of AEC Oil & Gas
Partnership, operates in excess of 3100 shallow
gas wells and 3200 km of flowlines on the Cana-
dian Forces Base Suffield military range located
in southeastern Alberta, Canada. The production
gathering and processing of shallow ( ~ 7 0 0m)
sweet gas commenced in 1976 from the Milk River,
Medicine Hat, and Second White Specs forma-
tions. To improve production, all formations were
6.27
CHAPTER 6 (PARTIII)
By J.W. Dusseault and J.H. Schulz
fractured as part of the well completion process.
Surface waters were commonly used as a medium
for carrying the propant (sand) into the formation.
Gas produced from these formations contain less
than 0.2% CO2 and no H2S. The operating pres-
sure of the gathering system has dropped from
3100 kPa in 1976 to less than 700 kPa in 1995.
Corrosion studies conducted on the Suff ield
shallow gas gathering system in 1980 identified
the presence of sulfate-reducing bacteria (SRB) as
a potential failure mechanism. A number of biocide
treatment programs were tried over the years to
control MIC but with little success. The first internal
corrosion pipeline failure was discovered in 1983.
Since that time internal corrosion related failures
have increased in frequency as the system aged.
The biocide treatment program, while appearing
to control planktonic bacteria, was not effective in
mitigating the corrosion that was occurring within
the gathering system.
To determine if corrosion by SRB was still the
dominant corrosion mechanism in the system, a
pipeline failure cutout was forwarded to a metallur-
gical laboratory for analysis. Examination results
pointed toward C02 corrosion as the primary fail-
ure mechanism based on the presence of iron car-
bonate and the pit morphology being indicative of
an acid type of attack resulting from CO2 disso-
lution in the water under system conditions. After
reviewing the system operating parameters, it was
concluded that the C02 partial pressure of 30 kPa
was not a significant factor in causing the degree
6.28 A Case Study-Microbially Induced Organic Acid Attack in a Natural Gas Gathering System

of corrosion damage that was found. A literature

search was undertaken to determine what other
corrosion mechanisms could produce a C02 type
of attack in carbon steel. The search produced sev-
eral that associated organic acid attack
of carbon steel with microbial activity. Samples
of corrosion by-products were removed from the
pitted areas and analyzed for organic acid compo-
sition. Organic acid analysis of the deposits con-
firmed the presence of acetate, butyrate, formate,
lactate, and propionate. Scrapings taken from the
corrosion sites tested positive for the presence of
acid-producing bacteria (APB) in addition to SRB.
The cause of the failures, previously identified as FIGURE 6.25
C02 corrosion, has now been attributed to micro- Example of acid type of attack in the examined south-
bially induced organic acid attack. eastern Alberta, Canada shallow gas production system.
To develop a better understanding of the cor- (See color plates.)
rosion mechanism(s) responsible for the increas-
ing failure rate a total of 44 line failure cutouts in close proximity of methanol injection points
were analyzed. The presence of both APB and (Figure 6.26).
SRB populations were identified in and around A dynamic bioassay evaluation utilizing
the pits where the failures originated. Failure sites Suffield produced fluids and solids was under-
where'SRB were the dominant species took on taken to select a biocide treatment product that
the appearance of isolated pitting (Figure 6.24), would be the most effective in controlling both
whereas APB dominant sites were characterized planktonic and sessile SRB and APB popula-
by a form of acid attack most pronounced in the tions. Results of the bioassay evaluation are
heat-affected zone of the Electric Resistance Weld summarized in Table 6.6 (Laboratory Bioassay
(ERW) (Figure 6.25). A type of attack charac- Results). A series of tests performed by a potential
teristic of oxygen was also observed on failures chemical supplier, to evaluate the use of corrosion
 TABLE 6.6
Laboratory Bioassay Results
1 Hour 5 Hours 24 Hours 48 Hours 168 Hours
Product Planktonic Sessile Planktonic Sessile Planktonic Sessile Planktonic Sessile Planktonic Sessile
Numbed") SRB APB AER SRB APB AER SRB APB AER SRB APB AER SRB APB AER SRB APB AER SRB APB AER SRB APB AER SRB APB AER SRB APB AER Total
1 9 7 7 9 1 0 1 0 9 9 9 1 0 8 8 8 9 10 10 10 10 8 10 10 8 10 9 7 10 10 8 10 9 271
2 1 0 0 8 9 7 0 0 0 6 8 8 0 0 0 6 6 6 0 0 0 3 8 8 0 0 0 3 9 5 101
3 0 1 0 6 6 5 0 1 1 9 5 5 1 0 1 1 9 5 4 1 0 0 2 1 0 1 0 3 0 0 3 1 0 1 0 118
4 1 2 1 6 6 5 1 1 1 8 5 5 1 0 2 2 5 5 5 0 1 1 5 5 5 1 0 0 3 5 3 100
5 8 5 4 9 5 5 9 10 9 8 10 10 8 9 9 10 10 10 10 9 9 5 10 10 9 8 9 5 9 1 0 251
6 9 9 8 9 9 9 7 8 9 9 1 0 1 0 8 9 9 10 10 10 I 0 8 9 9 9 9 1 0 6 9 8 9 9 269
7 9 8 9 1 0 9 9 8 7 7 6 1 0 1 0 6 1 0 1 0 6 7 7 5 8 3 3 8 5 3 0 0 3 3 3 192
8 3 2 1 8 8 5 1 1 0 7 8 7 6 3 1 6 5 6 0 3 0 5 5 5 0 3 0 5 9 3 116
9 9 8 8 4 9 9 6 9 9 1 0 1 0 9 10 6 6 1 0 7 7 5 1 1 9 6 6 0 0 0 3 3 3 183
10 9 1 0 8 10 9 9 7 9 7 8 1 0 9 9 9 9 10 10 10 6 1 0 5 8 7 3 0 0 5 3 3 203
11 9 9 9 1 0 5 5 9 9 10 9 10 10 9 9 8 10 10 10 4 3 2 5 8 9 3 0 0 5 3 3 205
12 7 6 7 1 0 5 5 9 8 8 9 9 9 9 6 10 9 10 10 9 1 1 9 8 8 4 0 0 8 5 5 204
13 9 9 9 4 8 8 8 9 9 5 8 8 8 8 6 5 6 5 10 7 1 0 5 5 5 1 0 9 6 5 9 9 222
14 8 7 9 9 5 4 8 8 1 0 8 5 5 8 8 6 9 1 0 1 0 8 9 1 0 5 8 9 9 9 6 5 8 9 232

NOTE: A value of 10 denotes maximum biocide effectivness; a value of 0 denotes complete ineffectiveness.
Comments:
SRB = Sulfate-Reducing Bacteria
APB = Acid-ProducingBacteria
AER = Aerobic Bacteria

(A) Product Chemistry:

No. 1 = Diamine Salts,
No. 2 = Silicon Defoamer,
No. 3 = Caustic Solution of Surfactant Salts,
No. 4 = Water Soluble, Caustic Cleaner,
No. 5 = Blend of Aldehydes,
No. 6 = Amine Salt,
No. 7 = AminelAcid Oil Soluble Corrosion Inhibitor,
No. 8 = Silica-Based Antioam,
No. 9 = Quat. "A" Surfactant and Aldehyde "A,
No. 10 = Quat. "B"Surfactant and Aldehyde "A*,
No. 11 = Surfactant Blend + Aldehyde "A",
No. 12 = Quat.,
No. 13 = Cocodiamine,
No. 14 = Quat. Diamine Blend
6.30 A Case Studv-Microbiallv Induced Oraanic Acid Attack in a Natural Gas Gathering System
inhibitors for corrosion control, revealed that cor-
rosion inhibitors had little effect on controlling mi-
crobially induced underdeposit acid attack on steel
coupons. These findings support the work of Pope
et aL7 on the effectiveness of biocides and corro-
sion inhibitors in the control of microbiologically
influenced corrosion. Products that performed the
best generally had higher surfactant tendencies,
indicating their ability to penetrate biofilms and de-
posits. The top two performing products were se-
lected for an extended field evaluation.
Production losses resulting from excessive
foaming of the treatment products in the flowlines
were also an important consideration. The majority
of the chemical formulations tested exhibited mod-
erate to high surfactant tendencies when mixed
with the produced water and agitated (Table 6.7).
Provisions would have to be made for the installa-
tion of anti foam injection points upstream of the
produced water separation facilities to prevent sys-
tem upsets.
Field Evaluation
Baseline Monitoring
The methodology of the field test was to evalu-
ate each biocide’s ability to control microbial activ-
ity against slightly different water chemistries and
produced solids. General corrosion monitoring
through the use of coupons and Electrical
FIGURE 6.27
Schematic of biofilm spool assembly as utilized for monitoring of the noted facility.
TABLE 6.7
Biocide Foaming Tendency Evaluation
Product Foaming Tendencies
Number (General Observations)
1 Moderate to High
2 Low
3 Low
4 Low to Moderate
5 Moderate to High
6 Moderate to High
7 Moderate
8 Low
9 Moderate to High
10 Low
11 Low
12 Low
13 High
14 High
Resistance (ER) probes was not included in the
evaluation. Microscopic examination of the bioplug
surface provided a means to quantify the corrosion
damage relative to each biocide tested and sys-
tem chemistries. Control of product foaming in the
system through the application of anti-foam chem-
icals was also evaluated. To provide a means of
monitoring microbial activity, nine biofilm spools
(Figure 6.27) were installed in the Suffield gas
gathering system in 1991 (Figure 6.28). Selec-
tion of the biofilm spool locations was based
on previous failure history, low lying areas that
A Case Study-Microbially Induced Organic Acid Attack in a Natural Gas Gathering System
FIGURE 6.28
Biofilm spool locations (red dots) at this southeastern
Alberta, Canada shallow gas production system. (See
color plates.)
would trap water and solids production, and
accessibiIity.
Prior to chemical treatment of the E, A l , and
B1 areas in the spring of 1992, a baseline mi-
crobial survey was carried out by retrieving four
biofilm studs from each of the nine spools and an-
alyzing for bacteria counts. Two of the four studs
were analyzed for organic acids while scrapings
taken off the remaining two studs were placed
into 40 ml of transport media to stabilize the bac-
teria entrapped in the biofilm, until they could
be analyzed. Field tests on APB and SRB con-
tamination were conducted within three hours of
sampling by serial dilution in triplicate. Bacterial
counts were determined by most probable num-
ber (MPN) calculation. A similar procedure was
followed for testing the produced water samples
for planktonic bacteria counts. An adenosine-5’-
phosphosulfate (APS) based reductace test for
SRB detection and a hydrogenase test were con-
ducted at the same time as the field APB and SRB
tests, using the same sessile bacterial sample.
Follow-up lab testing of SRB (modified
Postgate), APB (modified phenol red broth), and
Aerobic bacteria (tryptic soya media) by serial di-
lution and MPN was completed within 24 hours of
sampling. An organic acid analysis (using capillary
electrophoresis (CE) evaluation procedures) was
conducted on two of the studs, to identify acids
6.31
TABLE 6.8
Summary of Organic Acids
(Free Acid Form)
1 oxalate
2 formate
3 citrate
4 tartrate
5 succinate
6 acetate
7 glycolate
8 propionate
9 lactate
10 butyrate
that tend to be involved in corrosion processes at-
tributed to acid-producing bacteria. A list of these
organic acids in their free acid form is presented
in Table 6.8.
To ensure the consistancy and reproducability
of the microbiological monitoring data, produced
fluid samples were cultured within 2 hours of sam-
pling in the field and 24 hours in the laboratory.
Results of the laboratory and field baseline mon-
itoring data for the sessile SRB and APB popu-
lations (Table 6.9) showed that the time lag had
little effect on the quality of data. Field-measured
SRB populations were within one log factor of the
laboratory-measured data seven out of nine times
while the APB data were within one log factor six
out of nine times. While a great effort was made
to ensure the quality of the field cultured bacteria
data during the initial pilot test, it was not reason-
able to assume that the same attention could be
given over an extended field test. To maintain data
consistancy the field testing for microbially activity
was discontinued in favor of the controlled labo-
ratory environment. The APS reductase test and
the hydrogenasetests were dropped after the base
line monitoring interval since their sensitivity to low
levels of bacterial contamination did not meet the
requirements of the evaluation.
Biocide Application
The first application of biocides occurred in
the spring of 1992. Field treatment volumes
6.32 A Case Study-Microbially Induced Organic Acid Attack in a Natural Gas Gathering System

TABLE 6.9
Baseline Sessile Monitoring Data

Acid-Producing Bacteria Sulfate-Reducing Bacteria

(celIs/cm2) (cells/cm*) APS Reductase
TedA) Hydrogenase
Location Field Laboratory Field Laboratory (cells/cm2) TedA)
A1-1 >4.4+E5 1.6+E2 8.O+E1 6.O+E3 BDL@) +(W
A1-7 1.7+E2 tl.2+E2 3.7+E2 1.7+E3 BDL -03
A1 -9 >4.4+E5 1.8+E7 1.8+E3 9.6fE3 BDL -
E-4 8.4+E4 6.O+E5 1.8+E4 3.O+E4 1.0+E3(C) nta
E-7 6.O+E2 1.6+E2 3.7+E2 8.4+E2 1.O+E3 -
E-8 6.O+E3 tl.2+E2 9.3+E1 < I .2+E1 1.O+E3 nta
B1-1 3.7+E2 < I .2+E2 <1.2+E1 4.8+E3 nta nta
B1-3 1.8fE2 < I .2+E2 tl.2+El 1.6+E2 1.O+E3 -
B1-5 3.7+E3 tl.8+E9 1.7+E2 < I .2+E2 1.O+E3 -

(A)TheAPS reductace and hydrogenasetests were only performed in the field.

(@BDL= below detection limit.
reading of 1.O+E3 on the APS reductace test is at its practical detection limit.
(D)"+'' = low level of hydrogenase present.
(E)''-*' = no measurable hydrogenase present.

were based on laboratory test data, supplier- into the flowline would simulate a type of con-
recommended dosage information, and water tinuous biocide injection for longer term con-
production at the biofilm spool locations. With the trol (Figure 6.29). This type of treatment was
average shallow gas well water production in the limited to aforementioned locations because of
range of 0 to 0.1 m3 per day, it was considered nec- pressure-drop concerns in the small-diameter pro-
essary to dilute the neat chemical with water to en- duction strings (18 mm diameter) as a result of
sure adequate coverage and reduce the potential product foaming.
of corrosion due to high chemical concentration.
A biocide application schedule is presented in
Table 6.10 showing treatment products (nos. 1, 6, TABLE 6.10
and 13), volumes, and locations. Biocide Application Schedule
With the exception of location #5 in the B1
area (treated Sept. 1993), no chemical treatments
were performed on the biofilm spool monitor- Location
ing locations until Summer/Fall of 1994. Product A1 -1
no. 13 was removed from the study after the initial A1 -7
treatment because of foaming problems and rela- A1 -9
tively poor performance. E-4
E-7
In 1994 the biocide application method was
E-8
changed for the biofilm spool monitoring locations B1-1
whereby chemical batch treatments were injected B1-3
downhole rather than into the flowlines. By inject- B1-5
ing downhole it was reasoned that the biocide
cA)TheSpring and Fall 1992 Biocide applications were into the flowline.
would be targeted at the source of microbial @)The1994 and 1995 biocide applications were down the well bore.
contamination and that the production of fluids
A Case Study-Microbially Induced Organic Acid Attack in a Natural Gas Gathering System 6.33

FIGURE 6.29
Schematic showing a typical downhole chemical application.

Biocide Residual Testing residuals was performed in the laboratory by

Biocide residual testing of the produced wa-
ter, at the biofilm spool assemblies, was per-
formed on samples from monitoring Intervals #7
and #8 in an effort to correlate microbial activ-
ity and organic acid production on the biofilm
plugs with treatment dosages and frequency. By
accurately measuring the biocide residual at the
monitoring locations, it was possible to deter-
mine the relative effectiveness of the two prod-
ucts in a field setting. Measurement of the biocide
way of a capillary electrophoresis system. Re-
sults of the biocide residual study are presented in
Figure 6.30.
Monitoring Results
Microbiological monitoring was carried out at
nine biofilm spool locations over a two-year period.
These sites were subjected to sessile and plank-
tonic testing for acid-producing, sulfate-reducing,
6.34 A Case Study-Microbially Induced Organic Acid Attack in a Natural Gas Gathering System

-
Product No. 6 Residual Summary
Pilot Test Study
Product No. 6 (mglL)
1000000

+A1-7,1 well (Distance from well: 150m, Topography: Elevation drop to spool),6L
+Al-9, 1 well (Distance from well: 125111, Topography: Elevation drop to spool), 6L
100000 r C E - 4 , 1 well (Distance from well: 22m, Topography: Flat), 4L
+E-7,2 wells (Distance from wells: 55 8 900m, Topography: Elevation rise/drop to spool), 6L

10000 well turned on (A1-7)

1000

100

\ well shut in (Al-7)

0 20 40 60 80 100 120 140 160 180 200
Interval (days) -May 26 to November 2,1995

FIGURE 6.30
Product No. 6-Chemical residual (pilot test study).

and aerobic facultative bacteria populations. Test- Interval #5 = July/August 1993 (4th post-
ing also included trace organic acids analysis treatment evaluation)
and an examination of the bioplugs for corrosion Interval #6 = ApriVJune 1994 (baseline for
damage. Monitoring intervals were as follows: downhole treatment evaluation)
Interval #7 = September 1994 (lst post-
Interval #1 = March 1992 (baseline for treatment evaluation)
flowline treatment evaluation)
Interval #8 = December 1994 (2nd post-
Interval #2 = ApriVMay 1992 (lst post- treatment evaluation)
treatment evaluation)
Interval #9 = May 1995 (baseline for down-
Interval #3 = June/July 1992 (2nd post- hole treatment evaluation-biocide
treatment evaluation) residule study)
Interval #4 = November/December 1992 Interval #10 = June 1995 (lst post-
(Yd post-treatment evaluation) treatment evaluation)
A Case Study-Microbially Induced Organic Acid Attack in a Natural Gas Gathering System 6.35

Chemical Performance Evaluation

Bacterial b v e l (mpnlrm?)
-
(APBISRB Levels Lab Data, 1992-1995)
I.OE+OB

1.OE+06

1.OEM5

1. O E M

1.OEM3

1.OEM2

1.OEW
Ai-1 APB Al-1 SRB A?-7APB Ai-7 SRB Al-9APB A14 SRB
LocatlanlElscteriaIGroup

FIGURE 6.31
Chemical performance evaluation (APB/SRB levels-lab data, 1992-1 995): Part I.

Interval #11 = July 1995 (2nd post-
treatment evaluation)
Interval #12 = September 1995 (3rd post-
treatment evaluation)
Interval #13 = November 1995 (4th post-
treatment evaluation)
A summary of the monitoring data is presented in
Figures 6.31 through 6.34.
Please note, the reason why five of the moni-
toring intervals are stated as having occurred over
a period of two months, is because some sites in
three different gathering systems examined (E, A1 ,
and B1) were subjected to monitoring during the
first month in that interval, while others sites were
examined during the second month of the interval.
Also, biofilm spool locations Nos. 8 and 9 were not
monitored after May 1994 as the wells had watered
off and gas production ceased.
/nterva/#l (March 1992) entailed a baseline
microbial survey of all nine biofilm spool loca-
tions. Results of this survey provided a basis for
evaluating the effectiveness of the three biocide
treatment chemicals. Microbiological contamina-
tion levels were determined to be in the order of
lo2 to l o 9 cells/cm2 for APB, while SRB levels
tended to be 10' to l o 4 cells/cm2. Organic acid
levels ranged from a low of 5 pg/cm2 to a high of
4214 pg/cm2,
Interval #2 (AprWMay 1992) constituted a
first look at the effect and success of applied
6.36 A Case Studv-Microbiallv Induced Organic Acid Attack in a Natural Gas Gathering Svstem

Chemical Performance Evaluation

Bacterial Level (mpnlcm?)
-
(APBISRB Levels Lab Data, 1992-1895)
I.OE+M
Bars may indicate values that are actually below the test detection limit
Samples not cdlected from E-8 for the 6/92 intend

I.OEM7

I.OE+O6

11/92
1.OE+05

I.OE+04

l.OEM3

1.OEM2

I.OEM1

1.OE+OO
E-4 APB €4SRB E-7 APB E-7 SRB E-8 APB E-8 SRB
Location/BacterirlGrwp

FIGURE 6.32
Chemical performance evaluation (APB/SRB levels-lab data, 1992-1 995): Part II.

biocide treatments. The sessile biological mon-
itoring data for that interval clearly indicate the
dramatic decrease in bacteria populations at mon-
itoring sites. Levels of organic acids remained ex-
tremely high in the case of those monitoring sites
subjected to chemical treatment product no. 1.
Organic acid levels for chemical treatment prod-
uct no. 6 were found to be much lower at that
time.
lnterval #3 (June/July 7992) continued to
show microbiological contamination levels, as
pertaining to APB and SRB populations, much
lower than those encountered prior to the biocide
application. Organic acid levels, particularly for
product no.1, where very high levels had been
noted, had also dropped off significantly.
lnterval #4 (NovembedDecember 1992) sho-
wed a leveling off to a slight increase in APB
and SRB populations and organic acid pro-
duction for biofilm spool locations treated with
products nos. 6 and 13. Locations treated with
product No. 1 showed slightly better resutls in
two out of three cases. Microscopic examination
of the biofilm plugs revealed a higher level of
etching, edge attack, and pinpoint pitting in the
locations where products nos. 1 and 13 were
applied.
lnterval #5 (Ju/y/August 1993) indicated that
microbiological contamination of the biofilm plugs
tended to be relatively equal to those levels noted
during the Nov./Dec. 1992 interval, although, the
B1-5 (product no. 1) and the B1-3 (product no. 13)
A Case Study-Microbially Induced Organic Acid Attack in a Natural Gas Gathering System 6.37

Chemical Performance Evaluation

Yicrogramrlsquare cm
-
Field Monitoring Data Organic Acid Levels (A1 Area)
10000

I000

100
n
+Al-I
+A1-7
+AI-9

10

1
3/92 4/92 6/92 11/92 7/93 5/94 9/94 12/94 5/95 6/95 7/95 9/95 11/95
MonthNear

FIGURE 6.33
Chemical performance evaluation (field monitoring data-organic acid levels, "A1 area").

locations showed significantly higher concentra-
tions. Corrosion damage of the biofilm plugs ap-
pears to correlate with the bacteria activity levels,
which is based on APB and SRB population counts
and organic acid concentrations.
Interval #6 (Apri//June 7994) provided a base-
line to measure the performance of the 1994
downhole biocide application program. It also pro-
vided a long-term microbiological assessment of
the biofilm plugs since it had been two years
since the last biocide treatment. Monitoring re-
sults seemed to indicate that the period between
treatments was too long and opportunistic bac-
teria populations had increased, as the result
of the absence of any significant quantities of
biocide.
With the exception of E7 and E8 locations,
the measured APB and SRB populations and or-
ganic acid concentrations were lower than those
for Interval #5. Produced fluids, recovered from
the biofilm spools, were analyzed for residual bio-
cide concentrations to determine if the biocide was
still present and any effect it would have on the bio-
plug data. Locations where biocide residuals were
identified (Bl-1 and B1-5) indicated significantly
lower AER, APB, and SRB population levels,
organic acid concentrations, and corrosion dam-
age of the bioplugs. The presence of biocide
residuals at these locations was attributed to very
low gadwater production rates. Consequently, the
biocide was not carried down the line but was al-
lowed to sit in the vicinity of the bioplug spool
6.38 A Case Study-Microbially Induced Organic Acid Attack in a Natural Gas Gathering System

................................................................... .......... .... ............ ............ ......... ........ ... ............. ....
1000
t ...................... ............. .... .....
1

3/92 4/92 6/92 11/92 7/93 5/94 9/94 12/94 5/95 6/95 7/95 9/95 11/95
Monthwear

FIGURE 6.34
Chemical performance evaluation (field monitoring data-organic acid levels, “E” area).

where an indefinite contact time was primarily a downhole biocide application in June/August
responsible for the MIC control. Once again it 1994. At this time only two of the three monitor-
is interesting to note that despite the two-year ing areas were examined, specifically the A1 and
contact time there was still a viable bacteria E areas. There was no significant benefit in at-
population. taining monitoring data from the B1 area for this
For record purposes, bioplugs removed during cycle, as there was little production from the wells
the ApriVJune, 1994, monitoring Interval #6 were fitted with bioplug spools (Bl-1, B1-3, and B1-5).
new bioplugs, installed to replace bioplugs utilized Product no. 1 chemical treatments were applied at
during previous monitoring intervals. Accordingly, the A1 -1, A1 -7, and A1 -9 locations; while locations
bioplugs from Interval #6 can be considered as E-4, E-7, and E-8 were subjected to product
baseline monitoring samples, while bioplugs re- no. 6.
moved in early September, 1994, Interval #7 were Residual biocide concentration in the E sys-
monitoring specimens that had been exposed to a tem, as measured at the bioplug spools, ranged
recent biocide treatment. from 24 to 63 ppm (product no. 6), yet the
Interval #7 (September 7994) was the first bacteria populations remained at pre-treatment
post-treatment evaluation of the bioplugs following levels or slightly higher. The same applies for the
A Case Study-Microbially induced Organic Acid Attack in a Natural Gas Gathering System
A1 system that was treated with product no. 1 as far
as bacteria populations are concerned; however,
the biocide residual concentrations were below
detection limits. Lower gas production rates in the
A1 area may not have carried the biocide from
downhole to the flowline in time to be detected
by the monitoring interval. Inspection of the or-
ganic acid analysis data shows that in the case of
product no. 6 treatment sites there were low levels
of organic acids, reflecting the apparent long-term
filming capabilities of the biocide and its inherent
ability to reduce organic acid concentrations. The
general condition of the bioplugs was observed to
be better in the E area, which was treated with
product no. 6, as compared to the A1 area, which
was treated with product No. 1.
Interval #8 (December 7994) was the last
monitoring point of the 1994 downhole biocide
evaluation. Biocide residual levels ranged from 10
to 50 ppm for product no. 1 in the A1 area, while
biocide residuals for the E area dropped below
detection limits. Bacteria populations were signifi-
cantly reduced in both areas since Interval #7. The
condition of bioplugs that were exposed to prod-
uct no. 6 exhibited a superior surface condition as
compared to those subjected to product no. 1. Pit-
ting corrosion attack (primarily affecting those bio-
plugs that were treated with product no. 1) tended
to be concentrated along the edge of the bioplug
surfaces, whereas the center areas of these bio-
plugs tended to be subject to more uniform cor-
rosion attack. As noted in Interval #7 the organic
acid concentrations were slightly higher for the bio-
plugs in the A1 area that were treated with product
no. 1.
Produced water samples were recovered from
five of the nine biospool locations and analyzed
for planktonic SRB, APB, and AER concentrations
and biocide residuals. Bacteria populations in the
water ranged from one to three log factors higher
than those populations measured in the biofilm;
also, the biocide residual was slightly higher in the
biofilm than in the bulk fluid. This would suggest
that bacteria populations downhole are increas-
ing due to low biocide residual levels while sessile
populations remain constant as a result of the bio-
cide filming characteristics.
6.39
Interval #9 (May 7995) provided a baseline
for the 1995 downhole chemical residual pilot test
program. A marginal increase in the general bacte-
ria contamination levels was observed, suggesting
that the summer of 1994 biocide treatment pro-
gram benefits are beginning to diminish. The gen-
eral condition of the bioplugs removed at this time
have, in overall terms, not changed significantly
since the December 1994 monitoring interval. Cor-
respondingly low organic acid levels were noted,
although slight increases were observed at points
where an elevation in active bacteria populations
had occurred. The 1994 downhole biocide applica-
tion program has appeared thus far to yield more
long-term benefit than the previous flowline appli-
cation procedures.
+
Interval #70 (June 7995) at D 19 days (D =
0 interval was May 26, 1995) was the first post-
treatment evaluation. All biofilm spool monitor-
ing locations were treated with product no. 6, a
cocodiamine-based biocide. An increase in ses-
sile APB levels was observed at the A1-7, E-4,
E-7, and E-8 biofilm spool locations while the SRB
levels remained low. It should be noted that an in-
crease in planktonic APB levels was also noted. An
increase in planktonic bacterial levels after a down-
hole treatment is consistant with what was found
on other wells outside of this study. It appears that
the surfactant qualities of the biocide is responsible
for dislodging a large amount of downhole debris,
with attached biofilm matter, into the flowline. The
biocide may not be entirely effective in penetrat-
ing the produced biofilm matter (clays and other
produced solids can tie up the cocodiamine-based
biocide) during the contact time interval thereby
causing higher bacterial counts. A drop in the or-
ganic acid levels was noted for the E-4, E-7, and
E-8 locations while the A l - 1 and A1-7 locations
recorded a slight increase. Biocide chemical resid-
uals tended to peak ranging from a (low of 30 mg/L
to a high of 100,000 mg/L, with an average of
5,000 mg/L) several days prior to the bacterial
sampling on D = 19.
+
lnterval # 7 7 (July 7995) at D 51 days re-
vealed a general decrease in sessile bacteria
population densities, particularly APBs. In cases
where control of sessile APB populations is noted,
6.40 A Case Study-Microbially Induced Organic Acid Attack in a Natural Gas Gathering System
corresponding organic acid levels were below
detection limits. At locations where somewhat
higher APB populatioins were recorded (but still
below pre-treatment levels), some organic acids
are also detected. SRB populations generally
tended to be far lower than APB populations.
The gradual deterioration of the plug surfaces
appears to have slowed down, possibly due to
the filming characteristics of the treatment chem-
ical (product no. 6). Biocide residual measure-
ments averaged 1000 mg/L at the time of bacterial
sampling.
Interval #72 (September 7995) at D +
111 days showed sporadic increases in sessile
bacteria contamination levels along with signifi-
cant increases in both APB and SRB planktonic
populations. Organic acid levels were found to
be low but on the increase in three of the six
monitoring locations. Four of the six monitoring
locations showed biocide residual levels in excess
of 250 mg/L.
Interval#73 (November 7995) at D+182 days
showed a general decrease in APB sessile popu-
lations at all six biofilm spool monitoring locations
while SRB sessile populations remained constant
at zero or the detection limit. The E-8 and A1-9
monitoring locations recorded a drop in organic
acid production while the remaining four locations
showed an increase. Biocide residuals at the mon-
itoring locations ranged from 40 to 450 mg/L.
Discussion of Results
The field bioplug monitoring data correlated
very well with the laboratory bioassay results as
far as bacteria population control is concerned.
Product nos. 1 and 6 performed equally well with
product no. 13 coming in third (Table 6.1 1). This
once again confirms the importance of a product
bioassay evaluation prior to field application.
What the bioassay evaluation did not show
was the degree to which product no. 6 was able to
reduce serious deterioration of the bioplug surface
in the field. The general corrosion deterioration of
the examined bioplugs, in the case of product no. 1,
TABLE 6.11
Product Performance Summary
Product Product Product
No. 1 No. 6 No. 13
SRB 3 2 1
APB 3 2 1
AER 2 3 1
Organic Acid 3 2 1
Plug Condition 1 3 2
Total 12 12 6
exceeded the corrosion deterioration of the bio-
plugs that had been subject to treatment with
product no. 6. This is a critical finding and clearly
stresses the importance of not only monitoring the
relative biocidal effect of a given treatment product
(in terms of its ability to reduce or eliminate bacte-
ria contamination) but of also monitoring potential
corrosion effects of field-selected treatment
products.
The surfactancy of the treatment product was
shown to have an effect on its ability to penetrate
the bioplug and control bacteria populations as
well as organic acid concentrations. Product nos.
1 and 6 performed very well on sessile bacteria
populations but product no. 1 gave slightly better
results on organic acid reduction. Comments from
field operations staff indicated that while both prod-
uct nos. 1 and 6 foamed in the system, the ten-
dency of product no. 1 to foam was greater.
A good correlation was found between bacteria
and organic acid levels on the bioplugs. Decreases
in bacteria population levels were followed by a
decrease in measured organic acids. Increases in
bacteria levels brought a corresponding increase
in organic acids. In terms of the treatment prod-
ucts’ ability to reduce organic acid concentrations
on the bioplug plugs, product no. 1 performed sli-
ghtly better than product no. 6 during the course of
the monitoring period. It should be noted that the
performance of product no. 6 was superior over the
last two monitoring intervals; however, the scoring
methodology does not indicate this fact. The per-
formance of product no. 13 was a distant third.
A Case Study-Microbially Induced Organic Acid Attack in a Natural Gas Gathering System
In reviewing the general condition of bioplugs
that had been installed at the nine monitoring
locations during the period of 1992 to 1995, it
was noted that the majority of corrosion deposits
tended to accumulate along the edges of the in-
dividual bioplugs next to the bulk fluids. These
outer edge areas also tended to be most severely
affected by any potential corrosion process that
had occurred on these plugs. This might sug-
gest, as referenced in Pope et al.,’ that the early
phases of a corrosion process in a system, such
as the Suffield production system, may be most
affected by the presence of active microbial popu-
lations, whereas nonbiological reactions may dom-
inate corrosion thereafter. Biocides with significant
corrosion inhibition qualities can yield much more
surface metal protection by controlling the dam-
age caused by microbial activity as in the case of
product no. 6.
Conclusions
1. It is important to realize that microbio-
logically influenced corrosion can take
on forms resembling other types of
attack, such as C02 corrosion.
2. Present data show that the selection of
an effective biocidal cleaning product,
first through laboratory selection pro-
cedures and then through careful pilot
monitoring at the field level, is critical.
3. The inherent chemistry of the applied
biocidal treatment agent to kill bacte-
ria is important, but the ability of that
cleaning compound to penetrate accu-
mulated surface deposits effectively and
control microbial activity at the metal
surface is more critical.
4. Control of organic acid production can
be achieved through the application of
an effective biocide treatment agent.
5. Monitoring the corrosion damage of
bioplugs can be useful in determining
6.41
the effectiveness of biocides in the pre-
vention of nonbiological corrosion while
microbial activity is being brought under
control.
6. A corrosion evaluation of biocide chem-
icals can be useful in screening out
agents that would have a detrimental
effect on the gathering system flow-
lines and, at the same time, identifying
which products provide the best long-
term corrosion protection. This evalu-
ation must be carried ’out at system
operating conditions with respect to
temperature, pressure, water chemistry,
and anticipated chemical treatment con-
centration.
Acknowledgments
The authors would like to thank the manage-
ment, technical, and field staff of Alberta Energy
Company for their ongoing support of this
study. The support of all technical staff, par-
ticularly Michael Sheppard, at the facilities of
Bio-Chem Consulting Services Ltd. in Calgary,
Alberta, Canada is also gratefully acknowledged.
References
1. J.H. Schulz, J.W. Dusseault, “Microbially Induced
Organic Acid Attack in a Sweet Natural Gas
Gathering System” SPE 24862 (Washington, DC:
October 4-7, 1992.)
2. O.C. Dias and M.C. Bromel, “Microbially Induced Or-
ganic Acid Underdeposit Attack in a Gas Pipeline,”
MP April (1990): 53-56.
3. D.H. Pope, et al., “Microbiologically Influenced Cor-
rosion in the Gas Industry,” Pipeline 62, 5(1990):
8-9
4. R.A. Day and J.R. Frank, “Effect of Microbiologi-
cally Influenced Corrosion on Underground Steel
Gas Piping,” Publication No 87-DT-76 (Chicago, IL:
Gas Research Institute, 1987), pp. 112-1 13.
6.42 A Case Studv-Microbiallv Induced Oraanic Acid Attack in a Natural Gas Gatherina System

5. M. Walch and R. Mitchell, “Biological Aspects of Corrosion,” CORROSION/88, Paper no. 79

Corrosion of Offshore Structures,” Sweden Trade
Fair Foundation International Offshore and Ma-
rine Technology Conference, Proc. Session No. C1
(Gothenburg, Sweden: 83.03.01-04, 1983), 11 pp.
6. D.H. Pope, et al., “Organic Acid Corrosion of Carbon
Steel: A Mechanism of Microbiologically Influenced
(Houston, TX: NACE, 1988).
7. D.H. Pope, et al., “Laboratory and Field Tests
of Efficacy of Biocides and Corrosion Inhibitors
in the Control of Microbiologically Influenced
Corrosion,” CORROSION/90 (Houston, TX: NACE,
1990).

MIC in the Power Industry
Introduction
Microbiologically influenced corrosion (MIC)
has compromised the structural integrity of pip-
ing and numerous components in nuclear and
fossil-fueled power plants. Cooling water and ser-
vice water systems in these plants have been
designed with minimal corrosion allowances-a
reasonable approach for corrosion resistant ma-
terials exposed to environments that would nor-
mally be considered benign. Microbial influences
can cause localized corrosion, often at rates one
or more orders of magnitude greater than the ex-
pected general corrosion rates, for copper-based
alloys, carbon steels, and stainless steels. The flow
capabilities of some carbon steel lines have also
been affected as massive quantities of corrosion
products and deposits have seriously reduced the
pipe diameters, in some cases leading to complete
blockage.
Microbiologically influenced corrosion, the in-
teraction of biological activity with corrosion pro-
cesses, is a significant cause of degradation of
piping and heat transfer surfaces in such cool-
ing water systems. MIC can produce through-wall
penetration of piping and heat exchanger tubing
as localized corrosion, at rates 10 to 1000 times
more rapid than those normally encountered. As
noted in A Practical Manual on Microbiologically
lnfluenced Corrosion,' MIC has been observed in
essentially all raw waters including soft and hard
fresh waters, brackish waters, and seawater.
The impact of MIC on the operating and main-
tenance costs of power plants can be significant.
Those costs include costs of replacement power,
increased inspection, repairs and replacements,
7.1
CHAPTER 7
By GJ,Licina
and mitigation activities. Whenever plants must
be shut down for cleaning or repairs, the costs
of replacement power canbe extremely high. For
example, downtime for large nuclear units is of-
ten of the order of $1,000,000 per day. Similarly,
repairs and replacements of service water sys-
tems, part of the infrastructure of a power plant,
can be costly. Several large nuclear units have
repaired or refurbished their service water sys-
tems. Full system replacement costs are of the or-
der of $30,000,000 per unit; partial replacements
or weld overlay repairs cost $100,000 or more.2
Costs for biocide treatment include the cost of the
treatment chemical(s), delivery systems, monitor-
ing, discharge permits, and training. The annual
cost of mitigation can be $1,000,000.
Microbiologically influenced corrosion in nu-
clear plants has been the subject of commu-
niques from regulatory agencies and industry
organizations.= NACE International, the Chem-
ica! Processing Industry, and the Electric Power
Research Institute (EPRI) have sponsored a num-
ber of publications on MIC in nuclear plants and
fossil-fired plants7-15
Competing Requirements
Economic pressures force plant operators to
continually maintain or improve plant availability.
Unplanned downtime, the result of MIC or other
degradation mechanisms, cannot be tolerated.
Those same economic pressures dictate strict
controls on the costs of mitigation activities. Thus,
plant operators must maintain improved levels of
MIC control at lower operating cost, often with
less staff. In addition, restrictions on effluents are
7.2 MIC in the Power Industry

continually tightening. These factors make plant Once-Through

maintenance an increasingly challenging job.
Water treatments to mitigate MIC and biofilms ------ -
are expensive in terms of chemical delivery intake
systems, training, permits, and the chemicals
Plant Optional
themselves. Environmental requirements on dis- Heat Cooling
Tower
charges have become increasingly restrictive.
Over-treatment of water thus carries a double
penalty as the cost of the chemical is high and as-
Discharge
sociated penalties for excessive discharge ensue.
The propensity for MIC and biofouling in nuclear
and fossil plants and the costs of repairs indi-
cates the importance of improved biofilm monitor- Corrosion and Corrosion Control
ing methods. COOLING SYSTEM DESIGN
Open Recirculating
Background
The primary process water in power plants, the
boiler water in fossil-fired units or reactor coolant Makeup
system water in nuclear units, is virtually always a Water

treated water that starts from a high-purity dem- I -' '-1 Air Condenser
ineralized water, to which specific chemicals are J
added for the control of deposition and corrosion.
When the plant is in operation, the boiler water wn
or reactor cooling water also is boiled or raised to
a very high temperature (>25OoC) at which mi-
Closed Recirculating
crobes will not flourish and will typically be de-
stroyed. While MIC has been shown to occur in
high-purity waters,38 the overwhelming majority
of MIC incidents in power plants have been re- I
ported for cooling waters, both treated and un-
treated.
Cooling water loops may be open, where the
cooling water loop and the ultimate heat sink
are continuously exchanging fluid, or closed,
where only a small fraction of water, typically
treated water, is added to the closed cooling
water loop. Open loops are further subdivided
Q Generator

FIGURE 7.1
Heat
Exchanger
To Heat

Schematic illustrations of typical cooling systems.

as recirculating (e.g., with cooling towers) or
once-through. Several examples are provided in
Figure 7.1. All of these system designs have been
subject to MIC damage.7~10~12~13~15 Closed loops
offer the advantage that they can be continuously
treated with biocides, corrosion inhibitors, and de-
posit control chemicals. Once-through systems
are the most difficult to control by chemical meth-
ods since large quantities of treatment chemical
must be used, with the associated cost and envi-
ronmental ~ 0 n c e r n s . l ~
Power plant fire protection systems may be
closed systems, much like fire protection sys-
tems in buildings or on ships, but are often
MIC in the Power Industry
interconnected with service water systems or other
plant auxiliary systems. Unlike most other build-
ings, however, power plants must test their fire pro-
tection systems regularly. In most cases, fire pro-
tection system waters are untreated. MIC in fire
protection systems is much more common when
the system experiences intermittent flow condi-
tions than when the systems remain closed and
experience flow infrequentIy.16
A number of failures in power plants and
other industries have been attributed to MIC, re-
sulting from microorganisms introduced during
h y d r ~ t e s t i n g . ~ As ~ ~the
~ ~ fabrication
’ ~ ~ ~ ~ ~of’ ~a
system or a portion of a plant is completed, the
structural integrity of the systems is verified by
pressurizing the system to a pressure in excess
of the system’s design pressure. Most often, such
tests are done with water available at the time.
Rarely has that water been treated to remove po-
tentially harmful microbes. Often, the system is left
full or partially full of the hydrotest water for months
or years, until the system is ready for operation.
In that period, MIC can dramatically degrade the
system, such that it fails on start-up. Similar effects
have occurred during long shutdowns.20
The focus on MIC in the power industry has
been on nuclear plants. The focus is likely to re-
main there because of
the enormous costs of downtime,
design philosophy,
potential safety implications of failures
and public sensitivity to any and all
degradations at nuclear facilities, and
limiting conditions of operation (LCOs).
Nuclear plants are typically large, base-loaded
units that provide utilities with a steady supply of
clean power. Shutdown of a large nuclear unit, par-
ticularly an unplanned shutdown, requires that the
utility must replace that large quantity of electric
power with electricity generated from older, less
efficient, higher pollution units, or purchase the
power from other sources. The costs of downtime
for nuclear units are of the order of $300,000 per
7.3
day for smaller units and more than $1,000,000
per day for large units. In addition, the costs of re-
pairs to components in a nuclear plant are high.
For example, one utility has spent more than
$55,000,000, including the costs of replacement
power, replacement tube bundles, and inspection,
on critical heat exchangers that were degraded by
MC2’
Key words that describe the design philosophy
for nuclear plants are “diverse and redundant.” The
safe shutdown of the plant, via diverse, indepen-
dent systems, must be assured for an extremely
broad set of conditions. The diverse and redun-
dant approach permits the plant to be shut down
safely, even if a key component or system fails or is
unavailable for service as a result of maintenance
or other activity. This same approach requires that
numerous systems simply sit idly in wet lay-up, in
anticipation of a time when they might be needed
to provide emergency cooling, to remove residual
heat after a normal shutdown, or to cool equip-
ment that operates intermittently. This type of de-
sign requires extremely large and complex piping
systems. Each component or system also has its
redundant or parallel backup system to provide for
the safe shutdown of the plant. This redundancy
adds to the size and complexity of the piping sys-
tems and guarantees that a number of systems
will be kept full under stagnant or near-stagnant
conditions. Periodic testing of the numerous par-
allel or standby systems is required to assure that
the system will provide the required flow if and
when it may be needed. These long periods of
wet lay-up, interrupted by short periods of flow and
the introduction of new and fresh water, provide a
nearly ideal situation for biofilms to form on struc-
tural materials and for MIC to degrade the system’s
integrity.
Safety-related components in nuclear facili-
ties are those components that have a direct im-
pact on the safe shutdown of the plant. Such
safety-related systems are generally designed and
built to more restrictive standards and use more
corrosion-resistant materials to ensure their relia-
bility. Virtually all components in nuclear facilities
have some safety function, such as lube oil coolers
for pumps that support safety-related equipment.
7,4
Failure of even non-safety-related equipment can
ultimately lead to the degradation of safety-related
equipment that would have a measurable influence
on plant shutdown.22 The public’s typical percep-
tion is that any failure in a nuclear facility is related sil plants. When corrosion damage is observed in
to safety. The nuclear industry is appropriately sen-
sitive to that perception.
A part of the nuclear design philosophy is the
limiting condition of operation (LCO) that is asso-
ciated with many of the components in a nuclear
plant, including components that may be degraded
by MIC. The LCO requires that the component not
be out of service longer than a predefined time;
otherwise, the plant must be shut down. Failures
of piping or components or the discovery of unex-
pected fouling that requires an action can initiate
an LCO. The visibility and impact of MIC or other
forms of degradation is greater for a nuclear unit,
where the repair must be completed in a short pe-
riod of time. In other types of power plants, de-
graded components are simply cut out and re-
placed when convenient or are left in a degraded
condition and monitored to track the progress of
the degradation.
A number of examples of MIC in nuclear facil-
ities have been reported. Several of them will be
described in greater detail in the section on Mate-
rials.
Several examples of MIC have also been re-
ported for fossil-fired p l a n t ~ . Bibb, ~ - report-
~ ~ ~ ~ ~ject~ to~ general
ing on experience with MIC in the power genera-
tion industry in South A f r i ~ a , ’ ~noted
~ * ~that larger some tubercles. While the presence of tubercles
plants appeared more susceptible to MIC failures
because of the delays between hydrotest and
operation. She also noted apparent correlations
between MIC and the nutrient levels in surface wa-
ters (e.g., from chemical fertilizers) and with poorer
water quality (e.g., accompanying drought). Fos-
sil plants probably report MIC failures less often
than do nuclear facilities for several reasons. In
general, the turnaround times from construction
and hydrotest to operation is less, leaving less op-
portunity for extended or poor wet lay-up. Further,
far fewer systems in fossil units are as suscepti-
ble as their counterparts in nuclear units, which
are kept in wet lay-up conditions over the major-
ity of their lives, coupled with periodic operability
MIC in t h e Power Industry
demonstrations. The enormous time pressures ex-
erted by LCOs and stringent requirements for re-
porting events in nuclear units may also yield a
smaller number of MIC diagnoses reported for fos-
noncritical systems in a fossil plant, the damage
is repaired and the system brought back into ser-
vice. In a nuclear unit, removing that same system
from service may not be nearly as simple. When
degradation is observed, considerable resources
are brought into play to diagnose the problem and
correct it.
Materials
Steels and Cast Irons
Steels and cast iron are most often used for
piping, vessels, structures, and tanks. In addition
to concerns with MIC and other forms of corrosion
on internal surfaces, these components, especially
large-diameter pipes, are often buried, resulting in
concerns with MIC and other attack on external
surfaces, as described in the chapter of this vol-
ume by T.R. Jack that deals with MIC in under-
ground applications.
Piping and vessels that contain or deliver cool-
ing water or fire protection system water are sub-
~ corrosion, localized corrosion, and
tuberculation, with serious pitting attack under
does not signal the presence of MIC, tubercles on
steel or cast iron can indicate that MIC is occur-
ring beneath the tubercle. The underdeposit en-
vironment dictates whether MIC has occurred or
will occur. These systems will almost always be
built with a corrosion allowance to account for the
expected wall thinning due to general corrosion.
Figures 7.2 through 7.6 provide several examples
of the MIC attack that has been found in such ma-
terials and systems.
In some situations, the attack under tubercles
may be minor; however, the growth of the large
tubercles can reduce the effective cross section of
piping to the point that the fluid-carrying capacity
of the pipe is seriously decreased.
MIC in t h e Power Industry
FIGURE 7.2
MIC of carbon steel fire protection system piping. (Pho-
tograph provided courtesy of Buckman Laboratories in-
ternational, inc.) (See color plates.)
Copper A /loys
Copper alloys are often used for heat ex-
changer tubing and sometimes for piping and
other components depending upon the salinity of
the water. Despite copper’s reputation for toxicity,
copper alloys are not immune to MIC, especially
when long periods of stagnation are involved or
FIGURE 7.3
Attack at carbon steel welds on service water piping from
a nuclear plant. (See color plates.)
7.5
FIGURE 7.4
Attack at carbon steel welds on service water piping from
a nuclear plant.
flow is intermittent (Figure 7.7). During the pe-
riods of stagnation, especially with untreated or
inadequately treated waters, biofilms containing
sulfate-reducing bacteria can become established
and the protective oxide film on the copper is
enriched in the sulfides that were produced by
the SRB. When the system is subsequently sub-
jected to flowing, oxygenated water, the sulfide-
modified film is dissolved and rapid corrosion
occurs. Essentially all of the copper-based alloys
are subject to this form of degradation by water
FIGURE 7.5
MIC of carbon steel at a nuclear plant. (See color plates.)
7.6
FIGURE 7.6
MIC of carbon steel at a nuclear plant. (See color plates.)
flow over a sulfide-degraded, hence nonprotective,
film.
Stainless Steels
Stainless steels are generally used as raw wa-
ter piping for “essential” or “safety-related” cool-
ing water systems in fossil-fired or nuclear plants.
Stainless steels may also be used in heat exchang-
ers in such systems. MIC of these corrosion re-
sistant alloys in apparently benign raw water en-
vironments has been the subject of industry and
regulatory scrutiny.
Weldments have been by far the most MIC-
susceptible areas of stainless steel systems
(Figures 7.8-7.1 3). While the duplex microstruc-
ture of the weld metal has been the most frequent
FIGURE 7.7
M I C of 90-10 copper-nickel stator cooler. (See color
plates.)
MIC in the Power Industry
FIGURE,7.8
MIC of stainless steel weldments, showing pre-service
failure from a fossil-fired plant. (See color plates.)
location of MIC attack, other parts of the welded
structure, including heat-affected zones and heat
tint, have also been subject to MIC. Kearns,
Borenstein, Buchanan, and others have demon-
strated that the creation of local anodic sites (e.g.,
heat tint) or surface roughness in the weld filler
has a dramatic effect on the initiation of MlC.24-26
In some welds, preferential attack of the ferrite
phase is observed. In other welds, the austenite
phase is preferentially attacked. In a test program
at a power plant, Borenstein showed that the ferrite
FIGURE 7.9
MIC of stainless steel weldments, showing pre-service
failure from a fossil-fired plant. (See color plates.)
MIC in the Power Industry
FIGURE 7.10
MIC in stainless steel weldments at a nuclear plant.
content of the weld metal had no significant effect
on its MIC s~sceptibility.~~ She also showed that,
in a single length of pipe, one weld might experi-
ence preferential attack of the ferrite while a dif-
ferent weld in the same length of pipe exhibited
attack of the austenite. Chung and his colleagues
performed a very careful microstructural analy-
sis of MIC-degraded stainless steel weldments
from power plants.28Their results confirmed those
FIGURE 7.11
MIC in stainless steel weldments at a nuclear plant.
7.7
FIGURE 7.12
MIC in stainless steel weldments. (From Chung et
(See color plates.)
of Borenstein. In some cases, preferential attack
of ferrite and preferential attack of austenite oc-
curred in different locations in the same weld
(Figures 7.14-7.17).
Heat-affected zones from stainless steel weld-
ments also appear to exhibit an increased sus-
ceptibility to MIC (Figures 7.18 and 7.19). The
severe intergranular attack at welds in thin-wall
stainless steel pipes at the H. B. Robinson plant
(Figure 7.19) was identified as MIC.29 Sensitiza-
tion has not appeared to play a significant role in
FIGURE 7.13
MIC in stainless steel weldments. (From Chung et
(See color plates.)
7.8
FIGURE 7.14
MIC in stainless steel weldments. (From Chung et al.28)
MIC susceptibility. There appears to be no differ-
ence between low-carbon ("L")grades and normal
composition stainless steels.
Despite the greater propensity for MIC in weld-
ments, some MIC failures in stainless steels have
occurred in wrought materials, completely inde-
pendent of any welding (Figure 7.20).20
FIGURE 7.15
MIC in stainless steel weldments. (From Chung et al.28)
MIC in the Power Industry
FIGURE 7.16
MIC in stainless steel weldments: preferential attack of
ferrite. (From Chung et
Oxygen appears to have played a significant
role in MIC failures in stainless steels in the power
industry. Systems that have experienced fairly con-
tinuous low flow or intermittent flow (e.g., during
periodic operability demonstrations of standby
equipment) appear to be more susceptible than
systems that flow continuously at higher flow ve-
locities (>2m/s) or systems that are essentially
stagnant. Several test systems, each designed to
simulate a specific plant cooling water system,
have shown that much of the corrosion damage
during periods of flow follow extended periods of
tag nation.^^ During the stagnant periods them-
selves, little or no corrosion occurs, despite the
formation of an active biofilm replete with anaer-
obes, including SRB.
MIC in the Power Industry 7.9

FIGURE 7.19
MIC attack at heat-affected zone of a stainless steel weld-
ment in a nuclear plant.

FIGURE 7.1 7
MIC in stainless steel weldments: preferential attack of
austenite. (From Chung et a1.28)

FIGURE 7.1 8
MIC attack at heat-affected zone of a stainless steel weld- FIGURE 7.20
ment in a fossil plant. (See color plates.) MIC attack on heat exchanger tube. (See color plates.)
7.10 MIC in t h e Power Industry

Nickel-Based Alloys and Other

Corrosion-Resistant Materials
Nickel-based alloys or high molybdenum stain-
less steels are often selected as replacements for
stainless steels that have not provided the desired
degree of corrosion resistance. In general, this ap-
proach has proven to be justified. In at least one
case, however, critical heat exchangers, tubed with
nickel-based alloys (e.g., UNS N08800) have failed
as a result of MIC (Figure 7.21).31-33Unlike most
power industry heat exchangers, the cooling water
(lake water) is on the tube outer diameter. Silt, cal-
cium carbonate scale, and microbiological foulants
all collect on the tubes and at tube-tube support
plate crevices. Because of the design, cleaning
of the units is virtually impossible. The microbio-
logical fouling effectively “glues” the silt and other
nonbiological foulants together, producing more
effective differential aeration cells. The SRB ac-
tivity also produces sulfides that influence initi-
ation and growth of pits. On-line monitoring of
test systems that simulate these heat exchang-
ers has shown that corrosion activity is essentially
nonexistent during stagnant periods and is great-
est when flow is initiated. When oxygen is intro-
duced, the biogenically produced sulfides and the
oxygen interact to produce pitting, even in these
highly pitting resistant alloys.

Mitigation Approaches
~~

Water treatment, using biocides, biodisper-

sants, etc., is the most common approach for con-
trol or prevention of MIC. Biocide treatment is
primarily a preventive measure unless biofilms ac-
tually participate in the corrosion process. Both ox-
idizing and nonoxidizing biocides are commonly
used. Chlorine, chlorine compounds, and bromine
compounds remain the most common approaches
for microbiological control in the power industry.
Nonoxidizing biocides, such as glutaraldehyde,
quaternary amines, and dodecyl guanidine, are
being used more often, especially in closed sys-
tems. Water treatments that combine biocides,
dispersants, and other agents to increase the pen-
FIGURE 7.21
MIC of Alloy NO8800 heat exchanger tube.
etrating power of the treatment and its ability to
remove biomass and other deposits have been
shown to provide a reliable approach to control of
MIC in the power industry.
Concerns with both MIC and fouling in
power plant equipment have led to alternative
approaches to mitigation. One such approach,
targeted chlorination, treats a group of heat ex-
changer tubes with a high dosage of biocide for a
MIC in the Power Industry
relatively short period of time. That high concen-
tration of biocide is sufficiently diluted by mixing
with the effluent from the other tubes in the heat
exchanger that the concentration of chlorine in the
total effluent is less than plant and regulatory lim-
its. During the targeted treatment, the tubes see
a sufficiently high concentration of chlorine to ef-
fect a kill of the biofilm. Several approaches to tar-
geted treatments have been adopted on a plant
scale.
Although preventive treatments (e.g., biocide
and biodispersant chemicals, delivery systems, ef-
fluent permits) are expensive, they are far more
economical than remedial MIC control methods,
which will include mechanical and chemical clean-
ing, more extensive water treatment, thermal treat-
ments, or, in many cases, complete system re-
placement. These more extensive treatments have
been required when a thick biofilm and MIC con-
dition have been allowed to progress unchecked.
Simple and reliable techniques for monitoring
biofilm activity that permit an accurate and early
indication of biofilm formation provide a means to
improve MIC control, while reducing costs and de-
creasing environmental impacts. On-line methods
permit the system operator to take mitigation ac-
tions before a damaging biofilm becomes estab-
lished while using the optimum treatment regimen.
Cleaning, both by mechanical and chemical
methods, and on-line and off-line approaches have
been used as an effective and necessary part of
MIC mitigation procedures.’ 1,34,35 Off-line meth-
ods are effective; however, the additional down-
time associated with the cleaning procedure is
costly. On-line cleaning, using sponge balls or
brushes for heat exchanger tubing, or chemical
methods, has also been successfully applied to
plant equipment.35
The use of corrosion-resistant alloys seems to
be the “treatment” of choice for severely MIC dam-
aged systems.36 Replacement of lined or coated
carbon steel with 6% Mo stainless steels or car-
bon steels lined with high molybdenum nickel-
based alloys is expensive.* These highly alloyed
materials, used in conjunction with increased at-
tention to microbiological controls, offer a margin
against lapses in other mitigation approaches. The
7.1 1
more highly alloyed materials have shown a great
resistance to MIC. Of the commercial alloys, only
titanium has shown an apparent i m m ~ n i t y . ’ ~ , ~ ~
The feasibility of other approaches, such as
brief thermal treatments to “sterilize” surfaces or
the use of acoustic methods, has been demon-
strated on a small scale; however, these ap-
proaches have not yet been adopted for routine
plant application. The primary advantage of such
methods is that they offer the opportunity for mi-
crobiological control with no effluents.
References
1. G. Kobrin, ed., A Practical Manual on Microbiolog-
ically lnfluenced Corrosion, Vol. 1 (Houston, TX:
NACE, 1993).
2. S.W. Borenstein and G.J. Licina, “Avoid MIC-
Related Problems in Nuclear Cooling Systems,”
Power June (1990).
3. Mic robio IogicalIy Induced Corrosion of Co nt ai n-
“
ment Service Water System,” IE Information Notice
No. 85-30 (United States Nuclear Regulatory Com-
mission Office of Inspection and Enforcement, April
19, 1985).
4. “Microbiologically Influenced Corrosion (MIC),”
SER 73-84 (Institute of Nuclear Power Operations
Significant Event Report, 1984).
5. “Service Water System Problems Affecting Safety-
Related Equipment,” Generic Letter 89-13 (United
States Nuclear Regulatory Commission, July 18,
1989).
6.“Microbiologically Induced Corrosion of Emergency
Diesel Generator Service Water Piping,” NRC In-
formation Notice No. 94-79 (United States Nuclear
Regulatory Commission Office of Inspection and
Enforcement, November 23, 1994).
7. S.C. Dexter, ed., Biologically Induced Corrosion
(Houston, TX: NACE, 1986).
8. N.J. Dowling, M.W. Mittleman, and J.C. Danko,
eds., Microbially lnfluenced Corrosion (Houston,
TX: AWS and NACE, 1991).
9. 1995 International Conference on Microbially Influ-
enced Corrosion (Houston, TX: AWS and NACE,
1995).
10. D.H. Pope, D. Duquette, D.C. Wayner, and A.H.
Johannes, “Microbiologically Influenced Corrosion:
A State of the Art Review,” MTI Publ. No. 13
7.12
(Columbus, OH: Materials Technology Institute of
the Chemical Process Industries, 1984).
11. D.H. Pope, “A Study of Microbiologically Influenced
Corrosion in Nuclear Power Plants and a Practi-
cal Guide for Countermeasures,” EPRl NP-4582
(Palo Alto, CA: Electric Power Research Institute,
1986).
12. G.J. Licina, “Sourcebook for Microbiologically Influ-
enced Corrosion in Nuclear Power Plants,” EPRl
NP-5580 (Palo Alto, CA: Electric Power Research
Institute, 1988).
13. G.J. Licina, “Detection and Control-An Extension
of the Sourcebook for Microbiologically Influenced
Corrosion in Nuclear Power Plants,” EPRl NP-6815-
D (Palo Alto, CA: Electric Power Research Institute,
1990).
14. D.H. Pope, “Microbial Corrosion in Fossil-Fired
Power Plants-A Study of Microbiologically Influ-
enced Corrosion and a Practical Guide for Its Treat-
ment and Prevention,” EPRl CS-5495 (Palo Alto,
CA: Electric Power Research Institute, 1987).
15. G.J. Licina, “Electrochemical Aspects of Microbio-
logically Influenced Corrosion,” 1988 Proceedings
of EPRl Microbial Corrosion Workshop, ed. G.J.
Licina, EPRl ER-6345 (Palo Alto, CA: Electric
Power Research Institute, 1989).
16. “Program Reduces Fire Protection System Corro-
sion,” Power Eng. 99(1995): 21-23.
17. P.R. Puckorius, et. al., “Service Water System
Corrosion and Deposition Sourcebook,” EPRl TR-
103403 (Palo Alto, CA: Electric Power Research
Institute, 1993).
18. G.J. Licina, “An Overview of Microbiologically Influ-
enced Corrosion in Nuclear Power Plant Systems,”
MP 28( 1989): 55-60.
19. M. Bibb, “Bacterial Corrosion in the South African
Power Industry,” in Biologically lnduced Corro-
sion, ed. S.C. Dexter (Houston, TX: NACE, 1986),
pp. 96-1 01.
20. P.R. Puckorius, “Massive Condenser Failure
Caused by Sulfide Producing Bacteria,” MP
December (1983).
21. A.M. Brennenstuhl and P.E. Doherty, “The Eco-
nomic Impact of Microbiologically Influenced Cor-
rosion at Ontario Hydro’s Nuclear Power Plants,” in
Microbially lnfluenced Corrosion, eds. N.J. Dowl-
ing, M.W. Mittleman, and J.C. Danko (Houston, TX:
AWS and NACE, 1991).
22. D.C. Bley, V.M. Bier, D.H. Johnson, and J.W.
Stetkar, “Service Water Systems and Nuclear
MIC in the Power Industry
Plant Safety,” NSAC-148 (Nuclear Safety Analysis
Center/Electric Power Research Institute, May,
1990).
23. M. Bibb and K.W. Hartman, “Bacterial Corrosion,”
Corros. Coat. South Africa October (1984): 12-
29.
24. J.R. Kearns and G.E. Moller, “Reducing the
Heat Tint Effects on the Corrosion Resistance of
Austenitic Stainless Alloys,” MP May (1994): 57-
61.
25. J.R. Kearns and S.W. Borenstein, “Microbially In-
fluenced Corrosion Testing of Welded Stainless
Steel Alloys for Nuclear Power Plant Service Wa-
ter Systems,” CORROSION/91, paper no. 279
(Houston, TX: NACE, 1991).
26. P. Li, et. al., “Corrosion Studies of Stainless Steel
Weldments in a Microorganism-ContainingArizona
Ground Water System,” 1995 International Confer-
ence on Microbially Influenced Corrosion (Houston,
TX: AWS and NACE, 1995).
27. S.W. Borenstein, “Microbiologically Influenced Cor-
rosion Failures of Austenitic Stainless Steel Weld,”
MP August (1988): 62-68.
28. Y. Chung, H.J. Mantle, and G.E. Lakso, “Selective
Attack in Microbiologically Influenced Corrosion of
UNS S30800 and S32100 Welds,” 1995 Interna-
tional Conference on Microbially Influenced Corro-
sion (Houston, TX: AWS and NACE, 1995).
29. C.J. Johnson, “Keep the Water Flowing to Reduce
the Potential for MIC,” Power March (1987): 41-
43.
30. A.M. Brennenstuhl and T.S. Gendron, “The Use of
Field Tests and Electrochemical Noise to Define
Conditions for Accelerated Microbiologically Influ-
enced Corrosion (MIC) Testing,” in Microbiologically
lnfluenced Corrosion Testing, ASTM STP 1232,
eds. J.F. Kearns and B.J. Little (Philadelphia, PA:
American Society for Testing and Materials, 1994),
pp. 15-27.
31. A.M. Brennenstuhl, T.S. Gendron, and P.E. Do-
herty, “Fouling and Corrosion of Freshwater Heat
Exchangers,” 5th International Symposium on En-
vironmental Degradation of Materials in Nuclear
Power Systems-Water Reactors, American Nu-
clear Society, 1992.
32. A.M. Brennenstuhl, T.S. Gendron, and B. Cleland,
“Mechanism of Underdeposit Corrosion in Fresh-
water Cooled Austenitic Alloy Heat Exchangers,” In-
ternational Conference on Advances in Corrosion
and Protection, University of Manchester Institute
MIC in the Power Industry
of Science (UMIST), Manchester, United Kingdom,
June, 1992.
33. T.S. Gendron, R.D. Cleland, and P.A. Lavoie,
“The Role of Chloride and SRB in Underdeposit
Corrosion of Alloy 800 in Fresh Water,” in Microbially
Influenced Corrosion, eds. N.J. Dowling, M.W. Mit-
tleman, and J.C. Danko (Houston, TX: AWS and
NACE, 1991).
34. T.O. Brice and W.A. Glover, “Service Water Chem-
ical Cleaning at River Bend Gets Results,” COR-
ROSION/94, Paper no. 251 (Houston, TX: NACE,
1994).
35. R.W. Lutey and G.A. Lozier, “On-line Chem-
ical Cleaning for Once-through Service Water
System,” EPRl Service Water System Reliability
7.13
Improvement Seminar (Palo Alto, CA: Electric
Power Research Institute, 1992), pp. 75-89.
36. J.D. Redmond and C.M. Houska, “Service Water
System Materials Replacement Trends,” Service
Water Systems Reliability Improvement Seminar
(Palo Alto, CA: Electric Power Research Institute,
1993).
37. A.H. Tuthill, “Survey of Microbiological Influenced
Corrosion of Alloys Other Than Type 304 and 316,”
EPRl Service Water System Corrosion Seminar
(Palo Alto, CA: Electric Power Research Institute,
1992), pp. 281-294.
38. J.G. Stoecker and D.H. Pope, “Study of Biological
Corrosion in High Temperature Demineralized Wa-
ter,” MP 25( 1986): 56-58.

MIC in the Waste Treatment Industries
Introduction
Corrosion failures in biological waste treatment
processes from microbiologically influenced corro-
sion (MIC) have not been widely publicized. Infor-
mation appears limited to several case histories.’ s2
The small number of failures reported for such pro-
cesses probably is attributed to the lack of recog-
nition of MIC as a potential source and the lower
priority of corrosion prevention compared to the
overall importance of the process itself.
Biological waste treatment processes are natu-
rally conducive to MIC. These processes rely on
dense concentrations of microorganisms, inclu-
ding those commonly associated with MIC, to
effectively reduce or consume the wastes. Simi-
larly, environmental conditions are monitored and
maintained to enhance the activity and prolifera-
tion of the desired microorganisms.
Overview of Biological Waste
Treatment Processes
An increasing number of industries are de-
riving significant benefits by using biological pro-
cesses to treat wastes. Traditionally, biological
waste treatment processes have been used for the
ablution of industrial and municipal waste water.
However, in recent years they also are being suc-
cessfully used for the remediation of hazardous
waste spills and the enhanced reclamation of pre-
cious metals from mining waste piles.
Without the dissemination of information on
MIC and the implementation of preventative mea-
sures, the occurrence of failures of this type is
8.1
CHAPTER 8
By J.B. Soebbing
anticipated to increase with the expanded applica-
tion of new and existing biological waste treatment
processes.
Industrial and Municipal
Wastewater Treatment
Industrial and municipal waste water often is
treated or cleaned in a series of physical, biolog-
ical, and chemical processes prior to discharge
back into local rivers, lakes, and oceans. The bi-
ological processes, often called secondary treat-
ment, utilize microorganisms to remove carbona-
ceous organic matter and correspondingly reduce
the biological oxygen demand (BOD) of the waste
water. They also may include nitrification and nu-
trient removal.
One biological treatment process commonly
used in wastewater treatment is the return-
activated sludge process. In this process, waste
water containing organic waste and recycled, set-
tled sludge, called return activated sludge (RAS),
from settling tanks are continuously fed to an ae-
ration basin. Within the aeration basin, they are
mixed and aerated with a suspended, aerobic
microbiologic mass. The combined liquid com-
monly is called mixed l i q ~ o rIn
. ~time, the aerobic
microorganisms decompose the organic wastes
to carbon dioxide, water, some stable compounds,
and additional microorganism^.^ When the mixed
liquor reaches a specified age, it passes to a
settling tank, where effluent is separated from the
settled sludge (including microorganism^).^ Part
of the settled sludge is recycled (RAS) to the aera-
tion basin to maintain the desired concentration of
8.2
FIGURE 8.1
Flocculating and settling activated sludge with hetero-
trophic bacteria and protozoa (2000x1. (See color plates.)
microorganisms, and a portion is wasted (waste-
activated s l ~ d g e ) .Thus,
~ the return of living
microorganisms to the aeration basin is necessary
to sustain this biological waste treatment process.
The mixed liquor-activated sludge typically
contains largely heterotrophic microorganisms
and, to a lesser extent, autotrophic b a ~ t e r i a . ~
The heterotrophic microorganisms include bacte-
ria, protozoa, fungi, and multicellular organisms.
The types of waste and the process operation sig-
nificantly influence the predominant species of mi-
croorganisms present. Figures 8.1 and 8.2 show
flocculating and settling-activated sludge with pro-
tozoa and heterotrophic bacteria.
The microorganisms of such processes have
been shown to cause MIC on submerged metal
surfaces. Both carbon steel and stainless steel
(UNS S30400) components within an aeration
basin of one plant experienced rapid failure from
MIC.’ The interiors of carbon steel piping without
adequate coatings have experienced through-wall
penetrations from MIC attack in several plants.*
Figures 8.3 and 8.4 show tubercle mounds cov-
ered by a biofilm and a resultant deep, rounded
pit beneath a removed tubercle, respectively.
MIC in the Waste Treatment Industries
FIGURE 8.2
Bacillus subtilis and Sphaerotilis natans in activated
sludge (2000X). (See color plates.)
Submerged components constructed of materials
without inherent resistance or adequate protection
measures in other wastewater treatment facilities
could experience similar MIC attack.
Hazardous Waste Bioremediation
Bioremediation has been successfully used
on contaminated soils, groundwater, beaches and
shorelines, and on slicks on open waters. In
these processes either packaged or naturally oc-
curring microorganisms are used. For hydrocar-
bon wastes, the microbes bond to contaminant
molecules and exude enzymes that yield their
breakdown. Subsequently, the microorganisms
absorb and further digest the reduced molecules,
thus decreasing the contaminant concentration.
Bacterial genera commonly used for bioremedia-
tion of hydrocarbon contaminants include Pseu-
dornonas and Bacillus. Oxygen, nutrients, and
biological catalysts frequently are added to the
processes to accelerate microorganism activity.6
Bioremediation processes for contami-
nated soils include “land farming” and “in situ
MIC in the Waste Treatment Industries
FIGURE 8.3
Tubercles beneath the biofilm appear as mounds at ap-
proximately 3 and 5 o’clock on the pipe wall. (See color
plates.)
bioremediation.” In land farming, the contaminated
soils are excavated and placed in piles or spread
across the ground. The removed soils are regu-
larly wetted and tilled following enhancement of the
existing microorganisms or the addition of select
FIGURE 8.4
Deep, rounded pit identified beneath a removed
tubercle. (See color plates.)
8.3
microorganisms to complete the necessary re-
mediation. This technique uses few metallic and
nonmetallic components and, therefore, generally
would not be expected to exhibit significant MIC.
In situ bioremediation is used to remediate
both contaminated soils and groundwater “in
place.” In this process, numerous holes are drilled
to the contaminated zones, and solutions for the
enhancement of existing microorganisms or so-
lutions of select microorganisms are injected to
complete remediation. In situ bioremediation has
the potential for MIC-related failures on buried and
submerged components. The piping and screens
of injection, monitoring, and pumping wells, as well
as the sheet piling of barrier walls at clean-up sites,
are candidates for attack.
The potential for MIC attack also exists when
in situ bioremediation is utilized to treat hydrocar-
bon contaminants in flooded utility manholes. In
this submerged environment, MIC would be of con-
cern to both metallic and nonmetallic surfaces of
electrical and mechanical equipment.
Biocatalyzed Leaching of Precious
Metals from Waste Ores
Microorganisms are used to catalyze bio-
oxidation of low-grade, hard-to-treat sulfidic pre-
cious metal ores. The method currently is being
used by several gold producers to separate gold
from base-metal s ~ l f i d e s . ~
One such process used by a mining company
utilizes Thiobacillus ferroxidans to strip iron and
sulfur from low-grade gold ore in waste piles8
The result is a more concentrated ore that can be
economically recovered using conventional tech-
nologies. An additional benefit of the biological
treatment process is the acceleration of the natural
oxidation of the waste ore. The accelerated oxida-
tion causes a steady flow of sulfuric acid runoff
that is more efficiently collected and treated and
more promptly yields an environmentally inert ore
that can be stockpiled for future processing. Dur-
ing past operations, the oxidation rate of waste ore
yielded a slow, inconsistent production of waste
sulfuric acid.
8.4
Prevention of MIC
The experiences of diverse industries have
provided numerous methods for the prevention
and mitigation of MIC. However, as discussed
shortly, many mitigation methods are not appli-
cable to or have significant limitations in biologi-
cal waste treatment processes. Therefore, initial
prevention is the key to the avoidance of MIC
in such processes. Methods for initial prevention
include:
proper system design,
utilization of resistant materials,
correct fabrication, installation, and test-
ing, and
cathodic protection.
Proper Design
Proper design requires measures to eliminate
or reduce the occurrence of crevices, regions of
stagnation, and locations of low velocity. The de-
sign of vessels, piping, and associated equipment
with these precautions is recommended to prevent
the settling and accumulation of solids on surfaces
susceptible to MIC attack.
Crevices often can be eliminated by redesign-
ing the component to entirely eliminate the crevice
or to widen and smooth the crevice opening. Simi-
larly, they can be avoided by specifying the follow-
ing:
0 joining materials by welding rather than
bolting or coupling,
0 welding seams completely rather than in-
term itt ent Iy,
0 filling crevices with sealant or caulk, and
0 welding components using double-butt
or double-lap joints rather than single-
butt or single-lap joints.
Stagnant areas can exist in process vessels
without sufficient fluid movement. Proper vessel
MIC in the Waste Treatment Industries
configuration and agitation can minimize this oc-
currence. Agitation of fluids within vessels can be
completed using either diffused air or mechanical
methods.
Stagnant areas also can occur within piping
systems with dead legs or within an idle or re-
dundant pump. Dead legs should be avoided dur-
ing design, and where found in existing systems
they should be isolated, flushed, and dried. Dur-
ing the operation of process pumps, one pump, a
redundant unit, commonly remains idle. The flu-
ids within the idle pump and its associated suction
and discharge piping are stagnant. The installation
of a small-diameter, continuous-flowing bypass
header is one method for eliminating this stag-
nant condition. Two methods for reducing the stag-
nant period include cycling the pumps so that
each pump has equal idle time and shortening
the pump cycling time to minimize the actual idle
duration.
While it is commonly recognized that veloc-
ity affects the thickness and density of resultant
biofilms, it has little effect on the overall attachment
of microorganisms to exposed surfaces. However,
at greater fluid velocities, there is less tendency
for solids to settle out. Minimizing the settlement
of solids can reduce the potential for MIC attack.
Therefore, it is commonly recommended that the
velocity in piping systems be approximately 3 to
5 ft/s (0.9 to 1.5 m/s). Caution is warranted for
some piping materials with velocities exceeding
5 ft/s (1.5 m/s) because other forms of corrosion,
such as erosion-corrosion, may occur.
Figure 8.5 shows a thick biofilm on the inte-
rior walls of steel pipe conveying RAS with relati-
vely low velocity, 0.75 to 1.5 ft/s (0.23 to 0.46 m/s).
This piping system has experienced nume-
rous through-wall penetrations from MIC attack.
Utilization of Resistant Materials
The use of resistant materials is another
method of preventing MIC in biological waste
treatment processes. The identification of suit-
able materials includes researching the perfor-
mance of materials successfully used in similar
environments and, as necessary, in situ testing of
MIC in the Waste Treatment Industries
FIGURE 8.5
Thick biofilm on the interior of RAS piping. (See color
plates.)
candidate materials. Prior to finalizing the material
selection, the influence of the methods of fabrica-
tion, installation, and testing on the potential for
MIC in the completed system also would require
consideration. Resistant material alternatives in-
clude the use of protective linings, nonmetallic ma-
terials, and upgraded metallic alloys.
The application of protective organic linings,
such as coal tar epoxies that are amine-cured or
contain phenols, to the surfaces of ferrous metals
is one recognized method for preventing or retard-
ing corrosion, including MIC, for biological waste
treatment processes. These paint materials have
been used successfully on carbon steel, ductile
iron, and cast iron in many industrial and munic-
ipal wastewater treatment facilities. However, the
performance of these paint materials is strongly
dependent on their composition and long-term
durability as well as on their pinhole-free applica-
tion and final testing prior to service.
Carbon steel piping with poorly applied coal tar
epoxy linings has experienced numerous through-
wall penetrations in several wastewater treatment
facilities.2 Figure 8.6 shows small pinhole-type pits
in poorly applied coal tar epoxy lining on an interior
pipe wal I.
8.5
FIGURE 8.6
Small pinhole-type pit and nonuniform coal tar epoxy lin-
ing on the interior of the pipe sample. (See color plates.)
Similarly, the pigments and resins of some of
the organic coating systems actually can serve as
a food source for some bacteria, thus enhancing
their growth and yielding progressive degradation
of the organic lining systemUgSome asphalt coat-
ings, for example, experience more rapid degrada-
tion in environments containing microorganisms.
Polyamide-cured epoxies also are reported to be
consumed by bacteria common to wastewater
treatment environments.1° Again, epoxies that are
amine-cured or contain phenols have been shown
to have increased resistance and provide satis-
factory performance for most exposures. Alter-
nately, some coating systems incorporate fillers
or biocides that increase their resistance to such
microorganism^.^
The long-term durability of such lining systems
also is a concern. The breakdown of the lining
system would allow rapid, localized corrosion by
MIC at these locations. Similar results can occur
if pinholes or other anomalies exist in the lining
following application and are not repaired prior to
placement into service.’
Cement or cement mortar is another protective
coating material that can prevent MIC on underly-
ing ferrous metals in fully submerged conditions.
8.6
The protection afforded by this coating material is
attributed to its natural alkalinity, with pH values of
10 and above, and to the isolation of metal surfaces
from the environment containing the microorga-
nisms. The natural alkalinity of the cement may
slow or stifle the activity of some strains of sulfate-
reducing bacteria (SRB) on or immediately ad-
jacent to this lining with pH values greater than
10.51.~
Alternately, nonsubmerged, concrete, and
metal surfaces of wastewater collection and treat-
ment systems can experience aggressive attacks
attributed to sulfuric acid. In this process, sulfur
compounds in the wastewater are reduced by
anaerobic bacteria to sulfides, including hydrogen
sulfide and other compounds. Hydrogen sulfide
is released to gas space above the wastewater
and dissolves in the moisture on these surfaces.
In turn, it is oxidized by aerobic bacteria, such
as Thiobacillus, to form sulfuric acid which
causes corrosion. Although performance reports
can vary sharply, systems commonly used to
protect against these conditions include thick film,
reinforced-epoxy or polyurethane linings or acid
resistant, potassium silicate cement
While MIC is known to cause degradation of
some plastics and plastic composite^,^ several
are reported to be resistant to MIC and can be
used to prevent its occurrence in biological waste
treatment processes. In general, increased resis-
tance to MIC for plastic products is achieved with
increased polymer chain cross-linking. One plastic
material reported to be “unaffected by bacteria or
fungi or does not promote or support algae or bac-
teria growth” is extra high molecular weight, high-
density polyethylene (EHMW-HDPE).l5 Other
plastics, such as polyvinyl chloride (PVC) and
chlorinated polyvinyl chloride (CPVC), when highly
polymerized and formulated without additives sen-
sitive to microbial attack, also can be used in such
environments.
Another nonmetallic material, a plastic com-
posite, also is reported to be resistant to MIC
attack when constructed of select materials. One
such plastic composite is fiber-reinforced plastic
(FRP) with epoxy resin and carbon fibers. This
MIC in the Waste Treatment Industries
FRP has been shown to be resistant to bacteria
representing several degradation mechanisms.16
Alternately, glass-reinforcing fibers could be used
rather than carbon fibers, provided fabrication
methods are used to prevent exposure of the
glass fibers to the process fluids since some
microbes have been shown to cause degradation
of the organic surfactants applied to the exterior of
glass fibers.16
While many upgraded or exotic metallic alloys
have increased general corrosion resistance, they
are not necessarily immune to MIC. The failure of
stainless steels and other alloys by MIC is well doc-
umented. The failure of type 303 (UNS S30300)
and 304 (UNS S30400) stainless steel piping and
supports from MIC has been reported for an in-
dustrial wastewater treatment facility.’ Thus, up-
graded or exotic metallic alloys are not recom-
mended for biological waste treatment processes
without bench test results that show sufficient re-
sistance and, thus, extended service life to justify
the increased expense.
Table 8.1 summarizes materials recommended
for the prevention of MIC in biological waste treat-
ment processes.
Correct Fabrication, Installation,
and Testing
Fabrication, installation, and testing can influ-
ence the performance of otherwise resistant mate-
rials. Adequate cleaning and surface preparation
prior to lining application and subsequent holiday
testing and repairs are necessary for successful
coating systems. Similarly, seal welding using pro-
cedures that eliminate crevices caused by under-
cuts and spatter is essential. Other measures in-
dicated in the earlier Proper Design section also
are necessary.
In some industrial facilities, hydrostatic test-
ing of equipment and piping (particularly stain-
less steel ones) with waters contaminated with mi-
croorganisms has caused extensive damage from
MIC. The equipment and piping systems of bio-
logical waste treatment facilities could experience
similar failures because of MIC-laden hydrotesting
MIC in the Waste Treatment Industries 8.7

TABLE 8.1
Materials for Biological Waste Treatment Processes

Nonmetallic F
Plastic Extra high molecular weight, high density polyethylene (EHMW-HDPE)
Rigid polyvinyl chloride (PVC)(A)
Rigid chlorinated polyvinyl chloride (CPVC)(A)
Fiber-Reinforced Plastic Epoxy resin-carbon fiber
Epoxy resin-glass fiber (B)
Concrete (Nonsubmerged) Various types with thick film, reinforced epoxycD)or polyurethane linings
Various types with acid resistant, potasium silicate cement linings
Metallic F
Carbon Steel with Protective Various grades with cement cover or cement mortar liningcc)
Linings Various grades with coal tar linings(C),(D)
Ductile Iron Various grades with cement cover or cement mortar lining(c)
with Protective Linings Various grades with coal tar linings(C),(D)
Stainless Steel Type 304 (S30400)-Not recommended without demonstrated resistance(E)
Type 316 (S31600)-Not recommended without demonstrated resistance(E)
Others-Not recommended without demonstrated resistance(E)

(A) Highly polymerized grades without additives that are sensitive to microbial attack.
Fabrication methods are required to prevent exposure of glass fibers to environment.
(c)Cathodic protection may be desired where practical to supplement resistance in submerged or buried environments.
(O) Epoxy formulations should be the amine-cured type or contain phenols in submerged or buried environments.
(E) MIC resistance proven by identical service or on-site testing is recommended prior to full-scale service; some failures identified.
(F) Environment is submerged except where noted otherwise.

without taking precautions, such as immediate coatings and a -0.95 V minimum structure-to-
draining and drying following t e ~ t i n g Numerous
.~ wastewater potential (Cu/CuSO4) is achieved.
other options for hydrotesting are available, de- It can be used to protect submerged metal
pending on the materials of construction, type of surfaces of primary clarifiers, aeration basins,
test water (e.g., chlorinated, demineralized, etc.) and settling tanks of wastewater treatment facili-
and its disposal requirements, and funding. Each ties. However, because the amount of turbulence
location should be evaluated and approached on and the oxygen content of wastewater in aeration
a case-by-case basis. basins can vary by plant and by treatment objec-
tives, field testing is recommended prior to the de-
Cathodic Protection sign and installation of such systems.
The application of cathodic protection is not
For more than 40 years, cathodic protection recommended for the interiors of RAS piping, as
has been used successfully in many industries shown corroded herein. It is not considered practi-
to preclude corrosion, including MIC, on metal cal for the interiors of these pipes because of flow
surfaces in buried and submerged environments. disruption and excessively high current require-
Similarly, it can be applied to some biological treat- ments.
ment processes for the initial prevention of MIC in The application of cathodic protection to sheet
which the current requirement for protection is at- pile barrier walls and wells at in situ remediation
tainable and the installation of anodes is feasible. sites is achievable. In contrast, it is not consi-
Success in these environments is most com- dered applicable to surfaces exposed to sulfuric
monly achieved when cathodic protection is used acid waste discharge from biocatalyzed leaching
to supplement the protection afforded by protective at mining operations.
8.8
Mitigation of MIC
For most industries, the mitigation of MIC fol-
lowing its identification can be achieved by the ap-
plication of one or more of these measures:
internal cleaning (mechanical or chemi-
cal),
chemical treatments (disinfection, water
treatments, corrosion inhibitors, etc.),
biocide treatments, and
cathodic p r o t e c t i ~ n . ~ , ’
With exception of cathodic protection, most of
these otherwise successful methods have either
limited benefit or would be detrimental to the es-
sential microorganisms or potentially yield other
waste or contamination concerns.
Internal Cleaning
Cleaning the interiors of process tankage
and pipe surfaces removes corrosion products,
debris, and developed biofilms. However, neither
mechanical nor chemical cleaning is expected
to provide long-term benefits for biological waste
treatment processes. Following cleaning and
return to service, freshly exposed surfaces again
would be exposed to processes with dense
concentrations of microorganisms. One source
indicated that a biofilm could reestablish itself in
as little as 72 hours in such an environment17 and
the detrimental effects of MIC could recommence.
Chemical Treatments
Chemical treatments are used in other indus-
tries to clean and disinfect systems, treat wa-
ter to enhance biocide performance, or to inhibit
corrosion where MIC has been identified. These
treatments are applied in slug or continuous feed
arrangements or both.
These treatments generally are not considered
applicable to biological waste treatment processes
MIC in the Waste Treatment Industries
for the following reasons:
They could kill or inhibit the activity of mi-
croorganisms essential to the process.
They likely would be cost-prohibitive be-
cause most of the processes are consid-
ered once-through systems.
The duration of benefit may be limited be-
cause the processes contain high con-
centrations of microorganisms that could
be capable of reestablishing conditions
(biofilms, bulk fluid, etc.) conducive to
MIC.
Many of the treatment chemicals could
require additional treatment for their re-
moval from discharge streams or could
yield additional contamination to be re-
mediated.
Their accessibility to microorganisms ac-
tually causing the MIC may be greatly
limited by existing biofilms or corrosion
nodules.
Some may be detrimental to existing,
protective linings.
Biocide Treatmenfs
For the purpose of this discussion, the chem-
icals used to kill microorganisms (biocides) or
to inhibit the growth of microorganisms (biostats)
are grouped herein as biocide treatments. These
chemicals are used widely to mitigate MIC in other
industries. Similar to chemical treatments, biocide-
type treatments are not considered applicable to
biological waste treatment processes for the rea-
sons listed previously.
Cathodic Protection
As noted herein before, cathodic protection
can be an effective method for initially prevent-
ing MIC on submerged or buried metal surfaces
in biological waste treatment processes. However,
once detected, MIC in these environments is often
MIC in the Waste Treatment Industries
accompanied by mounds, tubercles, and corrosion
deposits that can shield underlying surfaces from
cathodic protection.
The recommended corrective action prior to
the application of cathodic protection in such in-
stances includes completely cleaning the sur-
faces, fully opening pits, preparing surfaces by
abrasive blasting, and applying protective linings.
Similar to the use of cathodic protection for the
initial prevention of MIC, its use for the mitigation
of MIC is usually suited to
submerged metal surfaces and equip-
ment of most primary clarifiers and set-
tling basins, and some aeration basins of
wastewater treatment facilities; and
buried sheet pile barrier walls and wells
at hazardous waste, in situ remediation
sites.
It is unlikely to be suitable for metal surfaces ex-
posed to sulfuric acid waste discharge from bio-
catalyzed leaching at mining operations, and the
interiors of RAS piping and exposed metal sur-
faces of highly turbulent aeration basins in waste-
water treatment facilities.
Summary
~ ~~
Although corrosion failures in biological waste
treatment processes from MIC have not been
widely publicized, they can and have been docu-
mented. The dense concentrations of microorgan-
isms and the preservation of process conditions
to enhance their activity and reproduction in the
processes yield conditions naturally conducive to
MIC.
Many methods commonly used to mitigate MIC
in other industries, including biocide and chemical
treatments and mechanical and chemical clean-
ing, as well as others, are not generally applicable
to biological treatment processes. These methods
could kill or inhibit the activity of microorganisms
essential to the continuation and effectiveness of
the process, require additional treatment for their
8,9
removal from discharge streams, cause additional
contamination to be remediated, provide benefits
for a very short duration, or be cost-prohibitive
because of the once-through nature of some of the
processes. The key to avoidance of MIC in these
processes is initial prevention through proper
system design, utilization of resistant materials or
protective coatings, the correct fabrication, instal-
lation, and testing of exposed components and
application of cathodic protection where suitable.
References
1. G. Kobrin and R. Strong, ‘Case 5-Corrosion in a
Waste Water Treatment Tank,” MP 20(1981): 46.
2. J. Soebbing and R. Yolo, “Microbiologically Influ-
enced Corr0s ion Wastewater Treatment PIants,”
CORROSION/95, paper no. 214 (Houston, TX:
NACE, 1995).
3. G. Tchobanoglous, Wastewater Engineering: Treat-
ment, Disposal, Reuse, 2nd ed. (Boston, MA:
Metcalf & Eddy, 1979), pp. 393-432.
4. P. Vesilind and J. Peirce, Environmental Engineer-
ing (Ann Arbor, MI: Ann Arbor Science, 1982), pp.
170, 171, and 270.
5. R. Noyes, ed., Unit Operations in Environmen-
tal Engineering (Park Ridge, NJ: Noyes, 1994),
pp. 10-12.
6. “Basic Bio remediat io n Concepts ,” Co r porate
Brochure (Bonita Springs, FL: Oettco Products
Corp).
7. “Cyanide-Free Biocatalyzed Leaching of Gold and
Silver Ore,” Corporate Brochure (Bonita Springs,
FL: Oettco Products Corp).
8. M. Charlier, “Newmont Mining Bets on Bugs to
Boost Gold Reserves,” The Wall Street Journal,
January 30, 1995, p. B4.
9. G. Kobrin, ed., A Practical Manual on Micro-
biologically Influenced Corrosion (Houston, TX:
NACE, 1993) pp. 13, 101-1 21.
10. C. Munger, Corrosion Prevention by Protective
Coatings (Houston, TX: NACE, 1984), p. 506.
1 1. S. Borenstein, Microbiologically Influenced Corro-
sion Handbook (New York: Industrial Press, 1994),
pp. 221-265.
12. J. Soebbing, et al., “Rehabilitating Water and
Wastewater Treatment PIant ,” J. Protect. Coatings
Linings 13 (1996): 54-64.
8.10
13. A. Cunningham, “Corrosion Protection in Sewage
Treatment Plants,” J. Protect. Coatings Linings 13
(1996): 66-74.
14. J. Redner, et al., “Evaluating Protective Coatings
for Concrete Exposed to Sulfide Generation in
Wastewater Treatment Facilities: An Update,” J.
Protect. Coatings Linings December (1994): 50-
61.
15. “9-92 A17, 820-91, 1089-91 A17, and 1091-91
MIC in the Waste Treatment Industries
A01 ,” Corporate Brochures (Richardson, TX:
Phillips Driscopipe).
16. P. Wagner, et al., “Microbiologically Influenced
Degradation of Fiber Reinforced Polymer Compos-
ites,” CORROSION/94, paper no. 255 (Houston,
TX: NACE, 1994).
17. D. Blackwood, et al., “Novel Sensors for On-Site
Detection of MIC,” CORROSION/94, paper no. 254
(Houston, TX: NACE, 1994).

Treatment for the Mitigation of MIC
Introduction
It is widely accepted that overcoming or mit-
igating MIC is difficult, time consuming, and
expensive.' Therefore, it would be logical to as-
sume that preventing MIC from being initially es-
tablished should be a top priority. At the present
time, increased awareness of the potential prob-
lems associated with MIC has made prevention a
high priority consideration in the strategy used to
treat cooling water systems. A totally coordinated
water treatment program should include elements
to prevent MIC.
Once the corrosion situation has been identi-
fied as MIC several decisions must be made about
how to deal with the corrosion. In most cases,
these decisions lead to a program of mitigation
or the elimination of the MIC, or at least prevent-
ing it from being a contributor to putting the sys-
tem out of operation. It must be noted that there
are some situations where mitigation is neither
practical nor possible. Under those circumstances,
the alternatives are to replace the system com-
ponents and implement a program to prevent
MIC from recurring or to simply allow the condi-
tion to continue until 'an alternative can be imple-
mented.
Most specialists agree that depending on the
system and the degree of severity of the MIC,
state-of-the-art technology provides some means
of mitigating most existing MIC conditions. The
procedures are typically situation specific, but
there are certain guidelines that can be used to
increase the probability of a successful mitigation
program in a majority of cases.* These procedures
are discussed in the following sections.
9.1
CHAPTER 9
By R. W. Lufey
Prevention of MIC
Sysfem Design
System design, whether it is the redesign of an
existing system or original design of a new plant or
system components, must incorporate sound en-
gineering concepts for total corrosion control, in-
cluding MIC. Design considerations for corrosion
control overlap several other areas of considera-
tion. Items to be coordinated into the total system
design include preconstruction, construction and
pre-operational phases, hydrostatic testing, ope-
rational phases, and preventive m a i n t e n a n ~ e . ~ , ~
Important factors within each of these items
are:
source water chemistry (including pH,
salinity, hardness, levels of suspended
solids or turbidity, organic contamina-
tion),
typical temperature ranges,
flow rates (including the increase or dec-
rease of flow rates within a process line),
and
type of operation (continuous, intermit-
tent, stagnant, once-through vs. circula-
tion, closed-loop circulation, buried pipe,
underwater, imbedded in concrete,
etc.).
Original system design and redesign must include
provisions for accessibility for cleaning and for
water treatment. Neither of these considerations
should be handled as an afterthought.
9.2
Stagnant or low flow conditions provide opti-
mum environments for the growth of microorgan-
isms and subsequent corrosion. These conditions
also make it more difficult to use traditional mi-
croorganism control procedures. Where possible,
the system design should provide control of the
flow velocity to a range that will be a limiting fac-
tor to the growth of MIC microflora. Generally, this
would involve a lower limit on flow velocity to the
extent that suspended solids will remain in the bulk
water stream. Continuous flow is preferred to inter-
mittent flow conditions. Dead-leg and bypass cir-
cuits should be avoided wherever possible. When
they are required and when standby components
are part of the system, the system design should
include provisions for drains, traps, recycle circuits,
monitoring equipment, and the capability to per-
mit periodic draining and cleaning when necessary
without interrupting the operation of the s y ~ t e m . ~ , ~high susceptibility to MIC and with serious conse-
Detailed designs should consider local sites
likely to create optimum environments for the
growth of microorganisms. When possible, the de-
sign of these sites should be changed. For ex-
ample, crevices generated by weld-backing rings
may act as a means to trap accumulations of
organic and inorganic deposit-forming materials.
This can be eliminated with proper design. Provi-
sions should be made for circulating water period-
ically or flushing the system in those components
that typically remain stagnant for long periods of
time (e.g., fire safety water systems). Side-stream
filtration and in-line filters and screens should be
included in the design when it is known that the
water flow will contain high levels of suspended
solids. Provisions must be made to purge the ac-
cumulations of suspended solids from the system
when it is not possible to prevent their existence.
Planned maintenance and routine housekeep-
ing procedures should be developed, and the
system design should include considerations of ef-
fective implementation of this type of preventive
maintenance. System design should consider the
need for periodic removal of deposits by physical or
mechanical cleaning. This involves providing ac-
cess ports for the insertion of pigs, air-bumping,
sand-jetting, or high-pressure water spray (hydro-
laz i ng) equi pment .
Treatment for the Mitigation of MIC
System design also should include the devel-
opment of a totally coordinated water treatment
program, which includes control of scale, deposits,
and microorganisms. The design must provide fa-
cilities to implement the water treatment program
in the most effective manner possible. Included
with these facilities should be equipment to moni-
tor the control parameters used in the water treat-
ment program and to detect any variation from the
criteria on which the water treatment program is
based.
Designing processes to provide the capability
of on-line cleaning of isolated components that are
particularly susceptible to biofouling or MIC must
be considered, especially when there are no other
alternatives to prevent potential problems.
Serious consideration of the use of closed-
loop design should be made for processes with a
quence of failure. In a closed-loop system, ingress
of contaminants can more readily be controlled,
and chemical treatment is less restricted by envi-
ronmental effluent limits. This approach, although
initially more capital-intensive, may prove to be the
most economical approach for preventing MIC for
safety-related systems or critical components in
the long run.
There are certain design considerations that
should be included in fire safety water systems for
purposes of preventing MIC. These include elimi-
nating the use of hydrant water, which will reduce
the need for adding makeup water to the system;
including in the design a makeup water reservoir
that facilitates chemical treatment of the system;
designing the capability to purge suspended solids
from the bulk water via bypass circulation and side-
stream filtration; and designing facilities to monitor
and test the system for potential or existing MIC.
Materials of Construction
In the past, selection of construction materials
was frequently done without direct consideration
of preventing MIC. Other criteria, including initial
cost of materials, were given higher priority. It has
only recently been accepted that prevention of MIC
is a top priority item. It was believed that in many
Treatment for the Mitiaation of MIC
systems, MIC could be controlled through proper
water treatment, such as the use of biocides, dis-
persants, and corrosion inhibitors. This was and
may still be true, particularly in closed-loop
and recirculating systems. However, in open-loop
and once-through systems, such as raw water or
service water systems, chemical treatment alone
is not adequate to prevent MIC. It very often proves
to be uneconomical and very difficult because of
the increased limitations on water treatment by en-
vironmental restrictions. Consequently, especially
in once-through systems, proper selection of ma-
terials of construction as related to MIC has be-
come more i m p ~ r t a n t . ~
Maintenance Cleaning
When addressing the question of preventing
MIC, the first factor that must be considered is
good housekeeping and cleanliness. Even though
MIC can occur in environments free of sludge, de-
posits, and foulants, basic microbiological control
technology stresses the need to maintain the sys-
tem and specific components in a condition as free
of sludge, deposits, and foulants as possible. Prac-
tical experience has shown that this can be done
only when there is a commitment to routine main-
tenance cleaning. This commitment to cleaning on
a routine basis is no different than committing to
changing the oil in an automobile on a mileage or
calendar schedule. System or component clean-
ing is typically done only when heat transfer effi-
ciency or flow rates become a limiting factor in the
operation of the system. In safety-related cooling
water systems, the decision to clean most likely re-
sults from the necessity to maintain heat rejection
capabilities for the design basis accident condition.
This philosophy must be modified to the extent
that the decision to perform routine maintenance
is based on preventing MIC.
Cleaning programs may involve a mechani-
cal procedure, a chemical treatment procedure,
or some combination of these. There are several
cleaning methods and alternatives to consider.
The selection of a routine cleaning procedure re-
quires consideration of technical, economic, and
practical factors. Routine cleaning projects must
9.3
be well planned and coordinated with both oper-
ational and maintenance projects, and with plant
personnel responsible for these activities. The pri-
mary objective of the cleaning project is to pre-
vent or minimize the existence of an environment
at any point in the system that supports the growth
of MIC microflora and to condition the surfaces of
the system in such a way that sessile growth of mi-
croorganisms is restricted. When this objective is
achieved, other preventive measures can readily
and effectively inhibit MIC.
Maintenance cleaning programs must be well
planned with attention to detail to ensure the suc-
cess of the program. It is important to define what
types of deposits are involved. Cleaning trials prior
to establishment of a routine procedure provide es-
sential information. The planning should involve all
disciplines and organizations responsible for the
operation and maintenance of the system. The
planned procedure should define each of the es-
sential stages of the cleaning. However, the pro-
cedure should be flexible to the degree that it can
be modified as the conditions require.
Routine cleaning becomes necessary as a
means for preventing MIC when procedures to
prevent fouling and deposition are inadequate. In
some situations, the operating conditions may be
too severe to be manageable with typical practical
preventive measures, and the only alternative is
routine cleaning.
Mechanical Cleaning
The selection of a method should consider the
cleaning objectives, as well as the function of the
component being cleaned. Generally, it is most
practical to carry out mechanical cleaning projects
on individual sites or components rather than
consider system-wide cleaning. In some cases,
mechanical cleaning is done prior to chemical
cleaning. Routine mechanical cleaning methods
(Table 9.1) have been designed for individual sites
or components, including piping systems, tanks,
and heat exchangers. Both on-line and off-line
methods may be considered. On-line mechanical
cleaning most often is considered as a preventive
method. However, off-line procedures may offer
alternative preventive methods.
9.4 Treatment for the Mitiaation of MIC

TABLE 9.1
Mechanical Cleaning Alternatives

Heat Exchangers Piping Systems Tankage

Batch or recirculation sponge balls High-pressure water lance High-pressure water lance
Scrapers High velocity and reverse velocity flushes Drain and flush
Brushes Sand jetting High-pressure air lance
High-pressure water lance Pigging methods Sand jetting
Component side-stream filtration Side-stream filtration
Air bumping

When evaluating the effectiveness of mecha- materials of construction and service

nical methods, it is expected that these will main-
tain the required heat transfer and specified flow
rates and prevent the establishment of sessile mi-
crobiological growth and existence of favorable
MIC environments. It cannot be assumed that the
procedure is totally effective. Therefore, it is es-
sential that the uniformity of cleaning be monitored
because underdeposit corrosion, galvanic effects,
and MIC may be promoted by nonuniform or in-
effective mechanical cleaning. Depending on the
specific cleaning method(s) used, inspection of
the system or component should be made before
and after the cleaning procedure. Where possible,
photographic records are useful in assessing the
effectiveness of the cleaning program when the
procedure extends over a long period of time.
Chemical Cleaning
The success of a routine chemical cleaning
program and the number of problems encountered
in the execution of it reflect the adequacy of plan-
ning. This emphasis on planning is not intended
to imply that chemical cleanings are extremely dif-
ficult to plan and carry out. It is simply to point
out that a technically sound chemical cleaning pro-
gram can be most effectively performed when the
proper procedures are f ~ l l o w e d . ~ , ~
There are several chemical cleaning alterna-
tives that can be considered. They can be classi-
fied according to the following criteria:
chemical characteristics of the contami-
nants to be controlled or removed,
function of the system or component to
be cleaned,
on-line vs. off-line cleaning, and
interaction with routine water treatment
program.
As with mechanical cleaning, the decision to im-
plement a cleaning project is usually based on
the need to maintain the design level of sys-
tem performance in heat transfer and flow velo-
city. Practical experience has taught industry that
preventive chemical cleaning is also an effective
method for preventing localized corrosion, inclu-
ding MIC.
Some of the most common chemical cleaning
agents may be classified according to the charac-
teristics of the materials to be removed as listed in
Table 9.2.
Selection of the chemical cleaning agent
must take into consideration the applicability to
the particular materials to be removed and the
compatibility with materials of construction. It must
be emphasized that chemical cleaning processes
used as a routine measure for preventing MIC
must be passive, nonaggressive procedures.
Uniform metal loss, even at moderate levels,
is generally not a primary concern with routine
chemical cleaning . However, metal rep recipitat ion
must be avoided and, when necessary, combina-
tions of chemical cleaning agents, which include
chelating agents, can be employed. Additional
considerations in selecting a chemical cleaning
Treatment for the Mitigation of MIC 9.5

Makeup Water
TABLE 9.2
Common Chemical Cleaning Agents Major considerations in the selection of the
makeup water source include the function of the
Scale and Metal Oxides3 system, the volume of makeup water required, and
Ammoniated citric acid Citric acid the design and operation of the system. Makeup
Phosphonatesiphosphorous acid Polyacrylic water sources are primarily surface sources such
acidisalts as lakes, reservoirs, and rivers or ground wa-
NaEDTA HEDTA
Hydrochloric acid Phosphoric acid
ter (wells). However, there is an increasing trend
Sulfamic acid Sulfuric acid to consider the use of treated waste water as a
Ammonium bifluoride/ HEDP makeup water source. The selection of makeup
hydrofluoric acid Oxalic acid water is now influenced by environmental impact
Organic Deposits considerations of how and where the blowdown or
Oxidizing agents (CIz, Brp, Polymeric ionic discharge of water from the system is being done.
NaMn04, Na202,0 3 ,C102) dispersants The quality of the makeup water is a pri-
Nonoxidizing biocides Alkaline detergents mary consideration for the potential of MIC occur-
(NaOH, polyphosphates, Organic Solvents ring in the system. Recognizing the importance
NaHS03, NaZCO3)
Non-ionic penetrantidispersants Non-ionic alkyl of preventing MIC, one must make every effort to
(dimethylamides of fatty acids) surfactants select high-quality makeup water. The important
quality criteria include: low organic content; essen-
tially no soluble iron and minimum suspended iron;
minimum microflora and fauna; minimum turbi-
procedure include: industrial safety and handling, dity and suspended solids; minimum dissolved or
waste treatment and disposal, environmental dispersed gases, including H2S, NH3, 0 2 , C02;
issues, temperature limitations, compatibility with and essentially no hydrocarbons such as oils and
water treatment programs, cost, and corrosion greases.
control. When there is no alternative to using a makeup
water source of low quality such as with waste-
water makeup, consideration must be given to pro-
Water Source viding capabilities for pretreatment and the routine
In many cases, few options relative to the wa- implementation of a water treatment program de-
ter source are available. Very often pretreatment, signed to prevent the establishment of a MIC con-
other than simple filtration, aeration, and sedimen- dition. Pretreatment procedures are based on the
tation, is not practical because of the large vol- characteristics of the specific water. These proce-
umes involved. While the microbiological activity dures include:
occurring in raw water leading to MIC has been
well documented, it 'is less recognized that the
use of deionized water or condensate may not eli- full-stream filtration,
minate microbiological activity that results in MIC
ion exchange/zeolite softening,
failures. Design modifications to provide closed-
loop or recirculation systems offer an extension anionic/cationic resin ion removal,
of water treatment capability. This, in effect, re-
aeration,
duces the volume of water requiring treatment
and also provides a means of internal water treat- degasification,
ment. This also permits the quality of the wa-
nitrate/phosphate removal,
ter to be upgraded and reduces the potential
for MIC. side-stream filtration,
9.6
lime-soda softening,
coagulation/flocculation clarification,
bio-oxidation, and
oil-water separation/emulsion breaking
Hydrostatic Test Water
Special emphasis should be given to the selec-
tion of hydrostatic testing water. There are numer-
ous case histories illustrating the severe MIC prob-
lems that can result from ignoring the quality of the
water used for hydrostatic tests and other preoper-
ational activities. The water sources for hydrostatic
tests are not necessarily limited by plant or com-
ponent design. Therefore, very few excuses exist
for using makeup water with an undesirable quality
that would contribute to potential MIC.
Quality factors that are important for hydro-
static testing are the same as those listed above
for operational makeup waters. If the available
sources are not of adequate quality, provisions for
treatment should be made. Treatment of hydro-
static test water is discussed in detail later in this
section.
Preventive Maintenance
Water Treatment
Changing or modifying the inorganic chemistry
of the system water has not proven to be of pri-
mary importance in preventing MIC. Some of the
alternatives investigated included pH adjustment,
sulfate ion removal, iron sequestration, phosphate
removal, and hardness ion removal. The use of tra-
ditional chemicalcorrosion inhibitors such as chro-
mates, phosphates, molybdates, zinc, and azoles
has not been effective in preventing MIC.
Nevertheless, considerable progress has been
made during the past few years in the technol-
ogy of chemically treating water to prevent MIC.
This progress encompasses both makeup water
pretreatment and routine maintenance treatment
of the system water. The concept of a totally co-
ordinated treatment program represents a major
part of that progress. The factors important to
the existence of MIC have been discussed from
Treatment for the Mitigation of MIC
a number of positions herein. However, it needs
to be stressed here that the prevention of MIC
is dependent not only on controlling the growth
of those microorganisms involved with MIC but
also on the operation of the system free of cor-
rosion problems, scale and deposits problems,
and maintenance problems that can, to some
degree, be controlled through water treatment
procedures.
A water treatment program focused on pre-
venting MIC must consist of three components.
The first is an optimized routine maintenance
chemical treatment to control microbiological prob-
lems, deposits, and corrosion. The second com-
ponent is a contingency treatment program that
is used only when the operating conditions of the
system change suddenly to the degree that the
maintenance treatment will not prevent the ini-
tiation of MIC. The contingency treatment must
be implemented immediately when the conditions
change rather than waiting until the problem gets
out of control. The third component is to plan and
implement a proactive maintenance program. This
would include scheduled on-line cleaning (me-
chanical and/or chemical) and other normal com-
ponent maintenance.
Control of Microorganisms
In the recent past, the application of biocides
to water for preservice use, hydrostatic tests, and
wet lay-up was rarely considered. The routine use
of treatment chemicals for the prevention of mi-
crobiological problems, including MIC, was either
an afterthought, or something that required consi-
derable persuasion to implement. The concept of
providing an insurance factor (optimized mainte-
nance treatment) against MIC problems was not
widely accepted. Very often, the use of corro-
sion inhibitors and deposit inhibitors received top
priority when dealing with preventive water treat-
ment. Under present-day requirements, it is, with-
out exception, necessary to give first consideration
to procedures required to prevent microbiological
problems. A definite commitment for the responsi-
bility of microorganism control must be made and
a system of accountability established as part of
the procedure to prevent MIC.
Treatment for the Mitigation of MIC
It also must be recognized that, without an ef-
fective microbiological control program in effect,
all other efforts to prevent corrosion and deposit
problems will be seriously limited. The concept of
applying biocides on a routine basis to prevent
MIC is based on the capability of the treatment
to maintain the population of the problem-causing
microorganisms at a low level where the rate of re-
production is no greater than the death rate. Prac-
tical experience has shown it is not economically
possible to sterilize a system to the extent that no
MIC organisms exist in the environment, especially
when there is a persistent source of microorgan-
isms (inoculum) being introduced into the system.
However, it is possible to keep the population un-
der control to the extent that MIC is prevented
when the biocide (a treatment that kills existing
microorganisms) is used as part of the total wa-
ter treatment program. The application of a biostat
(a treatment that eliminates or limits microorgan-
ism reproduction) may function in closed-loop sys-
tems where an inoculum source does not persist
and there is no limit on maintaining the concentra-
tion of the biostat in the treated watere819
Chlorine as well as other oxidizing agents,
such as bromine compounds, ozone, or hydrogen
peroxide, have been used for microorganism con-
trol in many industries for years. However, there
is no standard application procedure or specific
accepted level of chlorination used for preventing
MIC. Practical experience has shown that, at a pH
less than 7.8, chlorine treatment of once-through
and circulating water systems will provide an ef-
fective degree of control of MIC microorganisms in
the bulk water, that is, if the water is free of exces-
sive organic contaminants, suspended solids, and
other dechlorinating substances. At a pH greater
than 7.8, bromine compounds or chlorine dioxide
may be more effective than chlorine. Above pH 8.5,
none of the oxidant materials should be relied upon
alone to provide consistent prevention of MIC.
A total residual oxidant (TRO) of 0.2 to 0.5 ppm
appears to be the typical concentration required
to provide microorganism control applied contin-
uously in severe situations or during as short as
1 to 2 hours per 24 hours in less severe situa-
tions. Intermittent or slug dosages greater than
9.7
5.0 ppm of oxidizing agents are used to control
or eradicate biofouling, but generally these are not
used as a preventive procedure for controlling MIC.
Present environmental regulations related to dis-
charge limits place some restrictions on the con-
centration of TRO allowed in plant effluent. If the
MIC microflora reach a exponential growth phase,
treatment of the bulk water with oxidizing agents
will not be adequate to prevent the establishment
of MIC. It usually is not possible to apply sufficient
oxidant to meet the organic chemical demand with-
out contributing significantly to accelerated gen-
eral and pitting corrosion rates and also exceeding
the effluent discharge limits. Oxidizing agents are
not effective in penetrating sessile colonies of MIC
microorganisms, even at high dosage levels.
Ozone and hydrogen peroxide have greater
oxidizing potential than chlorine at levels of prac-
tical use. For this reason, these materials may be
more efficient in penetrating existing colonies of
sessile MIC microorganisms. There are, however,
a number of factors that limit the effectiveness of
ozone or peroxide for routine use as a preven-
tive treatment for MIC. These factors include cost
considerations, methods of application, personnel
safety regulations, and compatibility with materials
of construction and other components of a coordi-
nated water treatment program.
When circumstances prohibit the routine use
of oxidizing agents for preventing MIC, alternatives
that can be considered include the use of nonox-
idizing biocides. There are many organic, nonox-
idizing compounds that are capable of controlling
the growth of MIC microorganisms in industrial
process water systems. Very often, it is necessary
to test the efficacy of these compounds under ac-
tual operating conditions to establish the most ap-
propriate material and the most practical means
of applying it. Generally, the cost of treatment with
nonoxidizing biocides is greater than with oxidizing
agents. However, when oxidants cannot be used,
the increased cost of treatment with nonoxidizing
biocides is justified on the basis that the economic
losses due to MIC far exceed the cost of even the
nonoxidizing biocides .
In addition to efficacy and cost of the nonoxi-
dizing biocides, the environmental impact factors
9.8
must be considered. As with chlorine and other ox-
idants, there are effluent discharge limitations re-
lated to the use of nonoxidizing organic biocides.
Most of the nonoxidizing biocides in current use
and registered with the EPA are designed to
be nonpersistent in the environment. That is to
say, they degrade rapidly at use concentrations
into nontoxic or nonobjectionable substances. Be-
cause of this fact, most materials can be used with-
out concern when the effluent is discharged to a
conventional industrial wastewater treatment facil-
ity. This makes the use of nonoxidizing biocides
practical in open recirculating systems, closed-
loop systems, and hydrostatic testing procedures.
At use concentrations, most nonoxidizing bio-
cides are compatible with typical materials of
construction and do not contribute to corrosion.
Nonoxid izing biocides have Iimited appl icabi Iit y
for preventing MIC in once-through systems where
the water is discharged directly to regulated
receiving waters and where large volumes of
water must be treated for extended periods of
time.
The intermittent use (alternation treatment) of
nonoxidizing biocides, in conjunction with chlorine,
bromine, or other oxidants, is another alternative
that can be considered. This procedure provides
potential cost savings over the use of nonoxidizing
biocides alone. It also offers potential mechanisms
for overcoming specific environmental limitations
associated with the use of either type of material.
Recent technology has been developed that
deals with the use of penetrant-biodispersants in
conjunction with both oxidizing and nonoxidizing
biocides.’O~’l Chemically, these materials are
composed of nontoxic organic compounds with
penetrating and dispersing properties. Their use in
mitigating existing MIC has been important. How-
ever, the benefits of their use as routine compo-
nents of a preventive treatment program is becom-
ing more widely recognized. Continuous low-level
application of the penetrant-biodispersant enables
sessile colonies of the MIC microorganisms to
be penetrated by the biocide, which is typically
used at lower dosages with greater effectiveness.
The penetrant-biodispersant inhibits the biomass
produced by the microorganisms from becoming
so massive that oxidizing biocides cannot pen-
Treatment for the Mitigation of MIC
etrate the colony. Some of the penetrants are
hydrophobic to the extent that afilm forms on metal
surfaces making the surfaces less susceptible to
the deposition of biomass and sessile colonies
associated with MIC. Thus the use of penetrant-
biodispersants offers an important alternative for
consideration in preventing MIC. The possibility
exists that future technological advances will lead
to the use of nontoxic, low-cost, noncorrosive
materials classified as penetrant-biodispersants
as replacements for the traditional approach of
using oxidizing or nonoxidizing biocides.
Control of Suspended Solids
Current technology approaches the control of
suspended solids in two ways. The first is to
prevent suspended solids from entering or being
formed in the system. The second approach is to
prevent the existence of suspended solids from
causing problems in the system either by remov-
ing them by filtration, bleed, or flushing, dissolving
them, or by treating the system with chemicals,
such as dispersants and deflocculation agents.
No single procedure has proved to be entirely ef-
fective. Based on the importance of controlling
suspended solids as a factor in preventing MIC,
system-specific programs must be developed in
coordination with all elements of operation to pre-
vent the accumulation of deposits in the ~ y s t e m . ~ , ~
A specific program may involve a combination
of the use of chemical water treatment and me-
chanical or operational modifications. These pro-
grams must include consideration of pretreatment
of makeup water, selection of makeup water, rou-
tine cleaning and maintenance, system design,
and most importantly the coordination of each
component of the total water treatment program
with all others.
Control of Scale and Deposits
The existence of scale and other deposits in
the system has equal significance to each of the
other factors discussed in relation to preventing
MIC.3,4 Present-day technology provides the ca-
pability of controlling scale and deposits in two
ways. The first is by removal of ions or suspended
solids before the water is added to the system.
The second is to leave the materials in the water
Treatment for the Mitiaation of MIC
and treat it chemically or mechanically in a way to
prevent scale or deposit formation.
The availability of scale inhibitors, such as
phosphonic acid derivatives, specific chelants, an-
ionic polymeric dispersants, and deflocculation
agents, has provided adequate means of control-
ling scale and deposits in most closed-loop and
open-recirculation systems. However, these types
of chemical treatments have limited application in
once-through systems, which have a high poten-
tial for scale and deposit problems. Practical ex-
perience has shown that scale and deposit control
in once-through systems can best be achieved by
mechanical means. Compatibility of specific scale
and deposits inhibitors with biocides and corrosion
inhibitors must be considered when included as
part of the total water treatment program.
Control of Corrosion
MIC is an electrochemical corrosion process.
However, the traditional approaches used to con-
trol nonmicrobiological corrosion have not proved
to be effective in controlling MIC.3,4 Water treat-
ment corrosion inhibitors are generally ineffective
for the routine treatment under conditions where
MIC would occur. Indirectly, they do prove use-
ful as preventive measures only when the growth
of microorganisms is controlled by a biocide or
other means. For most water treatment corrosion
inhibitors to be effective, the chemical must be able
to contact the metal surfaces and anodically or ca-
thodically retard the half-reaction controlling corro-
sion. Uncontrolled growth of microorganisms often
prevents this from occurring. Some chemical in-
hibitors, including chromates, benzothiazoles, and
hydrazine, have a degree of biocidal activity. How-
ever, at the dosages used for corrosion inhibition,
these substances cannot be relied upon to prevent
the occurrence of MIC.
The corrosion inhibitors suggested for use in
wet lay-up and hydrostatic testing conditions of-
ten supplement the addition of a biocide in these
applications, and they can contribute to prevent-
ing MIC. It should be restated, however, that cor-
rosion inhibitors can be degraded or inactivated
by microbiological growth, including growth of
some microorganisms associated with MIC. Nitrite
borate inhibitors used in closed-loop systems are
9.9
particularly susceptible to degradation by nitric
acid-producing bacteria. Phosphate-based in-
hibitors can readily be metabolized by specific
bacteria, with the end result being more favorable
environments for MIC.
Cathodic protection (CP) has proven to be ef-
fective in preventing nonmicrobiological corrosion
in a number of applications. There are a few re-
ported cases where CP may have provided pro-
tection against MIC. These possible successes
have prompted further research on the subject, al-
though, the technology has not been developed
to the extent that cathodic inhibition can be relied
upon to prevent MIC in a wide range of applica-
tions. It is evident that not much is known about
the microbiological effects on CP effectiveness or
if MIC can actually be controlled consistently by
CP methods. However, CP in conjunction with a
good non-metallic lining such as epoxy-coal tar or
epoxy-fiberglass has a proven track record for cor-
rosion prevention in buried pipelines, wastewater
treatment vessels, and other applications.
Prevention of MIC in
Specific Systems
Fire-Safety Water Systems
Fire-safety water systems require specific con-
sideration regarding the prevention of MIC.12 Very
often, the makeup water sources are the same raw
water sources as used in the open-loop cooling
water systems. This water characteristically is high
in microbiological activity and often contains sub-
stantial organic contaminants. Suspended solids
may exist at levels that would contribute to the
accumulation of sludge under the stagnant con-
ditions of wet standby operation. These conditions
contribute to microbiological activity and a high po-
tential for MIC. Prevention of MIC is particularly im-
portant in fire-safety water systems because the
alternative of mitigating a MIC problem once it has
been established is difficult.
Cleaning a system for mitigation purposes is
often not practical because of system design.
System flushing may be possible, but flush-
ing can accelerate corrosion by introducing oxy-
genated water into a system containing hydrogen
9.10
sulfide and metal sulfides. Nonaggressive chemi-
cal cleaning of the entire system immediately prior
to putting it into service is the first and most im-
portant step in preventing MIC in fire-safety water
systems. When the system is clean at start-up,
subsequent efforts to prevent MIC will be more
effective. A discussion of MIC in fire-safety water
systems is presented in Chapter 6.
Selecting the best possible makeup water
source is the next step. Once the makeup wa-
ter source has been determined, a microbiological
control treatment program, based on the treatment
of the makeup water with nonoxidizing biocides
and biostats with efficacy against both aerobic
and anaerobic MIC microflora, should be im-
plemented. Biologically inert organic film-forming
inhibitors and pH adjustment can be used to sup-
plement the effect of the persistent biocide and/or
biostat treatment. In some situations, it may be
advisable to incorporate a chemical oxygen sca-
venger as part of the chemical treatment program.
It has been proposed that oxygen control may
be the most important control parameter since
it addresses all corrosion mechanisms, inclu-
ding MIC.
Microbiological surveys of the fire-safety water
systems should be made at least once per quar-
ter to ensure that the chemical treatment program
is functioning. Dead-end sites should be sampled
and tested for the presence of sulfate-reducing
bacteria and other microorganisms that may con-
tribute to MIC. Chemical analysis of the water
should be made monthly, monitoring the pH and
residual concentrations of the treatment chem-
icals, including the oxygen scavenger, if used.
When any of the.control parameters are not within
specifications, immediate steps should be taken to
correct the situation. When an increase in turbid-
ity or suspended solids is observed, bypass side-
stream filtration, or other alternatives, should be
instituted to purge the solids from the system.
Every effort should be made to reduce the
need for introducing oxygenated water into the
system once it has been put into service. All
makeup water added to the system must be
chemically treated to maintain the required treat-
ment chemical residuals.
Treatment for the Mitigation of MIC
Closed-Loop Systems
Closed-loop cooling water systems are sus-
ceptible to microbiological contamination and
subsequent MIC. However, cleaning is usually
considered only when a need exists to restore heat
transfer efficiency or when flow rates are restricted
by the formation of sludge and deposits in the sys-
tem. Like open-cooling water systems, the incen-
tive for routine cleaning may be increased when
prevention of MIC is considered.
Safety-related closed-loop systems of mixed
metallurgy should not be routinely chemically
cleaned with aggressive cleaning compounds.
Typically, these systems can be cleaned on a rou-
tine basis by on-line procedures when the sys-
tem design includes side-stream filtration. When
filtration is not available, flushing of the system by
“makeup and bleed” operations can be used. This
procedure requires the implementation of an ef-
fective water treatment program, which includes
nonoxidizing biocides, dispersants, and appropri-
ate corrosion inhibitor^.'^
Periodic treatment of the system with slug
treatments of chemicals that sequester metal ions
can be used to provide some degree of clean-
ing. Strong oxidizing agents generally are not
used for closed-loop cleaning simply because
they increase the potential for electrochemical
corrosion. Certain oxygen scavengers, such as
hydrazine, appear to provide some degree of bio-
static activity and also function to inhibit corrosion.
High-Purity Water Systems
There are a number of high-purity systems
that may experience potential MIC. The methods
for cleaning these systems may include mechani-
cal and chemical procedures, either off-line or on-
line. High-pressure water lancing has been suc-
cessful where access is available. The biomass
and other deposits can be satisfactorily removed.
However, the application of a nonoxidizing biocide
may be needed to prevent the need for immediate
recleaning.
Oxidizing agents are often considered for
chemically cleaning high-purity water systems,
inasmuch as both biocidal and cleaning effects are
Treatment for the Mitigation of MIC
obtained. Oxidants such as hydrogen peroxide do
not introduce additional contaminating solids into
the system when used for cleaning. The compat-
ibility of the oxidants with the materials of con-
struction of the system must be considered before
use. For example, hydrogen peroxide may cause
problems with some nonmetallic seal and gasket
materials. Cleaning with oxidants may not be en-
tirely effective if the oxidant does not penetrate into
the materials to be removed. The use of a non-
ionic penetrant-dispersant provides some means
of overcoming this limitation.
Prevention of MIC Under Specific
Operating Conditions
Outages and Wet Lay-Up
Scheduled outages and wet lay-up periods re-
quire special attention when developing a program
for preventing MIC. It is important that specific at-
tention be directed to preventing the uncontrolled
growth of microorganisms when environmental
conditions are substantially different from those
during operation of the system.
The most significant difference encountered
with outages and during lay-ups is that the rou-
tine procedure for biocide treatment during oper-
ation is not implemented. When this occurs, the
parameters used to specify the biocide treatment
to be used during operation are no longer relevant.
An entirely new set of parameters are needed to
prevent MIC during periods when the process is
not in operation. The basic fundamentals of bio-
cide application are quite pertinent to outage and
lay-up situations. However, two further consider-
ations must be taken’ into account: the half-life of
the biocide and whether the water is stagnant or
flowing.
Half-life of the Biocide at Existing pH and Tempera-
ture. Little consideration is given to the hydrolysis
rate or persistence of the biocide used when the
system is in operation. In fact, most of the nonoxi-
dizing biocides are selected because of their very
short half-life or rapid hydrolysis rate. During oper-
ating conditions, biocide application can be made
on a routine and frequent schedule. During out-
9.11
ages and lay-up, this may not be possible. Depend-
ing on the length of time involved for the outage
or lay-up, several alternative procedures are avail-
able to implement prevention of MIC.
The first is appropriate for use with an “as is”
lay-up. A selection is made of a persistent bio-
cide treatment, such as polymeric quaternary ni-
trogen or glutaraldehyde compounds, that can be
added to the process immediately prior to the shut-
down. Addition is made in a manner to ensure
that the treatment materials are adequately dis-
tributed throughout the system to be shut down.
In most cases, the biocide material used for rou-
tine preventive treatment would not be appropriate
for use with outages or lay-up because of a short
half-life. When assessing biocide persistency, the
half-life of the biocide at prevailing pH and temper-
ature conditions during the outage or lay-up must
be considered. The dosage levels of the biocide
should be based on the half-life of the biocide and
the time anticipated between applications or the
duration of the lay-up.
Another alternative is to drain the process,
flush the system with water treated with shock
dosages of a quick kill biocide with a very short
half-life such as hydrogen peroxide, and refill the
system with water treated with biostatic chemi-
cals including oxygen scavengers and corrosion
inhibitors, such as sodium sulfite or hydrazine.
This alternative requires frequent monitoring of
the treated water during the outage or lay-up and
provisions to make supplemental additions, if re-
quired, during the shutdown.
A third alternative would be to expand on
the routine preventive treatment used during sys-
tem operation, assuming a nonoxidizing biocide
has been used. Use of oxidizing biocides for this
application would be less effective because of
their short persistence and potential for increasing
corrosion. This option is dependent on the spe-
cific components of the system and the capabil-
ity for periodic circulation or bleed and makeup
procedures. Approximately one week prior to the
outage or lay-up, the maintenance dosage of the
biocide is increased three- to five-fold. Immediately
before shutdown, a slug addition of the biocide is
made at the maximum dosage allowed under EPA
9.12
registrations, based on the volume of the water in
the system.
Depending on the system and the biocide
used, a periodic circulation cycle should be initi-
ated. If this is not possible, a bleed and makeup
procedure is implemented where 10% of the vol-
ume of water in the system is bled per month. The
makeup water added to replace the bleed should
be treated with the biocide at the same dosage
made with the slug treatment. This alternative can
be used with short-term (6 to 16 weeks) “as is”
lay-up and wet lay-up situations. It provides the
advantage of not being required to drain, dispose
of the water, and refill the system before putting it
back into operation.
Stagnant vs. Flowing Water. Assuming it is not
possible to have the system drained and dried
during the outage or lay-up, provisions concern-
ing water flow must be considered. If design engi-
neering originally made water circulation possible,
then it should, by all means, be circulated at least
once per 1 to 4 weeks for a period long enough to
provide a 3 to 4 times turnover of the component
vol ume.
Care should be taken not to entrain air in the
circulating water. The system should be at maxi-
mum volume of water. Often during lay-up or out-
ages, parts of the system drain to less than full
volume levels. The flow velocity should be at or
above design rates to help move and transport any
sediment or sludge that may have settled out dur-
ing a stagnant period. Periodic sampling of the wa-
ter should be made before and after a flow period.
Any change in the pH, turbidity, or dissolved iron
level may indicate that further remedial steps to
prevent MIC may be necessary. Sampling of stag-
nant water may not provide sufficient information
to indicate whether or not MIC exists.
When it is not possible to drain and dry the sys-
tem, another alternative may be considered. The
pH of the water can be raised to a level greater
than 10.0. This will reduce the metabolic activity of
most of the microorganisms involved with MIC. Re-
member, however, that the pH adjustment will not
kill them. Most of the nonoxidizing biocides have
less efficacy at alkaline pHs. However, if the one
Treatment for the Mitigation of MIC
selected has an adequate half-life at the alkaline
pH, it probably will function well as a biostat at a pH
greater than 10.0. The polyquaternary ammonium
compounds generally fit into this category and
are recommended for use as a biostat at high pH
conditions.
Consideration must be given to the effect of the
high pH on the various materials of construction in
the specific components of the system. It is not
recommended that aluminum, copper, or copper
alloys be exposed to pH above 9.0 for extended
periods. This may be modified somewhat by in-
cluding azole anodic inhibitors as part of the pH
adjustment procedures. Buffered borate salts may
be a suitable alternate corrosion inhibitor in certain
situations. Before the decision is made to consider
this alternative, a plan for draining and discharg-
ing the treated water at the end of the outage or
lay-up must be made. In some cases, this may be
an important limiting factor.
Prior to putting the system into operation after
a wet lay-up or outage, the system should be thor-
oughly inspected to ensure that the potential for
MIC is minimal.
Preoperational and Hydrostatic Periods
There is limited factual documentation avail-
able to substantiate the claim that MIC often is
established during preoperational phases of plant
construction or during the preconditioning and hy-
drostatic testing phases when water is first intro-
duced into the system. However, past experiences
of the MIC specialists certainly have confirmed
that this period is critical when considering pro-
cedures for preventing MIC. It is the purpose of
this discussion to point out those factors that are
known to contribute to the MIC potential and those
factors that may help to prevent MIC during pre-
operational and hydrostatic t e ~ t i n g . ~
Preoperational Construction Phase. From the ini-
tiation of construction, through hydrostatic testing,
and into the operation phase, good housekeep-
ing and cleanliness are critical to the prevention of
MIC. This has been emphasized earlier. Keeping
components dry and free of contact with stagnant
water during this period is equally as important.
Treatment for the Mitigation of MIC
Stagnant water, such as rainwater in a pipe laying
on the ground, open tanks containing leak-test wa-
ter, or site-stored components exposed to the ele-
ments, can readily be found at every construction
site. Throughout construction and also extensive
maintenance outages, constant attention should
be paid to draining off stagnant water and drying
the components of the system. Dirt and construc-
tion debris should not be left in contact with materi-
als, particularly in the presence of moisture. If this
cannot be prevented, the components or materials
should be flushed with clean water, drained, and
dried. Drying can be achieved by the circulation
or blowing of warm air through or onto the com-
ponents. In large piping systems, drying can be
performed by the circulation of warm air or nitro-
gen gas and the moisture content of the discharge
gas monitored to ensure the desired dryness has
been achieved.
A thorough inspection of the system must be
made, component by component, on a routine
basis during the preoperational and construction
phase to confirm that the potential for MIC is
minimal.
Pretreatment Phase. The pretreatment phase is
the initial conditioning of a component or an en-
tire system, following initial construction or an
extensive maintenance project. Pretreatment ac-
tually is done in two steps. The first involves
general cleaning where construction debris, dirt,
grease, and mill scale are removed from those sur-
faces that ultimately will come in contact with the
process water. This cleaning should be done first
by mechanically removing as much foreign materi-
als as possible, and then following this by a passive
chemical cleaning flush.
The second step is to condition the cleaned
surfaces so that subsequent routine chemical
treatments will be effective. In some situations, it is
desirable to pretreat and passivate the metal sur-
faces with a high dosage of the corrosion inhibitor
to be used in the routine water treatment program.
In other cases, it may be necessary to pretreat
and passivate with materials other than those to
be used later during operations. In every case,
however, it is recommended that the pretreatment
9,13
solutions contain an adequate concentration of a
quick-kill, nonpersistent biocide proven to be effec-
tive against MIC microorganisms at the prevailing
pH and temperatures, as well as being compati-
ble with the pretreatment solution. Prior to moving
from the pretreatment phase to hydrostatic test-
ing and start-up, the system should be examined,
component by component, to confirm that the pre-
treatment procedures were completed.
Hydrostatic Testing Phase. It has been discussed
previously that selection of a high-purity water for
hydrostatic and leak testing is critical to the efforts
of preventing MIC. There are other factors that are
also important. These include how well the sys-
tem or component was cleaned prior to adding the
test water. If there was residual debris in the sys-
tem, it will often be transported to a site where
it accumulates and subsequently provides an op-
timum environment for MIC. Provisions must be
made to prevent this from occurring or to have
the capability of purging these materials following
testing.
System design is another factor that plays an
important role in the prevention of MIC during the
hydrostatic testing phase. Hydrostatic testing usu-
ally is done in progressive stages, testing each
segment of the system or individual component
as construction is completed. The system must be
designed in such a way that the individual seg-
ments can be drained completely and dried im-
mediately after hydrostatic testing. The segments
should not be allowed to stand idle even for a
few days with the test water still in them. Tanks
and vessels should be completely drained after
leak testing as well. The design of these compo-
nents should enable them to be completely drained
and not in a way that a few feet of water still re-
mains standing in the component below the drain
point.
Planning and scheduling the hydrostatic test-
ing sequence must take into consideration how
long the system will stand idle after hydrostatic
testing before the process is put into normal
operation. Every effort should be taken to do the
testing as near as possible to the time the process
will be put into operation. When it is known that
9.14
an extended period will occur between testing and
start-up, appropriate measures to reduce the po-
tential for MIC must be taken. The ideal situation
is to drain and dry.
Chemical treatment of the testing water pro-
vides some degree of assistance in preventing the
initiation of MIC during hydrostatic testing, espe-
cially when the considerations mentioned earlier
cannot be managed to the extent needed to pre-
vent MIC. However, it must be reemphasized that
water treatment alone should not be expected to
reduce the potential for MIC to zero. The water
treatment program for hydrostatic testing should
entail the use of biocides, penetrant-dispersants,
and/or corrosion inhibitors.
Biocides are perhaps the most critical part of
the water treatment program. The selection of the
biocide must be based on the specific job it is ex-
pected to do.8,9 If the quality of the makeup wa-
ter is such that a substantial MIC inoculum level
exists, a quick-kill biocide should be applied. Typi-
cally, a shock dosage of an oxidizing biocide, such
as chlorine, bromine, peroxide, or ozone, is ap-
propriate. If the makeup water contains high lev-
els of suspended solids, including organics, oils,
and greases, or if the system was not thoroughly
purged of deposit and sludge materials during pre-
treatment, or if the pH is higher than 7.8, then oxi-
dizing biocides should not be used. In any of these
situations, a quick-kill, nonoxidizing biocide is re-
quired because contact time is short and high lev-
els of suspended solids are present.
A persistent biocide-biostat should be used
when it is expected that the system cannot be com-
pletely drained or is going to be held idle in a wet
condition for more than a few days. It should be
noted that hydrostatic testing water treated with a
persistent biocide-biostat can be drained from the
system after testing and stored on site for use with
future testing. This type of biocide-biostat also pro-
vides some degree of protection from MIC when
the system cannot be completely drained or the
potential exists for residual debris in the system
after pretreatment .
~ e n e ~ r ~ n f - ~ i s ~ ecomplement
r s ~ n f s the effec-
tiveness of either oxidizing or nonoxidizing bio-
cides. Their use assists the penetration and/or
dispersion of those deposits that may exist in the
Treatment for the Mitigation of MIC
system after pretreatment. Others will suspend
residual debris in the test water and prevent
it from settling out. Some penetrant-dispersants
will form a hydrophobic film on metal surfaces
and provide some degree of short-term corrosion
inhibition.l0I1 The use of anionic polymeric disper-
sants is recommended when the test water con-
tains high levels of suspended solids and when the
metal surfaces of the system were not adequately
cleaned during pretreatment. Anionic dispersants
should be used when hydrostatic testing is done
under high flow velocity and it is possible to com-
pletely drain and dry the system after testing. This
prevents the accumulation of sludge at low flow
sites after testing is completed.
Corrosion inhibitors do not typically provide
significant benefits in preventing MIC to justify their
routine use in hydrostatic testing waters. Neverthe-
less, there are specific situations when anodic pas-
sivating agents, such as chromate, molybdate, or
orthophosphate-based inhibitors, will assist in pre-
venting corrosion of ferrous metals. Azole-based
inhibitors have been used with nonferrous metals,
such as aluminum and copper alloys. The pH ad-
justment of the makeup water to a level above 10.0
will reduce the potential for MIC where the system
can be maintained in a flooded condition follow-
ing testing and prior to start-up. Buffered borated
water may serve the same purpose under certain
conditions. Where corrosion inhibitors are used, it
is recommended that an appropriate biocide also
be used to ensure prevention of MIC.
System inspection must be done, component
by component, immediately before putting the sys-
tem into operation. This is the last time remedial
procedures can be taken to correct any situations
that occurred during preoperational phases.
Mitigation of Existing MIC
~~~ ~ ~~ ~~
Deciding on Whether Mitigation
is a Viable Option
When MIC has been identified as the cause
of the existing corrosion, it is necessary to
decide whether a mitigation program is feasible
or whether it will be necessary to remove and
Treatment for the Mitigation of MIC
FIGURE 9.1
Internal surface of carbon steel pipe that has been colo-
nized by iron-oxidizing bacteria forming tubercles. This
condition can be mitigated by mechanical/chemical
cleaning before pipe failure occurs. (See color plates.)
replace the corroded component. The following is
a series of photographs that illustrate frequently
encountered MIC. They can be used as exam-
ples of whether mitigation is a viable option for
eliminating the condition.
Figures 9.1 and 9.2 are examples of when
mechanical/chemical cleaning is a viable option.
Figures 9.3, 9.4, 9.5, 9.6, and 9.7 are examples
FIGURE 9.2
Internal surface of carbon steel pipe showing exten-
sive tuberculation caused by iron-oxidizing bacteria. The
tubercles could be removed by mechanical/chemical
cleaning, but there may be significant pitting corrosion
underneath the tubercles. (See color plates.)
9.15
FIGURE 9.3
Internal surface of carbon steel pipe and face of a
gate valve located in a fire protection system. Note
the "old" tubercles formed by iron-oxidizing bacteria
and the "new" growth on the surface of the tubercles
demonstrated by the orange-colored deposits. (Courtesy
Russ Green.) (See color plates.)
when chemical cleaning after flushing may be a vi-
able option. Figures 9.8,9.9, and 9.10 show condi-
tions where chemical cleaning would remove cor-
rosion products and result in substantial leaking.
Figures 9.1 1, 9.12, and 9.13 are examples of mi-
crobiological fouling that should be mitigated by
FIGURE 9.4
Internal surface of a carbon steel elbow covered with cor-
rosion products and tubercles formed by iron-oxidizing
bacteria. Note the aggressive attack of the weldment at
the socket welds covered by tubercles. (See color plates.)

9,16
FIGURE 9.5
Internal surface of carbon steel pipe showing corrosion
products and tubercles caused by iron-oxidizing bacte-
ria. Note that only some of the corrosion product and tu-
bercles have been removed by chemical cleaning (lower
half of split pipe). (See color plates.)
chemical cleaning before significant damage by
MIC occurs. Figures 9.1 4 and 9.1 5 illustrate dam-
age to welds on stainless steel tank walls that can-
not be mitigated by any means. Figures 9.1 6,9.17,
and 9.18 are photographs of pitting corrosion on
copper alloy materials. Pit depth or the extent of
FIGURE 9.6
Close-up view of pipe in Figure 9.5 showing the partially
removed tubercle and the pit area beneath it. To SUC-
cessfully mitigate this MIC, the cleaning solution must
penetrate though the deposited corrosion product. (See
color plates.)
Next Page
Treatment for the Mitigation of MIC
FIGURE 9.7
Internal surface of carbon steel pipe at a welded flange
colonized by iron-oxidizing bacteria. Note the black de-
posits on the metal surface where the tubercle has been
removed. (See color plates.)
penetration into the tube wall are the criteria that
are used to determine whether replacement or mit-
igation is the most practical procedure.
Preprogram Planning
Mitigation of MIC should be considered much
in the same way as a major maintenance program.
FIGURE 9.8
Exterior surface of pipe shown in Figure 9.7 showing the
through-wall penetrations of pits caused by growth of
sulfate-reducing bacteria underneath tubercles seen in
Figure 9.7. (See color plates.)
Previous Page
Treatment for the Mitigation of MIC
FIGURE 9.9
Cross section of carbon steel pipe with a large tubercle
on the interior surface. Note the stratification of layers
of deposited iron products that formed as the tubercle
grew in size. Note also the large pit and through-wall
penetration caused by sulfate-reducing bacteria growing
in the anaerobic environment underneath the tubercle.
(See color plates.)
It requires the same degree of planning and
coordination by all operating groups involved with
such activities. Before the initiation of the ac-
tual mitigation procedures, several considerations
must be taken into account to ensure the success
of the program.
FIGURE 9.10
Close-up view of the anaerobic pit area underneath the
tubercle shown in Figure 9.9. Note the through-wall pen-
etration. (See color plates.)
9.17
FIGURE 9.11
View of heat exchanger tube sheet covered with biomass
and corrosion product. Note the tuberculation on the in-
ner surfaces of the tubes. Unless removed by cleaning,
these will provide sites for pitting and reduce flow rate
through the tubes. (See color plates.)
Assessment of Severity and Extent of MIC
As with all corrosion problems, assessing the
severity of the problem is subjective up to the point
of component failure. With MIC, one must consider
that as long as microorganisms are involved, the
problem will continue to get more severe. Very few
MIC situations are self-passivating, nor will they
disappear by themselves.
FIGURE 9.12
View of heat exchanger tube sheet and tubes with tuber-
culation caused by iron-oxidizing bacteria. (See color
plates.)
9.18
FIGURE 9.1 3
View of heat exchanger tuber sheet and tubes fouled by
biomass and corrosion product. (See color plates.)
The primary types of corrosion as related to
MIC are described next.5
fitting Corrosion. Pitting corrosion is characteris-
tic of several different mechanisms of MIC. Pitting
corrosion rates can be very high, especially when
the MIC involves the growth of sulfate-reducing
bacteria in anaerobic environments. Anodic pitting
corrosion cells are very localized. Through-wall
penetrations of heat exchanger tubes and piping
represent the extreme of severity.
FIGURE 9.14
View of 304 stainless steel welded tank wall showing
attack by microorganisms. Note the rust streaks coming
from corrosion sites at the welds and the numerous small
corrosion sites scattered over the tank wall. (See color
p Iates.)
Treatment for the Mitigation of MIC
FIGURE 9.15
Close-up view of the corrosion site at the weld on the
tank wall shown in Figure 9.14. (See color plates.)
General (Lateral) Corrosion. Metal loss, as a re-
sult of lateral corrosion involving large anodic sur-
face areas, can be extensive with MIC. The metal
loss may be significant, but the severity of the cor-
rosion often is more related to the fouling caused
by the corrosion by-products. Reduction of water
flow rates, loss of heat transfer efficiency due to
deposits, and plugging of filters and strainers rep-
resent the extreme of severity.
FIGURE 9.16
View of the internal surface of a 90/10 copper-nickel heat
exchanger tube showing pits into the base metal and sur-
face covered with biofilm. (See color plates.)
Treatment for the Mitigation of MIC
FIGURE 9.1 7
Close-up view of a pit and deposition of corrosion pro-
duct on the surface of a 90/10 copper-nickel heat ex-
changer tube. This corrosion is caused by slime-forming
metal-oxidizing bacteria. (See color plates.)
Crevice Corrosion. Crevice corrosion is charac-
teristic of both nonmicrobiological and microbio-
logically influenced mechanisms. Most often, the
nonmicrobiological mechanisms are a result of dif-
ferential aeration under deposits and in stagnant
areas where gravitational factors are involved. This
is not the case with MIC crevice corrosion since it
can appear anywhere around the circumference of
FIGURE 9.18
Close-up view of a pit into the base metal of an admi-
ralty brass heat exchanger tube. Note (X) the absence of
corrosion product and the deposition of elemental cop-
per in the pit. Note also the surrounding surface of the
tube covered with dehydrated biofilm. This corrosion is
caused by slime-forming metal-oxidizing bacteria. (See
color plates.)
9.19
a component and on both vertical and horizontal
surfaces. Structural strength loss, metal cracking,
and through-wall penetration represent the ex-
treme of severity.
Stainless Steel Corrosion. Most cases of MIC on
stainless steel are characterized by the forma-
tion of pits or tunneling, most commonly at weld-
ments, crevices, and other stressed-metal sites.
The metal loss often is associated with attack of
the weld material near the fusion line or with sen-
sitization in the heat-affected zone. Base metal at-
tack is much less common. Two-phase weld metal
appears to be the most susceptible area, although
the relative susceptibilities of austenite and delta
ferrite phases have not been clearly defined. The
severity of stainless steel corrosion is difficult to as-
sess visually until component failure has occurred.
This is because the pits and metal loss are subsur-
face and result in cavities or tunnels within the wall
of the component. The extreme of severity is rep-
resented by through-wall penetration, leaks, and
loss of structural strength.
Nonferrous Alloy Corrosion. As discussed in other
sections, virtually all metals are susceptible to MIC.
The assessment of MIC severity on the nonfer-
rous materials are based on the same basic cri-
teria already discussed. The one further criterion
to be pointed out is related to erosion-corrosion
and denickelification of copper-nickel alloys, which
appears to be more severe when associated with
microbiological growth.
Identification of Limitations
System Design. When dealing with mitigation
of MIC, attention is usually focused on specific
components or isolated systems. Only under
unusual circumstances is it necessary to deal with
an entire process water system. When massive
systems are involved, it is advisable to divide the
system into manageable segments and deal with
each separately.
The site(s) where MIC exists must be precisely
defined. Accessibility to the sites must be evalu-
ated. Provisions to clean the system mechanically,
the capability to chemically clean, and the abi-
lity to apply chemical treatment must be assessed
with respect to system design. Most limitations
9.20
imposed on mitigation procedures by system de-
sign are related to availability of access ports re-
quired to do mechanical cleaning, to the capability
of recirculating chemical cleaning solutions, and
to the procedures required to discharge cleaning
solutions, corrosion debris and treated water from
the system. Once the general plan for the mitiga-
tion procedure has been made, suitable alterna-
tives must be developed to overcome the design
limitations that exist.
For example, an isolated heat exchanger sys-
tem and related piping were severely fouled with
deposits and tubercles formed by the growth of
Gallionella s p. (ae ro bic iro n-oxidiz ing bact eria).
Pitting corrosion also was occurring under the tu-
bercles. The design of the system did not provide
the capability to circulate the cleaning solution only
through the heat exchanger and related piping.
The piping consisted of several different internal
diameter pipes. This made mechanical cleaning
difficult.
Under the existing circumstances, it was not
possible to circulate a chemical cleaning solution
without circulating both the solution and all the
dirt and debris it removed through the entire sys-
tem. An alternative was considered to isolate the
heat exchanger and associated piping, valve off
the main circulation headers, and tie into a tempo-
rary circulation loop from a tanker truck equipped
with a 6,000-gal tank and pump. In-line filters on
the pipe from the tanker were used to remove the
corrosion by-products from the cleaning solution
being circulated from the tanker to the heat ex-
changer and back to the tanker.
Disposal of the cleaning solution and deposits
removed from the system were no longer a prob-
lem. The risk of removing deposits from one
site and redepositing them at another site was
eliminated. This is just one example of several
alternatives to consider when one is faced with
limitations created by system design factors. A
complete knowledge of the system and an under-
standing of what must be done to achieve mitiga-
tion of MIC will lead to other alternativesi4
Materials of Construction. Consideration of ma-
terials of construction must be made during the
preprogram planning phase. This is relevant to
Treatment for the Mitigation of MIC
both on-line and shutdown programs. Materials of
construction play a role in the selection of mecha-
nical, physical, or chemical cleaning procedures.
It must be noted here that additional considera-
tion must be made when dealing with mitigation
of an existing MIC situation. One is dealing with
materials that are already in a corroded condition,
and the purpose of the mitigation program is to
inhibit existing corrosion. Particular attention must
be paid to providing a means for protecting all the
various materials during the mitigation program.
Effluent Discharge. A defined plan for handling
the effluent of a mitigation program should be in
hand before the program is initiated. With shut-
down programs, highly alkaline or acidic effluent
should be anticipated. Very often, the effluent con-
tains high levels of suspended solids composed
of both organic (oils and greases) and inorganic
materials. Most industrial waste treatment facili-
ties are not designed to handle the effluent from a
shutdown mitigation procedure based on chemical
cleaning for the short period when the system is
not in operation. The effect of the shutdown on the
operation of the waste treatment facility must be
considered.
On-line mitigation programs do not usually
present major problems related to effluent dis-
charge. An important factor that must be con-
sidered, however, is the handling of suspended
solids, corrosion by-products, and the dirt and de-
bris that will be removed from the system during
the program. In-line or side-stream filtration is of-
ten the ideal solution, but these may not be avail-
able. Therefore, it is necessary to provide a means
of purging these materials from the system on a
routine basis that is compatible with the effluent
discharge process. Regulatory permits and reg-
istrations for chemicals used in both on-line and
shutdown programs must be reviewed as part of
the preprogram planning phase.
Deciding on On-Line or Shutdown Mitigation
An on-line mitigation program is described as
a procedure designed to immediately prevent a
MIC situation from becoming more severe and to
ultimately eliminate it. This is to be carried out
while the system or specific component is still in
Treatment for the Mitiaation of MIC
operation. A shutdown program involves taking the
system out of operation for the purpose of carrying
out procedures to eradicate MIC within a relatively
short period of time.15
On-line mitigation of MIC should be consid-
ered when it has been determined that shutting
the system down for the duration required to do
a shutdown program is not practical nor possible.
As a general rule, it is best to initiate the mitiga-
tion program as soon as possible. Delaying miti-
gation most likely will lead to more difficulties later
and also reduce the probability of a successful pro-
gram. A properly executed on-line program can be
started within a short time after the MIC problem
has been identified. Once the on-line program has
been initiated, it would be expected that the de-
gree of severity of the MIC will decrease to the
point where delay is no longer a consideration.
It is difficult to generalize how long an on-
line mitigation program will take to successfully
eliminate MIC. However, it appears that there is
a correlation between how long the MIC existed
before mitigation was implemented and the length
of time required for a successful on-line program.
The longer MIC has existed, the longer the time re-
quired to mitigate it. Past experiences have shown
that some on-line programs have been completed
within a six-week period. In other cases where
the MIC was a relatively severe chronic problem,
periods up to nine months were required to miti-
gate it.16
On-line mitigation may offer alternatives to
system-design limitations, which prohibit shut-
down mitigation. In many cases, on-line mitigation
solves effluent discharge problems associated
with shutdown procedures. Most on-line miti-
gation programs involve the use of specialized
water treatment chemicals, which are more adapt-
able to open recirculating systems, closed re-
circulation systems, and closed-loop systems.
Once-through systems are less suited to on-line
chemical treatment mitigation programs. On-line
physical and mechanical procedures discussed
later have been somewhat successful in certain
once-through systems.l
Shutdown mitigation should be scheduled to
coincide with major maintenance outages or other
major shutdown events when possible. However,
9.21
these events should not detract from time and
personnel priorities required to do the mitigation
properly.
Under certain circumstances, an on-line pro-
gram can be initiated to prevent the MIC from
becoming more acute and then followed by a shut-
down mitigation program coordinated with other
shutdown activities.
Cost Effectiveness vs. Anticipated Results
It is not within the scope of this chapter to dis-
cuss the cost effectiveness of the various alter-
natives available for mitigation of MIC. However,
it should be noted here that unmitigated MIC can
be catastrophic and, subsequently, extraordinar-
ily expensive.’ Because of this fact, when a mit-
igation program is to be done, it should be done
completely and not compromised because of cost
restraints. Cost considerations will affect the de-
cisions on whether to do an on-line or shutdown
program. Cost considerations will enter into the de-
cision to replace a component rather than attempt
to mitigate a MIC condition.
Assessment of cost effectiveness is first based
on anticipated results and then is finally deter-
mined at the time the mitigation program is com-
pleted. A risk is involved with on-line programs
because there is no way to guarantee that it will
be completely successful. The success may be a
matter of degrees. On-line mitigation is carried out
over an extended period of time. This may involve
substantial expenditures for treatment chemicals,
added labor, and accessory equipment. However,
it may be anticipated that a successful on-line
mitigation program will enable considerable sav-
ings in future chemical treatment costs, eliminate
need for replacement of equipment, and prevent
production loss due to shutdown. Also, a value
must be placed on the fact that the on-line mitiga-
tion should prevent the MIC from becoming more
severe.
These factors may justify the risk mentioned
earlier. Shutdown mitigation may be more expen-
sive initially, especially if lost production needs to
be included into the cost of the program. However,
when the shutdown programs are effectively car-
ried out, the risk factor is much less.
9.22
Implementing a Mitigation Program
Mechanical Cleaning
The first stage of a mitigation program, no mat-
ter what procedure is employed, is to remove the
loose or loosely adhering debris from the system
as much as possible. The debris typically consists
of corrosion by-products, deposited sludge of vari-
ous chemical compositions, and biomass. Routine
mechanical cleaning for MIC prevention was dis-
cussed earlier. Much of that discussion is relevant
to procedures used to mitigate MIC.3,6
Water Flushing and Draining. Removal of loose
debris associated with MIC is usually done first
by a water flushing and draining, repeated as many
times as possible. Water flushing and draining may
be supplemented with air bumping (pulsing high-
pressure air) through pipes or into a component
body. These techniques can effectively remove
loose deposits, but they will not do a complete job
of cleaning the metal surfaces to which the more
tenacious biomass and corrosion by-products ad-
here. Flushing and draining may be considered
as preparation for a more thorough cleaning pro-
cedure. In cases where the MIC is not extremely
severe and there is a limited amount of debris as-
sociated with it, the flushing and draining proce-
dure is adequate pretreatment prior to initiating an
on-line mitigation program.
Mechanical Removal (Pigging, Brushing, and
Hydrolazing). Once the loose materials have been
removed, the piping, heat exchangers, tanks, and
other components can be further cleaned by me-
chanical methods. Piping systems and heat ex-
changers may be cleaned using metal or vinyl
scraper plugs (pigs), which are propelled through
the pipe or heat exchanger tubes by pressurized
gas or water. Straight sections and smaller inter-
nal diameter pipe are most suited to the use of
pigs.
Piping runs uninterrupted by valves, diameter
reductions, or many changes in direction may be
cleaned in this manner, assuming there are access
ports for insertion and removal of the pig. Straight
tube heat exchangers also are readily cleaned by
this method and by brushing when manual manip-
Treatment for the Mitigation of MIC
ulation is required because of accessibility limita-
tions.
Sponge-ball cleaning systems provide an on-
line cleaning method for mechanically removing
MIC-related deposits from tubes and pipes in both
once-through and recirculation systems. Sponge
rubber balls, available in various degrees of stiff-
ness, with and without abrasive coatings, and of
a diameter slightly larger than the pipe or tube,
are periodically introduced into the fluid stream,
passed through the pipe or tubes, and then col-
lected in a downstream area of the system and
cycled back to the injection area. This type of on-
line cleaning can improve the removal of deposits,
but it must be used in conjunction with other pro-
cedures, such as water treatment using biocides
and dispersants.
Methods that utilize solids suspended in a
liquid stream may be effective in situations where
the deposition on pipe or vessel surfaces is not
severe. With relatively thin films, the abrasive
particles will flow along the filmed surface and
remove the deposit. The sandblasting or jetting
procedure, which involves suspending sandblast
materials in a dry nitrogen carrier, is used pri-
marily as a means for preparing surfaces to
be coated. Only under very extreme conditions
should sandblasting be considered when no
coating is to be applied. High-pressure water
sprays, such as in hydrolazing, have been used
extensively for removal of deposits in preparation
for subsequent water treatment procedures, and
for tubercle removal when accessibility was not
limited. Recent improvements in the hydrolazing
process allow equipment to access smaller and
more remote areas of a system.
The primary limitation to hydrolazing, sand-
blasting, manually brushing, and other mechani-
cal procedures is that they must be done off-line,
and single setups are limited to sites where no
changes in direction or bore exist. When abrasive
particles are used, it is necessary to provide for
the collection and removal of particles as well.
Chemical Cleaning
The mechanical cleaning methods discussed
earlier provide means for removal of the loose or
Treatment for the Mitigation of MIC
loosely adhering deposits associated with MIC.
Very often, it is necessary to do further cleaning
to remove the tubercles and other deposits that
are tightly adhering to the metal surfaces. Chem-
ical cleaning has become a widely used and ac-
cepted p r o c e d ~ r e .It~is, ~generally safer and more
economical than the labor intensive mechanical
and physical methods, which require extensive dis-
mantling.
Selection of Cleaning Chemicals. Selection of the
cleaning solvent or solution and how it is applied
is based on several factors. These include:
Chemical Composition of Deposits:
Some relevant information may already
be available from the analyses done
to detect and confirm MIC It is impor-
tant, however, to base cleaning chem-
ical selection on the composition of
the deposits adhering to the metal sur-
faces and not just on sludge or loosely
adhering materials found in the sys-
tem. Tube or pipe samples with intact
deposits are the best samples for analy-
sis. If these are not available, then de-
posits must be scraped from the metal
surfaces, with care taken to scrape down
to the base metal surface. Deposits usu-
ally vary in depth and often have dis-
tinct layers of different composition. The
location of sampling must be carefully
selected, with considerations given to
collection at the most trouble-prone
sites, such as sites of low-flow velo-
city and areas ,of known MIC. Areas of
catastrophic failures should be avoided
because the conditions caused by the
failure often wash out much of the
deposit, making the immediate area
unreliable for study. When practical,
simulated cleaning tests with specimens
taken from the system should be done in
the laboratory.
Materials of Construction: Mitigation
cleaning procedures require complete
consideration of the materials of con-
9.23
struction of all wetted surfaces and
parts in the system. This includes items
such as O-rings, packings, gaskets,
nonmetallic components, and coatings.
If there is any question as to the
compatibility of the cleaning solvent or
solution with specific materials of con-
struction, laboratory exposure tests, un-
der the most extreme conditions, should
be made before using the cleaning
chemicals.
Temperature Considerations: The sys-
tem design should be reviewed to es-
tablish the maximum safe temperature
that could be applied during cleaning
and to determine the maximum temper-
ature obtainable from a practical stand-
point. Often the system will tolerate a
higher temperature safely than can be
obtained during cleaning procedures.
Most cleaning solvents and solutions
have an optimum temperature range for
maximum performance and corrosion
protection.
Application Procedures: The ideal ap-
plication procedure is to make up the
cleaning chemical in a separate tank,
verify its composition, and then add it
to the system or component when refill-
ing after the final flushing. Once made
up, the system should be circulated
continuously or intermittently throughout
the project. If circulation is not possi-
ble and a “soak” procedure is neces-
sary, the cleaning chemicals must be
added as the system is being refilled
after draining. This ensures proper dis-
tribution of the cleaning chemicals. A re-
peated “bleed and makeup” procedure
may be necessary if circulation is not
possible.
Proper velocity is an important con-
sideration when circulation is employed.
Solvent movement is necessary to
prevent localized neutralization. Corro-
sion and erosion rates increase with
9.24
velocity, and usually not at a linear rate.
Cleaning solvents, based on inhibited
mineral acids such as hydrochloric and
sulfuric, should not be circulated at rates
exceeding 1 to 2 ft/s when circulated
for extended periods. Solvents, based
on chelants such as EDTA and HEDTA,
NTA, and organic acids, usually are
circulated continuously at velocities of
1 to 5 ft/s. Some cleaning and solvent
materials interact with the deposits to
release gases including CO2 and H2.
Provisions for venting should be made
prior to starting the procedure. Occa-
sionally, foam may be generated in the
system as the cleaning chemicals are
being circulated.
Some types of cleaning solvents can
be foam-applied. This has proven to
be particularly effective for large shell
and tube exchangers or surface con-
densers where circulation capability is a
limiting factor. Foam application has the
advantage of lightweight, direct applica-
tion and the ability to move insoluble or
sloughed pieces of deposit large in size.
The primary limiting factor for foam ap-
plication is accessibility.
Methods to propel a cleaning solvent
through a system with a gas, such as
air, steam, or nitrogen, are being deve-
loped. This can be an effective means
for cleaning piping where large volumes
are involved.
Water Requirements: Water manage-
ment should not be overlooked. The
availability of water is involved in decid-
ing the concentration of the cleaning sol-
vents and solutions. It is necessary to
have adequate quantities and delivery
rates for all rinses, flushes, and pas-
sivation stages. Minimum water quality
requirements should be addressed as
well.
Time Considerations: Time required to
do an adequate cleaning program is
Treatment for the Mitiaation of MIC
perhaps the most difficult factor to pre-
dict. The question is, “How much time
is available and how much time is it ex-
pected to take?” Past experiences have
shown that it is prudent to allow a safety
factor between the maximum available
time and the expected time. This may
influence the final choice of solvent, con-
centration of solvent, and/or application
method.
Other Considerations: Some other fac-
tors to consider, no less important than
those discussed herein, are:
disposal of spent cleaning and sol-
vent solutions,
safety practices to ensure all per-
sonnel are free from injury and that
losses are not suffered from any
work-related, unplanned incident,
corrosion monitoring,
criteria that the project has been
completed to the desired degree,
and
corrosion inhibition (passivation)
procedures during and following
completion of the project.
Chemical Application Procedures. The use of var-
ious chemical treatment procedures to mitigate
existing MIC is situation-specific and dependent
on the results of procedures carried out prior
to the application of the chemicals. This discus-
sion provides information related to the application
of chemicals during the chemical cleaning stage
and during subsequent steps to eradicate the mi-
croorganisms, to passivate active corrosion sites,
and to establish a preventive treatment program.
A coordinated chemical treatment approach has
been shown to be essential to obtain the most
effective results from chemical treatment. Any-
thing less than a total treatment program most
likely will create a potential for the continuation
of MIC or perhaps its reoccurrence within a short
time.
Treatment for the Mitigation of MIC
Taking into consideration what pretreatment
procedures were used, one can use three ba-
sic chemical treatment a p p r 0 a ~ h e s . l ~These
are:
Short-Term, Shut dow n, Ag gressive
Chemical Cleaning: This approach
to MIC mitigation has been discussed
to some extent earlier. The guidelines
highlighted therein must be followed.
It is used when a limited amount of
shutdown time is available, or when
the mitigation procedure must be timed
with some other maintenance activity or
to comply with a short-term outage. It
is usually necessary to use aggressive
chemical cleaning solvents to remove
the residue deposits not removed by
physical cleaning and flushing. Typi-
cally, the deposits are hard tubercles
that have developed over an extended
period of time. This approach often
is used to mitigate MIC at a readily
isolated site or component that has
ready access for adding the chemicals
and circulating the cleaning solution
under controlled conditions.
The use of a chemically stable, non-
ionic penetrant dispersant is recom-
mended when using aggressive clean-
ing chemicals.18 This type of chemical
expedites the penetration of the de-
posits by the cleaning chemical and in-
creases the rate of removal. It should
be added directly to the cleaning s o h -
tion as the system is being filled. Be-
cause the cleaning chemicals can more
readily penetrate the deposits, it reduces
the time that the metal surfaces are ex-
posed to the aggressive chemicals and,
in general, reduces the adverse effects
that this procedure has on unprotected
surfaces in the system. Certain types
of penetrant or dispersant form films on
metal surfaces that provide short-term
passivation to the aggressive cleaning
chemicals.
9.25
It should not be assumed that the
cleaning chemicals will eliminate the mi-
croorganisms responsible for MIC. lt is
necessary to include the addition of a
biocide as part of this procedure. In
severe situations, nonoxidizing biocides
can be added directly to the cleaning so-
lution, but the biocide must be stable in
the cleaning solution. Oxidizing biocides
are not effective as part of the cleaning
solution. However, chlorine, hypochlo-
rite, peroxide, and other oxidizing agents
can be applied with the rinse water
following discharge of the cleaning
solution.
The system must be passivated fol-
lowing the rinse step. This is usually
done by neutralization with an alkaline
solution, or by the application of a corro-
sion inhibitor at 3 to 5 times the main-
tenance dosage level. Nonoxidizing
biocides are typically added to the rinse
water or to the fresh makeup water fol-
lowing passivation. If added to the rinse
water, adequate contact time with the
biocide in the system must be provided.
In most cases, nonoxidizing biocides are
the materials of choice over oxidizing
agents because of the lower potential for
activation of corrosion.
Short-Term, Shut dow n, Nonaggressive
Cleaning: This approach is distin-
guished from the aggressive cleaning
approach only by the cleaning chemi-
cals used. It is most appropriate when
the residual deposits, following physical
and mechanical cleaning, are soft and
porous. The cleaning solutions are
based on neutral or alkaline chemicals
that have a degree of surfactant activity.
Included as part of the cleaning solution
are chemicals with anionic polyelec-
trolyte properties such as sodium
salts of polyacrylate, polyacrylate-
acrylamide copolymer, phosphonate,
or organophosphate. Alkaline chelating
9.26
agents can also be used. The use of
chemically stable non-ionic penetrants
and dispersants is recommended with
this procedure as a means for increased
penetration of the deposits. The ag-
gressive procedure described earlier
functions by dissolving much of the
deposited materials. The nonaggressive
procedure functions by penetrating and
dispersing or suspending the deposits.
The penetrant or dispersant increases
the probability of a complete cleaning.
This approach can be used only when it
is possible to circulate the cleaning solu-
tion through the system and when there
are facilities to remove the suspended
solids from the circulating solution. In
some situations, it may be necessary
to repeat the circulation stage of this
procedure to get a complete mitiga-
tion. Often the time required for the
nonaggressive cleaning approach will
be greater than that required for the
aggressive approach.
It must not be assumed that the
cleaning solution will eliminate the activ-
ity of the microorganisms contributing to
MIC. A biocide or biostat treatment must
be included as part of the procedure.
The pH and the oxidant demand of the
cleaning solution determine if an oxidiz-
ing agent can be used as the biocide. If
the pH is greater than 8.0 or the oxidant
demand ratio to provide a free residual
oxidant is greater than 10:1, oxidizing
agents should not be considered for use
in the procedure. Nonoxidizing biocides
and biostats with stability in the cleaning
solution and a half-life greater than the
duration of circulation, and with efficacy
to the MIC microflora, can be added
directly to the cleaning solution. A
supplemental addition of biocide should
be added to either the rinse water or
to the fresh makeup water following
cleaning. If it is added to the rinse water,
adequate contact time must be pro-
Treatment for the Mitigation of MIC
vided when nonoxidizing biocides are
used.
Long-Term, On-Line, Nonaggressive
Chemical Treatment: As discussed
earlier, the on-line cleaning approach to
mitigation is considered when it is not
practical to take the system or compo-
nent out of service. In some cases, the
primary objective of this approach is to
prevent the MIC from becoming more
severe, until other approaches can
be implemented.5112The basis for the
on-line treatment is the modification of
a maintenance or preventive treatment
program focusing on gradually eliminat-
ing MIC. The on-line mitigation treat-
ment is characterized by the fact that
it is a passive procedure, specifically
designed to reduce corrosion in a
corrosive environment.
Every step in the procedure must
be directed to reducing the potential for
corrosion as influenced both by microor-
ganisms and by nonmicrobiological fac-
tors. The greatest degree of success by
on-line mitigation is obtained when the
MIC is in early stages of development
and there is a minimum interaction with
other corrosion mechanisms.
The first step in this approach is
to remove as much as possible of the
sludge, corrosion by-products, and
other debris from the sites where MIC
exists. Draining and flushing the system
is highly recommended when possible.
This must be done as passively as possi-
ble and aeration of the flush and makeup
water should be minimized. The objec-
tive is to avoid stimulating or accelerat-
ing corrosion by the cleaning procedure.
If not already in place, good housekeep-
ing procedures must be implemented.
The next step is to include into
the routine water treatment program a
mechanism to penetrate and disperse
the biomass associated with the MIC.
Treatment for the Mitigation of MIC
Slug dosages of biodispersant should
be made at frequent intervals. Care
should be taken not to break loose
uncontrollable amounts of deposits in
severely fouled systems. As the slug
doses of biodispersant are applied,
the system should be operated in a
bleed-and-makeup cycle. Hydrophobic
biodispersants are the most effective
for use in once-through systems where
recirculation is not possible.1°
Following completion of the periodic
slug dosages of biodispersant, a routine
addition of the biodispersant should
be initiated and continued throughout
the duration of the mitigation program.
A penetrant or dispersant should be
included as part of the water treatment
program at that time when the majority
of the biomass has been dispersed from
the system surfaces. When possible, the
criteria for selection of the penetrant or
dispersant should include its filming and
passivating properties. The penetrant or
dispersant should be applied initially at
high dosage levels and then gradually
reduced to maintenance dosage levels.
Biocide addition should be initiated
concurrently with the addition of the
biodispersant and, subsequently, with
the penetrant or dispersant. Nonoxidiz-
ing biocides are the materials of choice,
at least until there is good evidence that
the production of biomass has been
inhibited. The penetrant or dispersant
will enhance the effectiveness of the
biocide by providing a mechanism for
the biocide to penetrate into the de-
posits and contact the microorganisms
at the corrosion site.
The gradual removal of residual
deposits and tubercles adhering to the
surfaces is implemented by the applica-
tion of anionic polyelectrolytes, such as
those discussed in the previous sec-
tion. Recent advances in water treat-
ment technology have provided multi-
9.27
functional dispersant-corrosion inhibitor
compounds that are particularly effec-
tive in on-line MIC mitigation programs.
The use of these materials is limited
to open-recirculation and closed-loop
systems, primarily because of cost.
Intermittent applications of anionic
polymeric dispersants are suggested
for once-through systems.
Specific attention must be paid to
the totally coordinated water treatment
program during the on-line mitigation
program. The chemical treatment used
for mitigation must be compatible
and complementary to the routine
maintenance water treatment program.
All deviations from the recommended
program and any variations in the
operating conditions of the system must
be compensated for.
Periodic inspections and monitoring
procedures should be implemented
at the start of the mitigation program.
Visual inspection of the MIC sites
should be made at every possible op-
portunity. When it appears necessary,
adjustments in the on-line treatments
should be made.
If the on-line mitigation procedure
is carried out in a passive mode, pas-
sivation is not a primary consideration.
However, in those situations where the
process water has corrosive properties,
regardless of MIC, conventional corro-
sion inhibitors should be used during
the mitigation program.
Inhibitors based on anodic passi-
vation typically are less effective when
used at traditional dosages because
of the residual materials on the metal
surfaces. Incomplete anodic passivation
may lead to localized pitting corrosion.
Corrosion inhibitors employing cathodic
inhibition or a combination of cathodic
and anodic mechanisms typically
provide the most effective results.
The use of the anionic polyelectrolyte
9,28
dispersants in the on-line mitigation
procedure complements the effective-
ness of the multifunctional corrosion
inhibitors.
The use of pH adjustment, appli-
cation of oxygen scavengers, and use of
other less-conventional corrosion inhi-
bitor treatment approaches also should
be considered as part of efforts to both
prevent MIC and to mitigate existing MIC
situations. These approaches are more
relevant to closed-loop or recirculating
processes, and the potential benefits
must be considered on a case-by-case
basis.
Chemicals used to mitigate MIC with each of
the approaches previously listed fall into four
general categories. These are:
Biocides/biostats-Chemicals designed to
kill existing microorganisms or prevent
the microflora from reaching critical pop-
ulation levels.
Penet rant/bi odispersants-C hem icals de-
signed to penetrate into the biomass,
disperse the materials deposited at or
near the corrosion sites, and provide a
mechanism for the biocide to contact
the sessile microflora associated with
MIC.
Anionic dispersants-Chemicals designed
to disperse and suspend the deposits,
corrosion by-products, and sludge as-
sociated with MIC. These materials also
provide a mechanism for the biocide to
contact the sessile microflora associ-
ated with MIC.
Electrochemical corrosion inhibitors-
Chemicals designed to inhibit the
corrosion process by anodic passi-
vation, cathodic passivation, physical
barrier film passivation, oxygen sca-
venging, or neutralization. Many of the
corrosion inhibitors currently in use
Treatment for the Mitigation of MIC
employ a combination of these mechan-
isms.
Maintenance and System Design Changes
Mitigation of MIC cannot be achieved by clean-
ing and chemical treatment alone. It is necessary
to go directly to the origin of the problem. As dis-
cussed earlier, this may involve certain mecha-
nical or operational conditions that contribute to
the perpetuation of MIC in spite of any preventive
measures and mitigation programs used to con-
trol MIC. Factors to consider during the prepro-
gram and implementation phases of the mitigation
of MIC follow.
Mitigation of MIC cannot repair a leaking ves-
sel or a through-wall pit. The only logical option is
to replace the equipment. A thorough diagnosis of
the cause of the MIC situation should provide in-
formation needed to ensure that the problem will
not recur. Replacement should be done as soon
as possible, not necessarily after the mitigation
is completed. The optimum situation would be to
complete the repairs or replacement during a shut-
down mitigation program.
System design modifications must be coordi-
nated with long-range planning of maintenance
and operational modifications. The several fac-
tors discussed here should be added to the list of
criteria that govern system design modifications.
The need to carry out a MIC mitigation proce-
dure demonstrates the need to consider relevant
system design modifications. Such modifications
include adjustment of flow rates, elimination of
stagnant or dead-leg flow sites, provision of chem-
ical addition facilities, provision for cleaning and
flushing facilities, side-stream filtration capabili-
ties, bypass designs to facilitate routine cleaning,
and alternative materials of construction. The pur-
pose of bringing this matter up is twofold. First,
there is no better time to observe what design mod-
ifications are needed than during a MIC mitigation
procedure. Second, there is no better time to im-
plement certain system modifications than during
a shutdown mitigation procedure.
It is advisable to use every possible method
of monitoring and inspection during both
Treatment for the Mitigation of MIC
shutdown and on-line mitigation procedures. Very
often, the facilities to do an effective job of
monitoring the progress of the mitigation program
are not available. Monitoring of MIC will be
discussed in another chapter of this book and
includes a description of some of the techniques
and equipment available. A monitoring process
should be planned prior to the start of a mitigation
procedure. If specific equipment is required and
not available, installation should be done at the
time the mitigation is begun.
Postmitigation Chemical Treatment
The last, but certainly not the least, important
step in the mitigation of an existing MIC problem
is the establishment of a program to prevent its
recurrence. The potential for recurrence of MIC in
a system that has experienced a mitigation pro-
cedure is much greater than in a system where
MIC has not yet occurred. There are several rea-
sons for this. However, the most important factor to
consider is that preventing MIC is generally more
successfully achieved than mitigating MIC.
Prevention of MIC should be given top priority,
especially after a successful mitigation has been
accomplished. A planned treatment and opera-
tions program for the prevention of MIC should be
initiated immediately upon completion of the miti-
gation program. Nothing should be left to chance.
All points discussed concerning prevention of MIC
should be reviewed and put into operation to pre-
vent MIC from recurring.
References
1. A.M. Brennenstuhl and P.E. Doherty, “The Eco-
nomic Impact of Microbiologically Influenced Cor-
rosion at Ontario Hydro’s Nuclear Power Plants,” in
Microbiologically lnfluenced Corrosion and Biode-
terioration, eds. N.J. Dowling, M.W. Mittleman,
and J.C. Danko (Knoxville, TN: Univ. Tennessee,
1991).
2. A Practical Manual on Microbiologically Influenced
Corrosion (Houston, TX: NACE, 1993).
3. R.W. Lutey, “Microbiologically Influenced Corrosion
9.29
(MIC),” 8/94 ed., EPRl TM 1001 (Palo Alto, CA:
Electric Power Research Institute, 1994).
4. D.H. Pope, “A Study of Microbiologically Influenced
Corrosion in Nuclear Power Plants and a Practi-
cal Guide for Countermeasures,” EPRl NP-4582
(Palo Alto, CA: Electric Power Research Institute,
1986).
5. G.J. Licina, “Source Book for Microbiologically In-
fluenced Corrosion in Nuclear Power Plants,” EPRl
NP-5580 Electric Power Research Institute, (Palo
Alto, CA: 1988).
6. T.O. Brice and W. A. Glover, “Service Water Chem-
ical Cleaning at River Bend Gets Results,” COR-
ROSION/94, Paper no. 251 (Houston, TX: NACE,
1994).
7. J.R. Antoine, et al., “Iron and Manganese Cooling
Water Deposits at SERI, Grand Gulf Nuclear,” pre-
sented at Service Water Systems Reliability Sem-
inar, held Oct. I7-1 9, 1988, Charlotte, NC, SWAP
Tech. Library No. 0-01 19.0-689.
8. ASTM E-645-85, “Standard Test for Effacy of Mi-
crobicides Used in Cooling Systems,” in ASTM
Standards on Materials and Environmental Micro-
biology, 1st ed., American Society for Testing and
Materials (Philadelphia, PA: 1987).
9. R.W. Lutey, “Process Cooling Water,” in Handbook
of Biocide and Preservative Use, ed. H.W. Ross-
moore (London: Chapman & Hall), Chap. 3, 1994.
10. R.W. Lutey, et al., “Mechanisms of Action of
Dimethylamides as a Penetrant/Dispersant in Cool-
ing Water Systems,” in Proceedings of the 50th
International Water Conference, held Oct. 1991,
Pittsburgh, PA, Engineer’s Society of Western PA.
11. C.G. Hollis and R.W. Lutey, “Method for the Con-
trol of Scale Using N, N-dimethyle amides of 18
Carbon Unsaturated Carboxylic Acids,” US. Patent
3,558,500, 1971.
12. B.D. Fellers, “Experiences With MIC at Comanche
Peak Steam Electric Station,” in Proceedings of the
EPRl Workshop on Microbe Induced Corrosion.
(Palo Alto, CA: Electric Power Research Institute
1986).
13. D.G. Honneysett, W.D. van den Berg, and P.F.
O’Brien, “Microbiological Corrosion in a Cooling
Water System,” MP 23(1985): 29-36.
14. R.W. Lutey and P. D. Mason, “Report: lndentification
of Root Cause Failure of Piping in a Service Water
System,” Power 25( 1992): 69-78.
15. R.W. Lutey and P.J. Allison, “Strategies for the
Mitigation of MIC in Industrial Water Systems,” in
9.30
Proceedings of the 52nd International Water Con-
ference, held Oct. 1991, Pittsburgh, PA, Engineer’s
Society of Western PA.
16. W.I.J. Poulton and R.W. Lutey, “Mitigation of Mi-
crobiologically Influenced Corrosion in Open Re-
ci rcuIat ion Coo Ii ng Systems ,” i n Microbiologically
Influenced Corrosion and Biodeterioration, eds.
N.J. Dowling, M.W. Mittleman, and J.C. Danko
(Knoxville, TN: Univ. Tennessee, 1991).
Treatment for the Mitigation of MIC
17. R.W. Lutey and G.M. Lozier, “On Line Cleaning
for Once Through Service Water Systems,” in Pro-
ceedings of the EPRl Service Water System Relia-
bility Improvement Seminar (Palo Alto, CA: Electric
Power Research Institute, 1992).
18. P.S. Zisson and T. I. Marks, “Corrosion Inhibition on
Mild Steel That Had Been Heavily Fouled with Iron
Oxide,” CORROSION/89, Paper no. 195 (Houston,
TX: NACE, 1989).

Techniques for MIC Monitoring
Importance
The annual costs of corrosion in industrialized
nations have been estimated at approximately 4%
of the gross national product (GNP).’ The esti-
mated cost of corrosion in the United States is
on the order of 300 billion dollars per year. That
same study estimated that at least 15% of those
costs are avoidable using existing technologies.
The costs for microbiologically influenced corro-
sion (MIC) are consistent with those estimates;
however, these costs could be significantly re-
duced since the control of MIC through the use
of timely treatments and scheduled maintenance
is often relatively simple.
In the past twenty years, MIC has been shown
to be a real and significant degradation mecha-
nism for industrial plant materials in a wide range
of areas, including nuclear and fossil-fueled power
plants, chemical processing facilities, refineries, oil
and gas production and distribution systems, pulp
and paper industries, and t r a n ~ p o r t a t i o n . MIC
~,~
has also been a problem for the military and for
building plumbing and ventilation systems, as well
as for numerous other industries and processes.
Unplanned downtime, a loss in production, and a
loss of efficiency manifest the costs of MIC, as pip-
ing and equipment are crippled by the localized
corrosion and the costs of the various mitigation
treatments themselves. Essentially all cooling wa-
ter and process water applications are susceptible
to MIC. Further, biological fouling, which is a pre-
cursor to most instances of MIC, can reduce the
efficiency of heat exchangers and gas and fluid dis-
tribution systems, and it can interfere with water-
based processes.
10.1
CHAPTER 10
By T.P.Zintel, G-J,Licina, and T.R. Jack
The most common approach to the mitigation
of MIC is to chemically treat the water or other
fluid. Chemical costs for a large power generation
facility are often on the order of one million dollars
per year. The toxicity of these chemicals is always
a concern for plant personnel as well as the envi-
ronment. Toxicity concerns are the basis for close
scrutiny and control of effluents and chemical in-
ventories by regulators, environmental agencies,
and plant and pipeline owners.
Probably the second-most common approach
to MIC mitigation is to do nothing and simply re-
place system piping or components when they fail.
Several nuclear plants have sustained extensive
corrosion damage to their service water systems;
much of the damage has been the result of MIC. In
many cases, extensive and expensive repairs and
replacements were required at costs of several mil-
lion dollars per system. At least three domestic nu-
clear plants have completely replaced the piping in
their service water systems. Costs per plant aver-
aged 30 million dollars.
Since MIC encompasses the full range of in-
teractions between microbiological activity on sur-
faces and corrosion processes, controlling or elim-
inating biofilms on such surfaces can prevent MIC
reliably and practically. The treatment of clean sur-
faces to keep them clean and biofilm-free is rela-
tively simple, using proven technologies. However,
a mature biofilm, replete with copious amounts of
exopolymeric saccharides, entrapped silt and de-
bris, and corrosion products, serves to protect the
underlying microbes on the metal surface from
all but the most aggressive treatments. As a re-
sult, the treatment of biofouled surfaces is much
more difficult and much more costly in terms of
downtime, the costs of the treatment, and in the
10.2
costs to the environment necessitated by toxic
chemical treatments or the generation of wastes.
Further, heavily microbiologically fouled surfaces
can establish conditions that are conducive to
rapid localized corrosion even after the living or-
ganisms have been killed. Such severely pitted
surfaces are almost impossible to salvage.
Water or fluid treatment remains the most com-
mon approach to the control of MIC. The costs of
such treatment include the costs of the biocide,
delivery system, and labor to install and maintain
the equipment as well as the costs of the opera-
tor training and permits to store and discharge the
toxic chemicals. The costs of chemical treatment
increase rapidly as the thickness and activity of the
microbiological fouling goes unchecked. Higher
concentrations of chemicals, the use of disper-
sants and surfactants, or the use of much more ag-
gressive chemical treatments are often required.
Monitoring to provide an early warning of the
onset of biocorrosion or biofilm formation and its
activity or deactivation by the selected treatment
is critical to maintaining control of surface cleanli-
ness when MIC prevention is still simple and inex-
pensive. Many of the MIC monitoring technologies
currently used or available are discussed in this
chapter.
Methods
MIC monitoring methods can be categorized
by the primary characteristic of the process that is
monitored. That is, there are techniques that mon-
itor microbiology; others detect microbiological in-
fluences, while other methods track corrosion.
An effective MIC monitor, like any monitor,
should exhibit the following characteristics:
User Friendly. The monitor must be sim-
ple to install, simple to use, and simple to
interpret by system operating personnel.
At least some interpretation functions
must be sufficiently developed so that the
system can be interfaced to alarms and
controllers for chemical treatment addi-
tions or on-line cleaning systems.
Techniques for MIC Monitoring
Rugged. The monitoring system must
be able to withstand the normal use and
abuse it is likely to experience in an in-
dustrial environment.
Sensitive. The monitor must be sensi-
tive to the onset of biofilm formation and
provide a definitive indication of biofilm
activity in real time that may be used
to evaluate the effectiveness of bio-
cide additions or other water treatments,
cleaning, or other mitigation measures.
Biofilm formation on the monitor must al-
ways “lead” biofilm formation on heat ex-
changer or piping surfaces. This degree
of enhancement of sensitivity provided
by the monitor and the prototypicality of
biofilms on monitoring probes vs. those
on component surfaces (the lead factor)
must be reasonable and quantifiable.
Accurate. False positives or indications
caused by interference from other ef-
fects such as flow, light, degree of aer-
ation, and fouling by nonbiological de-
posits must be minimized. A maximum of
two false positives per year is the target
rate. Lead factor can also impact accu-
racy requirements. An excessive or unre-
alistic lead factor will produce a positive
indication of biofilm activity that bears lit-
tle resemblance to fouling and corrosion
of system components.
Maintainable. Probes are expected to
become fouled in service. A minimum
time between servicing operations of
several months to several years will be
required for most applications. Periodic
servicing, consisting of cleaning with
readily available tools such as brushes
or abrasive tools, shall take less than one
hour per probe.
Cost Effective. The cost of the monitor
must be significantly less than the cost of
the downtime that is avoided or the treat-
ment costs that are saved. The speed
and accuracy of the technique are also
Techniques for MIC Monitoring
factors in the cost effectiveness of the
monitor.
Microbiology
Microbes are ubiquitous; they survive a wide
variety of environmental conditions, including ex-
tremes of temperature, aeration, and nutrient de-
pravation. The interaction of microbial metabolism
and corrosion processes can produce localized
attack at very high rates. Monitoring techniques
that detect the presence of microbes, especially
on metallic surfaces, can provide an early indica-
tion of incipient MIC or the potential for MIC. A
number of methods for the detection of microor-
ganisms, including specific types of organisms and
estimates of their numbers and activity, have been
developed.
Planktonic Organisms
Free-floating bacteria are commonly referred
to as “planktonic” organisms, but depending on
the type of industrial system, these may also in-
clude unattached algae, diatoms, fungi, and other
microorganisms present in a system’s bulk fluids.
In most cases, it is planktonic bacteria that are
the focus of monitoring for MIC using microbio-
logical detection techniques since system fluids
are generally easier to sample than metallic sur-
faces. Unfortunately, the levels of planktonic bac-
teria present in the liquids are not always indicative
as to whether MIC will occur or, if so, to what ex-
tent. At best, detection of viable planktonic bacteria
only serves as an indicator that living microorgan-
isms are present in a particular system. Some of
those organisms may be capable of participating in
the microbial attack of the system’s materials. It is
generally very important that additional monitoring
methods be performed to confirm that actual cor-
rosion due to microbial processes has occurred.
In some cases, monitoring for planktonic organ-
isms can be misleading. For example, following
biocide application, elimination or reduction of vi-
able planktonic organisms suggest to many op-
erators that they have implemented a successful
10.3
treatment program, when in reality, attached or-
ganisms may be quite unaffected by the biocide
treatment and were able to continue their attack
on the metal surfaces.
Biological deposits are the controlling factor
in degradation of heat transfer or initiation of
MIC. The monitoring approach should emphasize
counts, accumulation, activity, etc. of microbes on
surfaces. Microbe counts in the cooling tower wa-
ter have little or no correspondence to counts and
activity on surfaces. The primary value of “bug
counts” in the water is a regular and inexpen-
sive comparison of the effectiveness of the treat-
ment on the most readily controlled microorgan-
isms. Plots of total counts of bacteria, fungi, and
specific types of microorganisms (e.g., sulfate-
reducing bacteria) will show variations in organism
levels and reflect the level of control. Those counts
of planktonic organisms should be extremely low
for any effective biocide treatment program.
Sessile Organisms
Microorganisms that are attached to a sur-
face are termed “sessile” organisms. Bacteria and
other microorganisms are almost always present
as a consortium or community of organisms, col-
lectively referred to as a biofilm. Since MIC occurs
directly on metal surfaces, sessile organisms are
the ones that are most representative of poten-
tial problems and, therefore, are a more important
component to monitor. Monitoring sessile organ-
isms either requires that the system or pipeline be
regularly opened for sampling or that accommo-
dations be made in the system design to allow for
regular collection or on-line tracking of attached
organisms while the system continues to operate.
It should be pointed out, however, that the pres-
ence of viable sessile organisms does not always
translate into actual attack on the metal surfaces.
Again, it is a good idea to use additional methods
that directly determine the presence of active MIC.
Direc t Inspection
Surfaces coated with slime, the presence of
black iron sulfide deposits or algal growth, and
10.4
odors can all indicate the presence of a microbial
biofilm. The presence of microbes suspended in
the aqueous phase is usually not evident to the
unaided eye. Very high numbers of planktonic mi-
crobes (>l O7 cells/ml) are needed to cloud a water
sample. This level of turbidity is very rarely seen.
To see microorganisms directly in field samples re-
quires the use of a microscope capable of at least
400X magnification and preferably equipped to op-
erate in a phase contrast mode.
Direct inspection can allow detection and
enumeration of planktonic organisms. A simple
sample holder called a Petroff Hauser Counting
Chamber allows organisms in a known volume of
water to be c o ~ n t e d Populations
.~ of greater than
1O6 cells/ml can be conveniently enumerated. A
variety of dyes can enhance detection by staining
cells with bright colors or making them fluoresce
under ultraviolet In some cases the re-
sponse of the dye can be keyed to indicate the via-
bility of the cells, enabling live and dead organisms
to be distinguished. Enumeration of less dense
planktonic populations requires concentrating the
sample. This can be conveniently done by filtering
the organisms from a large volume of water and
then staining and counting the cells on the filter.8
Direct inspection is less useful for sessile pop-
ulations or dirty water systems where particles and
debris hide the microbial cells and interfere with
the use of dyes by picking up stain. Hydrocarbons,
deposits, and coating materials commonly seen
in industrial systems occasionally fluoresce under
ultraviolet light thereby preventing the use of flu-
orescent dyes. In effect direct inspection is often
limited to detection of microorganisms in field Sam-
ples. This limitation along with the cost and deli-
cacy of the microscope has left direct inspection a
lab technique.
Direct inspection has been used as a research
tool to investigate the arrangement of specific
kinds of bacteria and processes in microbial com-
munities. Tagged antibodies can bind dyes to spe-
cific kinds of b a ~ t e r i a . ~ -Such
’ ~ techniques can
provide insight into how microbial biofilms develop
and influence corrosion processes, but they are of
limited application in the routine management of
industrial operations.
Techniaues for MIC Monitorina
Growfh Assays
The most popular way to enumerate microor-
ganisms in industrial systems is through growth
assays.15 Commercial kits are widely available to
count different kinds of organisms that have been
related to specific industrial problems. These kits
may be used to analyze fluid samples or solid sam-
ples scraped from surfaces.
The type most commonly used in industrial ap-
plications involves a series of liquid vials. The kits
include all the tools needed to prepare the sam-
ple and dilute it quantitatively into vials of growth
medium. Different media are available to grow
sulfate-reducing bacteria (SRB), acid-producing
bacteria (APB), and general aerobic or anaero-
bic bacteria. The extent of growth seen in a di-
lution series after an appropriate time interval al-
lows estimation of the numbers of each type of
bacteria present in the original sample. This ap-
proach is called the Most Probable Number (MPN)
technique, reflecting the semiquantitative nature of
the counts obtained. Detection limits are very low
(1 to 10 cells/ml) but very high populations can
also be enumerated by extending the dilution se-
ries if needed. It is important that growth assays be
done at the salinity and temperature of the indus-
trial operating system. Commercial kits are offered
for different levels of salinity. In some kits, solid me-
dia in the form of agar stabs or dip slides are used
in place of liquid media in vials, but the general
approach remains similar.
Commercially available kits were compared in
a round-robin test performed by field personnel
in 1992.16These kits provide untrained personnel
with a relatively inexpensive way to monitor vari-
ous groups of bacteria thought to be important in
MIC over time. Changes in populations provide an
indication of emerging MIC problems or the effect
of biocide addition or other actions in the system.
Despite the successful use of growth assays,
only a small fraction of wild microorganisms ac-
tually grow in commonly supplied artificial media.
For example, less than one organism in a thousand
present in marine sediments can actually be grown
by standard procedures.17 Commercial growth as-
says do not count all the organisms present but do
Techniques for MIC Monitoring
characterize the composition of populations gen-
erally associated with industrial problems.
Enzyme Assays
Enzymes are proteins that act as catalysts for
specific chemical reactions. An increasingly popu-
lar approach is the use of commercial kits to assay
the presence of enzymes specifically associated
with organisms or processes implicated in MIC.
These assays do not depend on growth of the
organisms but focus instead on the chemical re-
actions that a microbial community can catalyze.
Commercial products are available for determin-
ing the presence of h y d r ~ g e n a s e ' ~
or, ~sulfate
~ by analyses based on the fatty acid profile of the
reductase20,21enzymes present in many species
of SRB. Correlation of enzyme activity with popu-
lation counts is variable. In general these kits have
a range of application that is narrower than growth-
based assays, making it important to select a kit
with a range of response appropriate to the prob-
lem under investigation. Test kits are generally a
little costlier and have a higher detection limit than
growth-based assay kits; however, results can be
obtained in less than an hour compared to several
days.
Metabolites
In some cases, microbial products are impli-
cated in MIC scenarios. One example is the pre-
cipitation of black iron sulfides as a corrosion prod-
uct by SRB in systems normally free of hydrogen
sulfide. The concentration of iron sulfide in corro-
sion products has been related to corrosion rates
seen in SRB-based' MIC.22 Organic acids have
been detected in corrosion deposits,23 implicating
acid-producing bacteria in some MIC scenarios.
An overall assessment of microbial activity
can be achieved by measuring the amount of
adenosine triphosphate (ATP) in field samples.24
This key metabolite drives many cellular reactions.
Commercial instruments are available for field use
but the method is best suited to clean aerobic
aqueous samples. The measurement is based on
fluorescence that can be chemically quenched
or blocked by particulate^.^^ Biofilm samples,
10.5
especially from highly reduced environments
where hydrogen sulfide is present, can prove dif-
ficult to measure. Natural variations in the amount
of ATP per cell make direct correlation with cell
counts unreliable, but the assay can be used to
monitor the general health and activity of a micro-
bial population in an industrial system.
Cell Components
A general index of biomass in field samples
can be obtained by classical analytical methods for
protein, lipopolysaccharides, or other cell compo-
nents. More specific information can be obtained
microbial cells or on nucleic acid samples derived
from field samples.
Analysis of fatty acid methyl ester (FAME) pro-
files is one of the best available ways to charac-
terize the composition of a naturally occurring mi-
crobial community.26-28The composition of fatty
acids in cellular components can be used to finger-
print specific organisms. Provided pertinent pro-
files are known, organisms can be identified with
c o n f i d e n ~ e .FAME
~ ~ ~ ~can
~ be used to identify
what organisms are present in an industrial sys-
tem, to monitor populations in the field, and to
assess the impact of operating actions such as
biocide addition on the makeup of sessile com-
munities. The technique involves separating fatty
acids from field samples and converting them
to the corresponding methyl esters suitable for
gas chromatographic analysis. Commercial sys-
tems including instrumentation, procedures, and
databases of FAME profiles for a library of known
organisms are available.
Nucleic acids are the blueprints for construc-
tion of cell components. The sequence of nu-
cleotides in nucleic acid polymers provides a code
for protein synthesis. The master blueprint (DNA)
is transcribed to form working copies (RNA) spe-
cific to various cell components. Assays based on
the sequence of nucleic acids can be used to iden-
tify specific organisms, kinds of organisms, or the
presence of enzymes at a general or specific level
of discretion depending on the approach used. For
example, a gene probe designed to detect [NiFe]
10.6
hydrogenase enzyme has been used to character-
ize SRB in oil-field production waters3’ Because
gene probes are highly targeted, a battery of dif-
ferent probes would be needed to characterize a
microbial community broadly.
A more general approach is to use the whole
DNA genome as a fingerprint for the identification
of organisms. A practical technique called Reverse
Sample Genome Probing (RSGP) allows DNA
separated from field samples to be cross-reacted
with standard samples prepared from organisms
cultured from previous MIC sites.32 In effect the
method can show, in a semiquantitative manner,
whether any of the known organisms are present.
A problem faced by nucleic acid-based as-
says is the separation of sufficient material from
a field sample to allow analysis. A special tech-
nique based on the polymerase chain reaction
(PCR) can replicate targeted genetic material in
a sample millions of times.33 Initial tests identified
over 300 strains of bacteria using this ~ r 0 c e d u r - e . ~ ~tions of elements involved in the corrosion can
While the technique is extremely sensitive, the ex-
tent of amplification varies for nucleic acid material
from various organisms. Results are best regarded
as qualitative. A comparison of this approach with
FAME has been published.35
Analysis of cell components requires skilled
staff in an appropriately equipped laboratory, but
many such assays are available on a fee-for-
service basis. Costs are high relative to the use
of commercial kits for assaying microbial growth
or enzyme activity.
Detailed Coupon Examinations
A great deal of information can be learned by
careful, in-depth examination of corrosion coupon
surfaces using commonly available analytical
techniques. These coupons can yield far more
information than a simple loss of weight, which
may be the original purpose for their installation.
The condition of the coupon surfaces themselves,
as well as their deposits, corrosion products,
and biofilms can all yield useful data to help the
corrosion engineer diagnose corrosive conditions
at key locations in a pipeline or industrial sys-
tem. Special handling of coupons after removal
Techniques for MIC Monitorina
from the system being monitored is crucial to
ensure that subsequent laboratory tests provide
representative information. Biofilms in particular
are highly sensitive to dehydration, exposure to
air, temperature, mechanical damage, and other
gross environmental changes that can occur
during removal and transport of the coupon. The
steps necessary to preserve the components of
interest that may exist on the coupon should be
planned well in advance of coupon removal.
With special preservation and handling,
coupons may be examined both chemically and
physically for macro- and microstructural corro-
sion effects. Chemical composition of the coupon
surface can be performed using energy disper-
sive X-ray spectroscopy (EDS) in combination
with scanning electron microscopy (SEM), trans-
mission electron microscopy (TEM) of replicas,
or environmental scanning electron microscopy
(ESEM). The distribution and relative concentra-
also be identified in some cases, which is partic-
ularly valuable where pitting has occurred. These
techniques are also beneficial when investigating
scales and other deposits. Both optical microscopy
and electron microscopy are useful in assessing
the nature of corrosion attack on coupons and in
determining the corrosion mechanism(s) present.
The morphological characteristics of the corro-
sion observed on coupons can be beneficial in
diagnosing the corrosion mechanism(s); however,
the interpretation of the data must also consider
the surface chemistry and microbial analysis of the
coupon and the operating environment.
Examination of coupons for microbial popula-
tions can be performed either directly (which is
destructive to surface conditions intended for sub-
sequent analyses) or indirectly, using histological
embedding techniques to preserve and remove
the biofilm. Although fairly involved, the embed-
ding technique offers several advantages over di-
rect observation in that the biofilm and corrosion
products are preserved for future analysis. ESEM
may also be utilized to examine biofilms on test
coupons; however, exopolymers and corrosion
products often obscure the cells, making quantifi-
cation and identification difficult with this method.
Techniques for MIC Monitoring 10.7

FIGURE 10.1 (a)

Biofilm sampling device with removable "buttons."

A wide variety of samplers for introducing
metallic surfaces of interest into the system are
available. Examples of such sampling devices are
shown in Figures 10.1-1 0.3.
Influence
The presence of a biofilm on a metallic sur-
face changes the local chemistry, which can mod-
ify the local anodic and cathodic processes and
initiate or dramatically alter corrosion processes.
In addition to the electrochemical changes that af-
fect corrosion, those same biofilms can also mod-
ify other readily measured characteristics such as
pressure drop or heat transfer resistance. Moni-
toring such microbiological influences can provide
a useful indicator that a biofilm is present and
that action should be taken to mitigate potential
MIC.
Deposition A ccurn ulation Monitors
Methods for monitoring deposits can provide
an indication of the accumulation of biofilm and
other solids on surfaces or in orifices. For exam-
ple, monitoring pressure drop across an orifice
provides a simple method for continuous monitor-
ing of deposit accumulation that can be used as
a method for detecting biofilm accumulation and
serve as a monitor for incipient MIC. The disadvan-
tage of such a monitor is that the total deposition
is tracked and that the pressure drop technique is
not specific to biofilm.
 10.8 Techniques for MIC Monitoring

CPVC SAMPLE CYLINDER COVER

r GALV STEEL HANGER

/ I
314 SCH 80 C SAMPLE STUBS 11 " POLYPROPYLENE
FLANGE CONNECTION

SIDE VIEW

SAMPLE CYLINDERS
( 563'' ID)
1 1 ,-CPVC SAMPLECYLINDERCOVER

1 I,,
1625 OD
~LC P
SAMPLE TUBEV C

TUBE

SECTION "A - A SECTION "B - B"

SAMPLE STUB PLACEMENT SAMPLE CYLINDER PLACEMENT

FIGURE 10.1 (b)

Biofilm sampling tube with removable stub-type coupons. (From Don1at-1.~~)

FIGURE 10.2(a) FIGURE 10.2(b)

Biofilm sampler with removable stubs. (From Videla Close-up of biofilm sample holder. (From Videla et
et al.48) (Copyright ASTM. Reprinted with permission) (Copyright ASTM. Reprinted with permission)
Techniques for MIC Monitoring
FIGURE 10.3(a)
Photo of the tube and ring column sampler. (From von
Rege and Sand.”)
Model heat exchangers also monitor total ac-
cumulation by continuously tracking deposition un-
der carefully controlled flow and heat flux. Such
methods (Figure 10.4) can be extremely sensi-
tive to deposit accumulation, as reflected by an
increase in the heat transfer resistance across one
or more heat transfer tubes. In many applications,
the degradation of heat transfer capabilities is a
primary concern that will be monitored routinely.
Additional information from those same monitor-
ing tools can provide useful information regarding
biofilm accumulation and incipient corrosion due
to microorganisms. The presence of the heat flux
can accelerate the deposition of microbes, as well
as other solids, both dissolved and suspended,
10.9
providing an accelerated condition that is useful
to the system operator.
In a laboratory environment, Geesey used a
quartz microbalance to monitor the accumulation
of biofilm on polished surfaces.36 The technique
provides an extremely sensitive method for detect-
ing biofilms on surfaces and for tracking the growth
of those films. When used in conjunction with other
techniques, including removal and visual exami-
nation of the surfaces, the influence of the biofilm
on corrosion can be demonstrated. The technique
has not yet been demonstrated to be feasible for
operating systems, however.
Deposit accumulation monitors provide a use-
ful and rapid method for the detection of fouling;
however, used alone, they are not specific to the
accumulation of microbiological fouling that can or
will lead to MIC.
Electrochemical Methods
An electrochemical method for on-line moni-
toring of biofilm activity has been developed. This
device (Figure 10.5) was motivated by the need for
continuous monitoring of biofilm formation without
the need for excessive involvement of plant per-
sonnel. A series of stainless steel or titanium disks
are exposed to the plant environment. One set of
disks is polarized (relative to the other set) for a
short period of time each day. The electrodes are
connected through a shunt the remainder of the
time. Biofilm activity, which is also an electrochem-
ical process, is monitored by tracking changes
in the applied current (i.e., when the external po-
tential is on) and the generated current (when the
potential is off). The onset of biofilm formation on
the probe is indicated when either of these in-
dependent indicators deviates from the baseline
level (Figure 10.6). The level of biofilm activity is
also measured by the amount of variation from the
baseline. The applied and generated currents from
a well-controlled system will be a flat line, devoid of
any significant deviations. The design of the probe
and results from plant exposures have been de-
scribed e l ~ e w h e r e . ~ ~ - ~ ~
Blackwood and c o - w ~ r k e r shave
~ ~ taken a
slightly different electrochemical approach. They
10.10
sterile loop
ring column:
of miniaturized
sensors
FIGURE 10.3(b)
Scheme of a laboratory test apparatus for MIC monitoring. (From D ~ n l a and
used several very small (0.12 cm2) silver elec-
trodes, plated onto platinum electrodes of the
same size, with the entire array on a ceramic sub-
strate. The silver was exposed as the metal, as
AgCI, or as Ag2S. The silver and Ag2S electrode
pair acts as a sulfide sensor while the silver and
AgCl electrode pair acts as a chloride sensor. The
production of sulfides or concentration of chlorides
by microbial action produces a nearly instanta-
neous change in the potential of the electrode
pair, providing an indication of specific microbial
activity.
Corrosion Monitoring
MIC is a form of localized corrosion. Standard
and specialized corrosion monitors have been de-
veloped that provide an alert that the system be-
ing monitored (or an accelerated and disposable
simulation of the system) is corroding, how it is
corroding, and at what rate. The corrosion monitor
may or may not provide information that MIC is the
operative form of corrosion.
Techniques for MIC Monitorina
inoculated loop
conventional sensors for
medium control
valve and fining for serial
arrangement of the loops
n ~ from
~ Eul and he it^.^')
Coupons
Traditio nal corros io n mo nito ring coupons are
most commonly referred to as “weight-loss”
coupons since that is the measurement most
often associated and performed with these de-
vices. Weight-loss coupons are fabricated from
different alloys and in many different sizes and
shapes to fit a variety of applications. The sur-
faces of such coupons are usually ground to
improve the reproducibility of weight-loss mea-
surements. Coupons that are rough or have mill
scale on surfaces may only allow visual or macro-
scopic examinations (e.g., low magnification with
a stereoscope) for gross pitting. Often, only cor-
rosion rates are determined using weight-loss
coupons. Since MIC is most often a localized cor-
rosion phenomenon, weight-loss measurements
are typically poor indicators of even serious MIC
problems. The weight-loss coupon can still be
of significant value as a MIC monitor if surfaces
are examined carefully for the presence of mi-
crobes and their viability, and by characterizing
the numbers and depths of pits (which must be
assumed to be due to bacterial attack, especially
Techniaues for MIC Monitoring 10.11

\ Series Connection /
Install piping in position shown

0 316'' 81 Union
@ * 316'' Steam Strainer
@ * 3i6" Impulse Steam Trap
@ 316'' x 6 BI Nipple
@ 112'' x 6 81 Nipple
@ V2" Tee Parallel Connection Shown
@ * Armored Thermometer and Well
@ 1g" x 114" BI Bushing
@ * Pressure Gauge
@ * 150 ccimim Rotameter with Valve
0 * Armored Thermometer and Well
@ * Pressure Snubber
0 * Insulation-minimum 1" Fiberglass
@ Condenser Tubes-3 Feet Long

*Steam Control Package

U.S. PATENT NO. 4,093,020

FIGURE 10.4
Model heat exchanger.

in the absence of other contributors, e.g., C02,
H2S, 0 2 ) .
A variety of different coupon configurations
and designs are commercially available today,
allowing the corrosion engineer to monitor corro-
sive conditions, which may be unique to a system.
For example, if crevice corrosion is a particular
concern in a pipeline because of the way field
joints were made, special coupons incorporating
a similar crevice design may be used for monitor-
ing. Special coupons can be designed to evaluate
galvanic corrosion between adjoining materials,
mimic geometry and flow conditions, and evaluate
protective coatings. Coupons may also be used to
evaluate the effectiveness of different alloys, heat
treatments, or fabricating methods in controlling
corrosion. All of these physical coupon conditions
can have some effect on surface microbiology and,
subsequently, on corrosion. When monitoring for
the presence or influence of microorganisms in
corrosion, it is important to match the coupon or
probe material to that of the system being moni-
tored. Low carbon steels, for example, tend to gen-
erate larger amounts of corrosion products than do
stainless steels, which in turn impacts the biofilm
that is formed. The surface condition of the coupon
is also an important consideration when moni-
toring for the effects of microbes on corrosion.
The preparation and surface finish of the coupon
must be selected to facilitate analysis, yet permit
10.12 Techniques for MIC Monitoring

When attempting to utilize any coupon design

to monitor for MIC, the nature of microbial involve-
ment in the corrosion mechanism should not be
assumed. Microbes may facilitate corrosion initia-
tion, contribute to deposit formation, act as cata-
lysts to predominantly electrochemical corrosion,
form concentration cells, fix anodic sites, and/or
any combination of these functions. Most likely,
one “standard” exposure duration will not suffice
to reveal the true effects of microbial involvement
unless some level of experience with the system
being monitored has been acquired. Thus, when
evaluating any system for microbial contribution
to corrosion, a number of coupon exposure times
should be employed, if at all possible. As with any
type of coupon monitoring program, placement
of the coupons in a system environment repre-
sentative of where corrosion has occurred is of
the greatest importance. Prior evaluation of en-
vironmental and material conditions in locations
where corrosion is known to occur is valuable
in designing a monitoring program using special
FIGURE 10.5
Electrochemical biofilm activity probe. (From L i ~ i n a . ~ ~ )
coupons.

Galvanic Probes
attachment and colonization of bacteria. Placing
coupons in inhibitor-treated storage bags is one A number of investigators have utilized
way that the coupon surface chemistry can be pre- galvanic probes to evaluate corrosion in oil-
vented from being inadvertently affected and alter- field waters, in cooling waters, and in other
ing the representative attachment of organisms. e n v i r o n m e n t ~ . ~A~typical
~ ~ * galvanic probe (Fig-
ure 10.7) will electrically connect the material of
interest (e.g., carbon steel) to a more noble metal
Essential Equipment Cooling Water System (e.g., brass) in order to initiate corrosion on the
40
material of interest and to perpetuate conditions
30 that are conducive to continuing corrosion (e.g.,
the formation of biofilms comprised of microbes
f 20
that are attracted to anodic sites). The result is ac-
=2
U”
10 celerated corrosion of the active member in the
5
0 0

-10

-20
10/20/93 12119/93 02117/94 04118/94 06117/94 08/16/94

FIGURE 10.6
Typical data from electrochemical biofilm activity probe. FIGURE 10.7
(From Licina and N e k ~ k s a . ~ ~ ) Galvanic probe. (From Smart and P i ~ k t h a l l . ~ ~ )
Techniaues for MIC Monitorina
pair. Comparison of the performance of the gal-
vanic probe in the environment being monitored
(where the effects of microbial action on the corro-
sion are unknown) to the performance in a similar
environment, which does not have a microbiolog-
ical influence, provides insight into the probability
that MIC is a significant contributor, rates of att-
ack, etc.
Galvanic probes are simple devices with no
moving parts. The polarization of the carbon steel
from the galvanic coupling produces conditions
that are conducive to biofilm formation on the metal
surfaces. It should be noted that the polarization
potential is not adjustable for a single probe. How-
ever, the use of a different noble member, or a
series of different probes with a variety of different
metals, can provide a broad spectrum of corrosion
conditions.
Electrical Resistance Probes
Electrical resistance (ER) probes determine
metal loss by measuring the increase in resistance
of a metal specimen as its cross-sectional area
is reduced by corrosion. These probes are some-
times referred to as “electric coupons.” The probe
should be made of an alloy similar to the metal in
the system and inserted into the system through
an access fitting. A baseline instrument reading is
made after the probe is installed and a suitable
time has elapsed for the probe to come to equilib-
rium with the environment (i.e., temperature, sur-
face conditioning). At prescribed time intervals, the
instrument measures the resistance. A simple al-
gorithm supplied by the manufacturer is used to
correlate the change in resistance to metal loss.
Evaluating the change in resistance and metal loss
over time produces a time-wise history of metal
loss. The corrosion rate in mils per year (mpy) is
determined as the average metal loss between any
two points in time.
Interpretations of the data obtained with the
electrical resistance probe are subject to the
same general limitations for traditional weight-loss
coupons. For example, deposits on the probe sur-
face can shield the element from the corrosive en-
vironment. In some cases, iron sulfide scale laid
10,13
down on the element is electrically conductive,
causing an apparent increase in the cross section
of the exposed element. This results in a lower
corrosion rate measurement, zero apparent corro-
sion, or even a negative reading (as an apparent
increase in metal rather than a decrease through
corrosive attack). Localized corrosion can produce
a very dramatic decrease in the cross section at
the point of the local attack and a measured resis-
tance that is artificially high.
Attempting to correlate corrosion rate mea-
surements with MIC (sessile or planktonic organ-
isms) instead of determining whether actual met-
allurgical evidence of microbial attack exists could
potentially mislead the corrosion engineer to an
incorrect diagnosis and subsequent mitigative ac-
tion that is unnecessary. Unless the probe is phys-
ically removed from service and the attached de-
posits are analyzed for chemical composition, or
morphological characteristics of corrosion on the
probe surface are identified, correct diagnosis of
the corrosion mechanism(s) will be unlikely.
Even when the measured changes in electri-
cal resistance are due to corrosion, the indication
provided by the ER probe would not be specific to
MIC. Further, ER probes are typically poor for the
detection of localized corrosion. It should be noted
that the use of specially configured resistance ele-
ments can provide a “fuse” that is very sensitive to
localized corrosion, including MIC; however, that
sensitivity comes at the expense of sensor life.
Linear Polarization Resistance
Probes
Linear polarization resistance (LPR) probes
measure instantaneous corrosion rates and qual-
itatively measure the pitting tendency of metals
in electrolytes. The technique involves measuring
the current required to change the electrical poten-
tial of a specimen corroding in a conductive fluid.
Both two-electrode and three-electrode linear po-
larization probes are available for corrosion rate
measurements. The electrodes should be made
of an alloy similar to the metal in the system. Use
10.14
of the linear polarization resistance technique for
corrosion rate measurements is limited to electri-
cally conductive solutions since current must flow
from one electrode to another through the solution.
Corrosion rates are determined by measuring the
applied current required to polarize the electrodes
to a small potential difference (20 mV). Users of
these instruments should seek advice from the
manufacturer pertaining to instrument function in
a specific system.
As with using coupons, when attempting to
use any probe configuration to monitor for MIC,
the nature of microbial involvement in the corro-
sion mechanism should not be assumed. Specially
configured LPR probes can provide useful infor-
mation relative to localized corrosion mechanisms,
including MIC; however, the indicated corrosion
is not specific to MIC. Such probes will typically
use oversized electrodes and may incorporate
crevices to facilitate microbiological growth. The
use of different levels of polarization may also en-
courage and accelerate microbiological settlement
on the probe electrodes.
Whenever evaluating any system for micro-
bial contribution to corrosion, several monitoring
parameters should be employed and correlated
to provide corroborative evidence. Many times
the employment of only a single device will raise
more questions than the corrosion engineer can
answer.
As with any monitoring program, placement
of the LPR probes in a system’s environment is
of paramount importance. Typically, locations that
are representative of where corrosion has oc-
curred in the past or where it is predicted to be
most likely to occur in the future are the most rea-
sonable starting points. However, when selecting
these monitoring sites, it must be reinforced that
LPR probes require immersion in a conductive so-
lution (electrolyte) to function accurately and they
are subject to fouling by hydrocarbons. Therefore,
prior evaluations of the environment and mate-
rial conditions in locations where corrosion has
been known to occur are probably among the most
valuable commodities when designing an inter-
nal corrosion monitoring program and deciding on
monitoring technologies to use, especially when
MIC is a concern.
Techniques for MIC Monitoring
Electrochemic a1 lmpedance
Spectroscopy
Electrochemical impedance spectroscopy
(EIS) is an alternating current (AC) technique
that uses small-amplitude polarization of a test
electrode to characterize the impedance and ca-
pacitance of the operative corrosion process(es).
Direct current (DC) techniques such as linear
polarization resistance rely upon determinations
of the current between sensor electrodes. That
current is affected by the total resistance between
the electrodes, where the total resistance consists
of the polarization resistance (the parameter that
is actually an indicator of the corrosion kinetics)
and the solution resistance. As the solution
resistance increases, the error in the apparent
polarization resistance increases. Further, as
nonconductive or poorly conductive films form on
surfaces, the capacitance of the film will change,
possibly very dramatically, and the “error” in the
measured signal will increase. EIS examines
both the resistive and capacitive nature of the
response to the small-amplitude AC polarization
by examining that response of potential and
current and the phase angle between the two
over a range of frequencies. From an analysis of
the outputs, the specifics of the overall process
can be revealed. Silverman’s “Primer on the AC
Impedance Technique”43 describes the methods
involved in making the measurements and in data
analysis.
Most often, an “equivalent circuit” for the pro-
cess, consisting of resistors, capacitors, and in-
ductors, is developed as a predictive tool for the
nature of the expected impedance. Many research
activities have used EIS to characterize the in-
fluence of microbial films on c o r r o ~ i o n Most
.~~~
often, the primary parameter that was measured
was the polarization resistance. In some of those
studies, the nature of the microbiological influence,
produced by changes in the diffusion characteris-
tics, or the charge transfer through the biofilm was
characterized. For example, the steeper slope and
greater frequency dependence of the impedance
for copper in an inoculated environment shown
in Figure 10.8 is indicative of a greater influ-
ence of the electrochemical properties of the films
Techniques for MIC Monitoring 10.15

2 I I I I I I -50 I I I I I I

(versus a greater relative contribution from diffu-
sion through the film in the sterile control).
EIS work on MIC has been done in both labo-
ratory and field The equipment,
including hardware, computers, and data analy-
sis software, is expensive and the interpretation of
the data requires considerable expertise. Still, the
technique can be used in the field, particularly in
dedicated side streams.
potential raw data are collected every few sec-
onds, over long periods, and analyzed using a per-
sonal computer. Analyzing the resulting transients
using a variety of statistical approaches can pro-
vide insight into the controlling mechanisms of the
corrosion.
A major advantage of electrochemical noise
techniques is that the testing itself is nonintrusive.
That is, no potentials are applied to force corrosion

TYPICAL EN EQUIPMENT
Electrochemical Noise
Electrochemical noise (ECN) methods monitor
and characterize small-amplitude, low-frequency,

z?-E3
and random fluctuations of the current and po-
tential of corroding electrodes that are observed
in typical corrosion processes. Most simplistically, @YOLTMETER
the current and potential fluctuations mark specific
anodic or cathodic events.
Most often, three electrodes are used as
shown in Figure 10.9. Current fluctuations be-
tween nominally identical electrodes are moni- COUNTER WORKING REFERENCE
ELECTRODE ELECTRODE ELECTRODE
tored using a zero resistance ammeter (ZRA)
while potential noise is measured between a test FIGURE 10.9
electrode and a reference electrode. Current and Typical electrochemical noise setup.
10.16
l I I 111 P I ' I I
I require that an enormous amount of data be col-
ECN Data for the Sample Exposed
to Untreated Stagnant Water - Summary
Arrow Indicates when Oxygenated .
Water was Allowed to Enter the System
FIGURE 10.10
Electrochemical noise results. (From Brennenstuhl and
Gendr~n.~ (Copyright
~) ASTM. Reprinted with permis-
sion)
to occur. Initiation and propagation of the corrosion
on the test electrodes will produce natural fluctu-
ations in the current and potential. Different forms
of corrosion will have very different noise charac-
teristics. Interpretation software is trainable (see,
for example, Reference 47).
ECN was used to monitor microbiological
influences on Type 304L stainless steel exposed
to untreated Lake Erie water in a side-stream test
stand at a power plant. Selected electrode sets
were exposed to slowly flowing lake water, periods
of stagnation, and oxidizing biocide treatments.
The most interesting exposure involved exposing
the ECN probes to stagnant lake water conditions
for 30 days and then opening the inlet valve only
(Figure 10.10). As shown, during the stagnation
period, both the potential and current noise
were very small, as would be expected for a
stainless steel exposed to deaerated conditions.
Techniques for MIC Monitoring
The dramatic increases in the mean value of
the potential and the current immediately upon
opening the valve, and the increase in both the
potential and current noise about 100 seconds
after opening the valve, provided a very dramatic
indication of the effects of the introduction of
oxygen to the system following the extended
period of stagnation. The current values from a
sterile test leg exposed to the same flow history
exhibited essentially no change when the inlet
valve was opened. The potentials in that leg did
change; however, the potential noise did not.
Although electrochemical noise methods do
lected and processed, those tasks are readily han-
dled by modern personal computers. A number of
commercial software packages are available for
real time or nearly real time analysis of the data.
The application of ECN techniques to MIC and var-
ious other corrosion processes is increasing.
A variety of techniques are available to
monitor MIC. The techniques include methods for
monitoring numbers or types of either planktonic or
sessile microorganisms, for tracking biofilm accu-
mulation (e.g., pressure drop, degradation in heat
transfer resistance), and for ascertaining the in-
fluence of biofilms on surface properties (on-line
electrochemical methods). Techniques to modify
and refine standard corrosion monitoring methods
such as coupons, linear polarization resistance,
electrochemical impedance spectroscopy, or elec-
trochemical noise are also in use. Unfortunately,
the techniques that may be chosen to best mon-
itor for MIC and other corrosion are often limited
by economics, available monitoring equipment and
analytical devices, operator expertise, system de-
sign, or any other number of parameters.
Acknowledgments
The authors would like to thank Bruce A. Cook-
ingham and Richard B. Eckert of ANR Pipeline
Company for their contributions to this chapter.
Techniques for MIC Monitoring
References
1. “Cost of Corrosion Study: $300 Billion a Year,” MP
June (1980): June, 1995.
2. G. Kobrin, ed., A Practical Manual on Microbiolog-
ically Influenced Corrosion (Houston, TX: NACE,
1993).
3. S.W. Borenstein, Microbiologically Influenced Cor-
rosion Handbook (Industrial Press, 1994).
4. P. Gerhardt, R.G.E. Murray, R.N. Costilow, E.W.
Nester, W.A. Wood, N.R. Krieg, and G.B. Phillips,
eds., Manual of Methods for General Bacteriology
(Washington, DC: American Society of Microbiol-
ogy, 1981).
5. P. Snyder and D.B. Greenberg, “Viable Microorgan-
isms Detection by Induced Fluorescence,” Biotech-
nol. Bioeng. 26( 1984): 1395-1 397.
6. G. Schaule, H.C. Flemming, and H.F. Ridgway,
“Use of 5-cyano-2,3-ditolyl Tetrazolium Chloride for
Quantifying Planktonic and Sessile Respiring Bac-
teria in Drinking Water,” Appl. Environ. Microbiol. 59
(1993): 3850-3857.
7. T.M. Kenney and D.H. Pope, “Microbiological Con-
siderations in Electric Power Generating Stations:
Monitoring Techniques and Case Histories,” in Pro-
ceedings of the 1995 International Conference on
Microbially Influenced Corrosion, eds. P. Angell,
S.W. Borenstein, R.A. Buchanan et al. (Houston,
TX: NACE, 1995), pp. 33/1-33/10.
8. R.J. Daley, “Direct Epifluorescence Enumeration
of Native Aquatic Bacteria: Uses, Limitations and
Comparative Accuracy,” in Native Aquatic Bacte-
ria: Enumeration, Activity and Ecology, eds. J.W.
Costerton and R.R. Colwell, ASTM Special Publ.
695 (Philadelphia, PA: American Society for Test-
ing and Materials, 1977), pp. 29-45.
9. P.M. Stanley, M.A. Gage, and E. Schmidt, “Enu-
meration of Specific Populations by Immunofluo-
rescence,” in Native Aquatic Bacteria: Enumeration,
Activity and Ecology, eds. J.W. Costerton and R.R.
Colwell, ASTM Special Publ. 695 (Philadelphia, PA:
American Society for Testing and Materials, 1977),
pp. 46-55.
10. S. Bobowski and D.B. Nedwell, “A Serological
Method, Using a Micro ELSA Technique for Detect-
ing and Enumerating Sulfate Reducing Bacteria,” in
Industrial Microbiological Testing,eds. J.W. Hopton
and E.C. Hill (London: Blackwell Scientific, 1987),
pp. 171-179.
11. J.H. Hunik, M.P. van den Hoogen, W. de Boer,
M. Smit, and J. Tramper, “Quantitative Determina-
10.17
tion of Nitrosomonas europea and Nitrobacter ag-
ilis Cells Immobilized in k-Carageenan Gel Beads
by a Specific Fluorescent-Antibody Labelling Tech-
nique,” Appl. Environ. Microbiol. 59(1993): 1951-
1954.
12. R.I. Amman, J. Stromley, R. Devereux, R. Key, and
D.A. Stahl, “Molecular and Microscopic Identifica-
tion of Sulfate Reducing Bacteria in Multispecies
Biofilms,” Appl. Environ. Microbiol. 58(1992): 614-
623.
13. W. Manz, U. Szewzyk, P. Ericsson, R. Amann, K.H.
Schliefer, and T.A. Stenstrom, “In Situ Identification
of Bacteria in Drinking Water and Adjoining Biofilms
by Hybridization with 16s and 23s rRNA-Directed
Fluorescent Oligonucleotide Probes,” Appl. Envi-
ron. Microbiol. 59(1993): 2293-2298.
14. L.K. Poulsen, G. Ballard, and D.A. Stahl, “Use of
rRNA Fluorescence In Situ Hybridization for Mea-
suring Activity of Single Cells in Young and Estab-
lished Biofilms,” Appl. Environ. Microbiol. 59(1993):
1354-1 360.
15. J.W. Costerton and R.R. Colwell, eds. Native
Aquatic Bacteria: Enumeration, Activity and Ecol-
ogy. ASTM Special Publ. 695 (Philadelphia, PA:
American Society for Testing and Materials, 1977).
16. P.J.B. Scott and M. Davies, “Survey of Field Kits
for Studying Microbial Corrosion,” in Microbial
Corrosion-I, eds. C.A.C. Sequeira and A.K. Tiller
(New York: Elsevier Applied Science, 1988).
17. B.B. Jorgenson, “A Comparison of Methods for
Quantification of Bacterial Sulfate Reduction in
Coastal Marine Sediments,” Geomicrobiol. J. 1
(1978): 49-64.
18. J. Boivin, E.J. Laishley, R. Bryant, and J.W. Coster-
ton, “The Hydrogenase Test-A Rapid Enzyme
Based Test for Corrosion Causing Bacteria,” in
Microbially Influenced Corrosion and Biodeterio-
ration, eds. N.J. Dowling, M.W. Mittleman, and
J.C. Danko (Knoxville: Univ. Tennessee, 1990), pp.
8-27-8-32.
19. R.D. Bryant, W. Jansen, J. Boivin, E.J. Laishley, and
J.W. Costerton, “Effect of Hydrogenase and Mixed
Sulfate Reducing Bacterial Populations on the Cor-
rosion of Steel,” Appl. Environ. Microbiol. 57(1991):
2804-2809.
20. R.E. Tatnall, “New Perspectives on Testing for Sul-
fate Reducing Bacteria,” in Microbially Influenced
Corrosion and Biodeterioration, eds. N.J. Dowling,
M.W. Mittleman, and J.C. Danko (Knoxville: Univ.
Tennessee, 1990), pp. 5-17-5-32.
21. J.M. Odom, K. Jessie, E. Knodel, and M. Emptage,
“Immunological Cross-Reactivities of Adenosine-
10.18
5’-Phosphosulfate Reductase from Sulfate Reduc-
ing and Sulfide Oxidizing Bacteria,” Appl. Environ.
Microbiol. 57 (1991): 727-733.
22. T.R. Jack, M.J. Wilmott, R.L. Sutherby, and R.G.
Worthingham, “External Corrosion in Line Pipe-A
Summary of Research Activities,” MP 35(3)( 1996):
18-24.
23. D.H. Pope, “State-of-the-Art Report on Monitor-
ing, Prevention and Mitigation of Microbiologically
Influenced Corrosion in the Natural Gas Indus-
try,” Topical Report GRI-92/0382 (Chicago, IL: Gas
Research Institute, 1992).
24. L.H. Stevenson, T.H. Chrzanowski, and C.W.
Erkenbrecher, “The Adenosine Triphosphate As-
say: Conceptions and Misconceptions,” in Native
Aquatic Bacteria: Enumeration, Activity and Ecol-
ogy, eds. J.W. Costerton and R.R. Colwell, ASTM
Special Publ. 695 (Philadelphia, PA: American So-
ciety for Testing and Materials, 1977), pp. 99-1 16.
25. G.G. Geesey and J.W. Costerton, “Bacterial
Biomass Determinations in a Silt Laden River:
Comparison of Direct Count Epifluorescence Mi-
croscopy and Extractable Adenosine Triphosphate
Techniques,” in Native Aquatic Bacteria: Enumer-
ation, Activity and Ecology, eds. J.W. Costerton
and R.R. Colwell, ASTM Special Publ. 695 (Phila-
delphia, PA: American Society for Testing and
Materials, 1977), pp. 117-1 27.
26. R.J. Bobbie and D.C. White, “Characterization of
Benthic Microbial Community Structure by High
Resolution Gas Chromatography of Fatty Acid
Methyl Esters,” Appl. Environ. Microbiol. 39(1980):
1212-1 222.
27. A.G. O’Donnell, “Fatty Acid Analysis in the Identi-
fication of Natural Isolates: Possibilities for in situ
Identification Using Multivariate Pattern Recogni-
tion,” in Recent Advances in Microbial Ecology.
Proceedings of the Fifth International Symposium
on Microbial Ecology (Tokyo: Japan Scientific
Societies Press, 1989).
28. “Identification of Bacteria by Analysis of Cellular
Fatty Acids,” Technical Bulletin 767 (Bellafonte, PA:
Supelco Inc.).
29. M. Vainshtein, H. Hippe, and R.M. Kroppenstadt,
“Cellular Fatty Acid Composition of Desulfovibrio
Species and its Use in the Classification of Sulfate-
Reducing Bacteria,” System. Appl. Microbiol. 15
(1992): 554-566.
30. N.J.E. Dowling, F. Widdel, and D. White, “Phos-
pholipid Ester Linked Fatty Acid Biomarkers of
Techniques for MIC Monitoring
Acetate-Oxidizing Sulfate-Reducers and Other
Sulfide Forming Bacteria,” J. Gen. Microbiol. 132
(1986): 1812-1 825.
31. G. Voordouw, A.J. Telang, T.R. Jack, J. Foght, PM.
Fedorak, and D.W.S. Westlake, “Identification of
Sulfate-Reducing Bacteria by Hydrogenase Gene
Probes and Reverse Sample Genome Probing,” in
Applications of Molecular Biology in Environmen-
tal Chemistry, eds. R.A. Minear, A.M. Ford, L.L.
Needham, and M.J. Karch (Boca Raton, FL: Lewis,
1995), Chap. 7.
32. G. Voordouw, Y. Shen, C.S. Harrington, A.J. Telang,
T.R. Jack, and D.W.S. Westlake, “Quantitative
Reverse Sample Genome Probing of Microbial
Communities and Its Application to Oil Field Pro-
duction Waters,” Appl. Environ. Microbiol. 59(1993):
4101-4114.
33. M.A. Jensen, J.A. Webster, and N. Straus, “Rapid
Identification of Bacteria on the Basis of Poly-
merase Chain Reaction Amplified Ribosomal DNA
Spacer PoIy morphis ms ,” AppI. Enviro n. Mic robio I.
59( 1993): 945-952.
34. Y.L. Tsai and B.H. Olson, “Rapid Method for
Separation of Bacterial DNA from Humic Sub-
stances in Sediments for Polymerase Chain Re-
action,” Appl. Environ. Microbiol. 58( 1992): 2292-
2295.
35. E.C. Bottger, “Approaches for Identification of
Microorganisms,” ASM News 62( 1996): 247-
250.
36. G.G. Geesey and P.J. Bremer, “Evaluation of Biofilm
Microorganisms in Copper Corrosion,” in Micro-
bially Influenced Corrosion and Biodeterioration,
eds. N.J. Dowling, M.W. Mittleman, and J.C. Danko
(Knoxville: Univ. Tennessee, 1990), pp. 1-19-
1-24.
37. G.J. Licina, G. Nekoksa, and R.L. Howard, “An
Electrochemical Method for On-Line Monitoring
of Biofilm Activity in Cooling Water Using the
B loGEORGETM Probe,” in Microbiologically Influ-
enced Corrosion Testing, eds. J.F. Kearns and B.J.
Little, ASTM STP-1232 (Philadelphia, PA: Amer-
ican Society for Testing and Materials, 1993),
pp. 118-1 27.
38. G.J. Licina and G. Nekoksa, “The Influence of Water
Chemistry and Biocide Additions on the Response
of an On-Line Biofilm Monitor,” CORROSION/95,
Paper no. 527 (Houston, TX: NACE, 1995).
39. G.J. Licina, “Monitoring Biofilm Formation in a
Brackish Water Cooled Power Plant Environment,”
Techniques for MIC Monitoring
CORROSION/97, Paper no. 222 (Houston, TX:
NACE, 1997).
40. D.J. Blackwood, J.L. deRome, D.L. Oakly, and A.M.
Pritchard, “Novel Sensors for On-Line Detection of
MIC,” CORROSION/94, Paper no. 254 (Houston,
TX: NACE, 1994).
41. U. Eul and E. Heitz, “Sensor Application for MIC
on Metals by a Mobile Monitoring Apparatus,” 1995
International Conference on Microbiologically In-
fluenced Corrosion May (Houston, TX: American
Welding Society and NACE, 1995).
42. J.S. Smart and T. Pickthall, “A New System for On-
Line Monitoring of Internal Corrosion and Bacte-
ria in Pipelines,” CORROSION/92, Paper no. 15
(Houston, TX: NACE, 1992).
43. D.C. Silverman, “Primer on the AC Impedance
Technique,” in Electrochemical Techniques for Cor-
rosion Engineering, eds. R.A. Baboian (Houston,
TX: NACE, 1986), pp. 73-79.
44. F. Mansfeld and H. Xiao, “Electrochemical Tech-
niques for Detection of Localized Corrosion Phe-
nomena,” in Microbiologically Influenced Corrosion
Testing,eds. J.F. Kearns and B.J. Little, ASTM STP-
1232 (Philadelphia, PA: American Society for Test-
ing and Materials, 1993), pp. 42-61.
45. B.J. Webster and R.C. Newman, “Producing Rapid
Sulfate-Reducting Bacteria (SRB)-Influenced Cor-
rosion in the Laboratory,” in Microbiologically Influ-
enced Corrosion Testing, eds. J.F. Kearns and B.J.
Little, ASTM STP-1232 (Philadelphia, PA: Amer-
ican Society for Testing and Materials, 1993),
pp. 28-41.
46. F. Mansfeld and B.J. Little, “A Critical Review of
the Application of Electrochemical Techniques to
the Study of MIC,” in Microbially Influenced Corro-
sion and Biodeterioration, eds. N.J. Dowling, M.W.
10.19
Mittleman, and J.C. Danko (Knoxville: Univ. Ten-
nessee, 1990), pp. 5-33-5-39.
47. S. Reid, G.E.C. Bell, and G.L. Edgemon, ”The Use
of Skewness, Kurtosis and Neural Networks for De-
termining Corrosion Mechanism from Electrochem-
ical Noise Data,” CORROSION/98, Paper no. 176
(Houston, TX: NACE, 1998).
48. H.A. Videla, F. Bianchi, M.M.S. Freitas, C.G.
Canales, and J.F. Wilkes, “Monitoring Biocorro-
sion in Industrial Waters: A Practical Approach,”
in Microbiologically Influenced Corrosion Testing,
eds. J.F. Kearns and B.J. Little, ASTM STP-1232
(Philadelphia, PA: American Society for Testing and
Materials, 1994).
49. R.M. Donlan, “Correlation Between Sulfate Reduc-
ing Bacterial Colonization and Metabolic Activity on
Selected Metals in a Recirculating Cooling Water
System,” CORROSION/92, Paper no. 183 (Hous-
ton, TX: NACE, 1992).
50. H. von Rege and W. Sand, “Identification and Simu-
lation of MIC on Metals by a Mobile Test Apparatus,”
1995 International Conference on Microbially Influ-
enced Corrosion (Houston, TX: American Welding
Society and NACE, 1995), p. 58.
51. B.J. Webster, D.B. Wells, and P.J. Bremer, “The In-
fluence of Potable Water Biofilms on Copper Cor-
rosion,” CORROSION/96, Paper no. 294 (Houston,
TX: NACE, 1996).
52. A.M. Brennenstuhl and T.S. Gendron, “The Use
of Field Tests and Electrochemical Noise to De-
fine Conditions for Accelerated Microbiologically In-
fluenced Corrosion (MIC) Testing,” in Microbiologi-
cally Influenced Corrosion Testing,eds. J. F. Kearns
and B.J. Little, ASTM STP-1232 (Philadelphia, PA:
American Society for Testing and Materials, 1993),
pp. 15-27.
 CHAPTER 1 1

MIC Case Histories

Compiled b y Hector A. Videla

Microorganisms are ubiquitous, and microbiologically influenced corrosion (MIC) can be encountered
in a diversity of natural and industrial environments. MIC failures of technical equipment often occur
under more varied operational conditions than those of inorganic or abiotic corrosion. Practical cases
can help illustrate a number of situations where failure by corrosion or fouling are always due to the
interaction between microorganisms and the structural materials. In each case, the applied solution must
be tailored to particular requirements, taking into account the influencing elements. These elements
include microorganisms, materials, physicochemical characteristics of the environment, fluid dynamics,
the type of protection applied to the system, and others.
The case histories presented in this chapter were selected to cover different situations frequently
encountered in practice.

Carbon Steel (CS)

CS-3: Marine Microbial Corrosion
CS-4: The Detection and Mitigation of MIC
Note: CS-1 and CS-2 located in Volume 1
Mixed Metals (MM)
MM-3: Microbiologically Influenced Corrosion in Geothermal Fields in Mexico
Note: MM- 1 and MM-2 located in Volume 1
Stone (S)
S-1 : Microbial Corrosion of Cultural Heritage Stone Works
Stainless Steels (SS)
SS-13: Localized Corrosion of Stainless Steel Milk Sterilizers
Note: SS- 1 through SS- 12 located in Volume 1

The MIC of carbon steel in marine environments CS-3 is described in case histories involving European
harbor pilings’ internal surfaces of ships’ ballast tanks, and ships’ hull bottom plates. Although it can not
be strictly classified as a carbon steel case, the fourth case history in marine environments describes
the tin-oxide corrosion of the white-metal bearing surfaces used in the main propulsion engines of five
different vessels.
The practical aspects of detection and mitigation of the MIC of carbon steel CS-4 are illustrated by
case histories from South African industrial plants: the mechanical removal of tubercles from a pipeline
used for water transports the use of an organic wetting agent and an anionic iron-dispersing copolymer in
a fire-water system to mitigate MIC, and the use of biocides and biodispersants to control MIC in a power
station.
The MIC of carbon steel and stainless steel is described jointly with the microbial biodeterioration of
other materials such as the reinforced fiberglass and wood MM-3 that are used in the cooling towers of
geothermal power plants in Mexico.
11.1
11.2 MIC Case Histories

The two last case histories of this chapter refer to a case of localized corrosion of stainless steel and
to the biodeterioration of stone works.
The stone case history S-1 describes the biodeterioration or the discoloration of stone work by the
action of the microorganisms. It must be emphasized here that when a material (e.g., stone) has a cultural
value, a staining process or the formation of patina could affect the esthetic value of the material even in
the absence of a noticeable material decay.
The stainless steel case (SS-13) describes the localized corrosion of (UHT) milk sterilizers. In this
peculiar case history, microorganisms are not involved in the metal attack. The corrosion is due to the
combined action of biological substances from the milk (e.g., caseinates), chemical cleaning agents and
high levels of chlorides in the water. The term “biodeterioration” should be used in replacement of MIC for
stone and non-metallic materials. Conversely, MIC would be used to denote the electrochemical process
of metal dissolution initiated or accelerated by microorganisms.
Some case histories have a complete description of symptoms, analytical findings, possible mech-
anisms, and corrective measures. Others are a brief description from original cases, and include only
significant details. However, in all cases the relevant role of the microorganisms or biological factors is
highlighted.
CASE HISTORY CS-3
Marine Microbial Corrosion
By 1. B. Beech, S.A. Campbell, and F.C. Walsh
Introduction
Marine conditions represent an aggressive
and unforgiving environment for the degradation
of metals used in harbor constructions and on
board vessels. The corrosion of marine engineer-
ing components and structures can arise as the
result of shortcomings in materials selection, de-
sign, or fabrication, poor choice of the protec-
tion technique, or inadequate maintenance and
housekeeping.’ In comparison to land-based sys-
tems, the failure of shipping components via cor-
rosion presents additional problems owing to the
possibility of failure at sea, restricted access for
inspection of corrosion failures, and, for remedial
work, the inconveniences and costs involved in lost
sailing time or decreased speeds and the need to
berth or dry dock the vessel when severe problems
exist.
Many cases of marine microbial corrosion
have been discovered at an advanced stage, when
mechanical damage or process inefficiencies have
forced hasty remedial action or it was not rea-
lized that microbial corrosion processes were
causing the initiation, or propagation of attack. In
some cases, the accelerated rate of attack on the
metal or its localized nature has been correctly at-
tributed to a particular corrosion mechanism but
the underlying cause is not understood. Emphasis
is often placed on rapid removal and replacement
of damaged components or structures, because
of short-term commercial or strategic pressures.
In extreme cases, the lack of diagnosis may lead
to repetitive or more serious failures.
Four case studies have been selected for this
review. These are based on types of corrosion that
have received insufficient attention in the literature,
despite their importance. Several cases related
to each type of failure have been experienced, in
several ports and on various ships over the past
decade.
Case #1: Low Water Corrosion of
Constructional Steel Piling
Background
Severe corrosion and perforation of steel piling
at the low water level has been reported in several
European ports and harbors (Figures 11.1 and
11.2). Steel sheet piles are usually produced from
grade 43A and 50A carbon steel (e.g., BS 4360).
The maximum length of the pile can be rolled
up to 30 m, and its thickness is typically within
the range 10-28 mm. Steel piles are used in
many types of temporary works and permanent
structures such as retaining walls, river frontages,
quays, dock harbor works, or land reclamation
and sea defense works.
The corrosion profile of steel pilings in tidal
waters has five different characteristic zones: at-
mospheric, splash, tidal, permanent immersion,
and subsoil.* Corrosion mechanisms operating in
these zones are generally well understood3 and,
for UK harbours, the average corrosion rate of
each zone has been predicted4 (Figure 11.3).
Recently, a large number of piling walls in
quays, jetties, river embankments, and piers have
needed repair or even replacement after as lit-
tle as 20 years; their effective life, according to
estimates of normal corrosion rates in seawater
11.4
FIGURE 11.1
General view of steel piling, showing zones affected by
low water corrosion. (See color plates.)
environments, should be greater than 50 years. In
some cases, the rate of corrosion reached 0.5 mm
per year, resulting in perforation of sheets of steel
welded over existing holes within six months of the
installation of such repair panels.
To determine the cause of steel failure, in-
strumentation has been installed at a UK port to
continuously monitor electrical potentials and gal-
vanic current flow between steel panels mounted
at various levels on sheet piling walls (Figure 11.4).
This monitoring program, carried out over a pe-
riod of one year, clearly showed that although
FIGURE 11.2
A close-up of a particular section of steel piling, show-
ing severe perforation at the low water level. (See color
plates.)
Marine Microbial Corrosion
~0.03
Bedzone
9
Corrosion
profile
FIGURE 11.3
Typical corrosion profile of steel piling in tidal seawater,
showing the general rates of penetration observed.
macro-anodic and macro-cathodic regions were
initially formed, these did not persist for much
longer than 100-1 50 days and that after that time
there can be no viable electrochemical explana-
tion for the very severe corrosion experienced
at the low water level. Attention was then turned to
the involvement of a biological component in the
deterioration of steel pilings.
Findings
The present study was carried out in the
United Kingdom to elucidate the contribution
of biofilms to low water (tidal zone) corrosion
of steel pilings in Portsmouth Harbour. Samples of
biofilms recovered from the surface of corroding
and noncorroding areas of pilings were collected
and analysed microbiologically to determine the
types and numbers of organisms present using
API identification kits and MPN counts. Char-
acterization of corrosion products accumulated
Marine Microbial Corrosion
Low water zone
lol Bed zone
FIGURE 11.4
Arrangement of steel test panels (approximately
30 cm x 30 cm) in various tidal zones during a test pro-
gram of galvanic current monitoring using the zero resis-
tance ammeter technique. Samples were placed on the
“outpan” (0)or “inpan” (I) regions of the piling.
in biofilms was carried out by energy dispersive
X-ray analysis (EDXA) and by X-ray diffraction
(XRD). Electrochemical measurements using lin-
ear polarization resistance (LPR) were performed
under laboratory conditions to determine the
corrosion rates of steel in the presence of pure
and mixed microbial isolates.
The outcome of the microbiological studies re-
vealed that the biofilms contained diverse genera
of aerobic, facultatively anaerobic, and anaero-
bic bacteria such as Pseudornonas, Vibrio, and
sulphate-reducing bacteria (SRB), all of which
are known to have a role in marine corrosion of
The composition of microbial consortia var-
ied depending on the region from which sam-
ples were taken. In general, higher levels of all
types of bacteria were detected in biofilms re-
covered from corroding areas of the piling, typ-
ically 3 x 10’ cells cm-2, compared to biofilms
removed from the noncorroding sites, typically
3 x lo4 cells cm-* (lo2 SRB cells). The number
of SRB present in biofilms associated with corrod-
ing parts of the piling (1 O4 or 1 O5 SRB cells cm-2)
exceeded the number of SRB detected in biofilms
removed from the noncorroding sites, by one to
two orders of magnitude.
Biofilms recovered from sites that did not ex-
hibit corrosion showed the prevalence of either
Pseudornonas or Vibrio species (typically contri-
buting to between 70% and 90% of the total spe-
cies detected) and only up to 10% SRB, whereas
biofilms collected from corroding areas contained
a mixture of all bacterial genera with SRB being a
dominating species (up to 60%) and high levels of
either Pseudornonas or Vibrio (up to 40%).
Phase analysis of surface products by XRD
revealed differences between samples from
corroding and noncorroding sites. The former
consisted largely of iron sulphides whereas the
latter showed the presence of oxyhydroxides
and magnetites. EDXA analysis confirmed the
accumulation of relatively high levels of sulphur in
samples taken from the corroding areas of piling.
These findings were in good agreement with
microbiological data, which showed a high level
of SRB (up to lo6 cells cm-2) associated with the
corroding sites.
Linear polarization resistance measurements
of averaged corrosion rates revealed that the most
rapid failure of steel would occur in the presence
of a mixed population of SRB and Vibrio species
(1 :1 ratio). In this culture a corrosion rate of 1.4mm
per year was recorded. Rates of 0.38 mm per
year and 0.30 mm per year, respectively, were ob-
served for steel exposed to a mixed population of
Pseudornonas and SRB (1:l ratio) and to SRB
species. These corrosion rates were significantly
higher than the rate of 0.019 mm per year mea-
sured in sterile seawater.
Summary
The overall results of this investigation, based
on microbiological, electrochemical, and mate-
rial analysis, indicate that biofilms formed in tidal
zones on the surface of steel piling were likely
to contribute to the localized corrosion of the
structure and that the composition of microbial
consortia could be a key factor in determin-
ing whether and to what extent the biocorrosion
11.6 Marine Microbial Corrosion

influences the performance of the piling material.

A more detailed treatment of microbial corrosion
of steel pilings at the low water level is provided
e l ~ e w h e r e Further
.~ studies are being carried out
on the effectiveness of (a) cathodic protection,
(b) protecting organic coatings, (c) mechanical re-
moval of the biofilm by high-pressure water jets,
and (d) replacing the existing material by low alloy
steels, to determine the most effective method, or
combination of methods, in controlling marine bio-
corrosion of steel pilings.

Case ## 2: Pitting and Perforation of

the Internal Surfaces of Ship’s
Ballast Tanks

Background
During pressure testing of a ballast tank near
the bottom of a ship, pitting and some perforation
was discovered. The damage to the 12-mm steel
hull plate was located under mud slimes in the tank
bottoms (Figure 11.5). Consultation of the vessel’s
records indicated that the corrosion probably oc-
curred within a nine-month period and that the ves-
sel had undergone constructional work to increase
its size and load-carrying capacity. During this con-
structional work, the ship was floated in a harbor
that was later found to have high levels of sulphate-
reducing bacteria (up to 1O6 cells ~ m - ~This
) . type
of problem has been experienced by the authors
on seven other vessels (unpublished results).
Findings
A thorough manual inspection of the tank
was carried out in dry dock and sections of hull
plate were removed from the vessel for anal-
ysis (Figures 11.6 and 11.7). Sludge, mud
(Figure 11.6), and corrosion products from the
pitted regions (Figure 11.7) were brought to
the laboratory for rapid analysis. Damaged sec-
tions were cut out and samples were retained for
metallographic and Scanning Electron Micro-
scopy (SEM)/EDXA analysis. Chemical and mi-
crobial analysis of samples from this ship (and
FIGURE 11.5
View of the underside of a ship’s hull bottom plate in a
dry dock, with a corroded section removed for analysis
and repair. (See color plates.)
a sister vessel) revealed high levels of sulphide
in the sludge (up to 3600 ppm) together with
significant levels of both anaerobic (103-l O5 ~ m - ~ )
and aerobic (103-106 ~ m - bacteria.
~ ) In partic-
ular, active sulphate-reducing bacteria up to a
level of 1O5 cells ~ m were- ~found via microscopic
and standard microbial culture techniques. A dam-
aged section of hull plate is shown in Figure 11.8,
which gives an indication of the severity of the
pitting attack and the attendant reduction in the
thickness of the hull plate. EDXA analysis of a
damaged section of the steel plate showed an
increasing sulphur content near pit bottoms
Figure 11.9a. XRD and chemical analysis demon-
strated the presence of iron sulphides in these
regions, and high levels of magnetite were also
Marine Microbial Corrosion

FIGURE 11.7
General view of the inside surface of a section of hull
plate, showing extensive pitting corrosion and crater
formation. (See color plates.)

the result of classical corrosion mechanisms.10

FIGURE 11.6
Photograph of the inside surface of a ship’s bottom plate
removed from the vessel, showing pitting of the steel re-
vealed by clearing away the mud film. (See color plates.)
The analytical results revealed the presence of
high levels of SRB in mud samples and signifi-
cant sulphide ion and iron sulphide formation in
pitted regions. Damage was largely attributable
to microbially influenced corrosion, primarily due
to the presence of SRB action. The mud slimes
and sludge act as a supportive matrix for micro-
bial growth. The formation of localized corrosion

found. Figure 11.9b provides a schematic to indi-

cate the corrosion cells that can form inside the
pits.
It was discovered that the harbor berth used
for constructional work on the vessel was located
a short distance away from the discharge from
a fish processing plant, which could provide a
high level of nutrient-rich material during ballasting
operations.

Summary FIGURE 11.8

Cross section of the hull plate, showing the reduction in
The rapidity, severity, and localized nature Of normal thickness (1 2 mm) due to microbial attack result-
this attack exceeded those expected to occur as ing in severe pitting. (See color plates.)
11.8
8
0,5K
d
c1
0 i N W
FIGURE 11.9a
Energy dispersive X-ray analysis spectrum taken in the bottom of a pit on the surface of a steel ballast tank plate suffering
microbial corrosion under mud slimes.
cells, mainly the result of differential aeration cells,
and the existence of magnetite as an efficient ca-
thodic site for oxygen reduction were likely to have
contributed to the corrosion rate.
Remedial Work
Damaged areas of the vessel were replated.
A careful survey of the affected tank (and others)
was carried out. The ballast tanks were thoroughly
cleaned to remove mud and sludge and then re-
coated with a nonsetting organic coating where
necessary. The sister vessels were also inspected.
Early stages of pitting corrosion were detected
in localized regions but cleaning, followed by in-
filling and the application of protective organic
coatings and biocide, precluded the need for re-
plating. Where feasible, ballasting with fresh water
was recommended.
Marine Microbial Corrosion
Ln W P co a 0
rl
Case # 3: Tin-Oxide Corrosion of
White Metal Bearing Surfaces
Background
Over the past ten years, the authors have in-
vestigated the failure of thirteen white metal faced
bearings from various parts of main propulsion
engines on five vessels. The majority of these
have been journal bearings from both diesel and
steam turbine engines, although thrust pad sur-
faces have also been involved. In all cases, the
bearing failures resulted in the need for partial
stripping and rebuilding of the ship’s engine. Typ-
ical examples of bearing compositions are pro-
vided in Table 11.1. While most of the bearing
surfaces were tin-based, several examples of lead-
based materials have been encountered. All of the
bearing surfaces showed severe pitting together
 low O2 concentration

I iron k d p h i d e and oxides

arising fran action of
sulphides (anodic site)
pit b o t t c h n remains
active leading t o perforation

FIGURE 11.9b
Corrosion cells that can arise under mud films and in the presence of biofilms.

with scoring wiping and other types of mechanical
damage in many cases. Examples of a journal and
a camshaft bearing are shown in Figures 11.10
and 11.12 while Figures 11.11 and 11.13 show
more detailed photographs of pit formation on the
surface of these bearings.
Findings
In each case analysis was made on a wide
range of samples, including the lubricating oil,
sludge from the oil purification system and water
phases, and the bearing surfaces. In all cases,
analysis of the bulk lubricating oil by plasma
emission spectroscopy (for dissolved wear metals)
and standard ASTMAP tests (e.g., for viscosity,
viscosity index, flash point, and total base num-
ber) showed the oils to be suitable for further ser-
vice. However, many of the oil samples showed
significantly reduced demulsification properties in
comparison to fresh oil. Bearings A and B were 10-
cated near a water header tank, and water leakage
was observed onto the camshaft area of the en-
gine. Analysis of the water showed a pH of 7.7 and
a low conductivity (250 mS cm-I) together with a
very low chloride ion level (t25ppm).
The surface of these bearings showed exten-
sive pitting and mechanical damage as indicated
in Figures 11.11 and 11.13. In addition, large sec-
tions of white metal had been removed. In some
areas, the steel shell was exposed. Metallographic
and SEM observations revealed a wide range of
11.10 Marine Microbial Corrosion

~~ ~ ~ __.__ ___
TABLE 11.1
Composition of White Metal Bearing Alloys (Determined by Atomic Absorption Spectroscopy)

Percentage by Weight of Metal

Bearing Sample Tin Antimony Copper Lead Sum
Bearing A 80.3 7.7 7.5 4.6 100.1
(main camshaft)
(o.d.(A)-l1 cm)
Bearing B 15.2 7.5 0.8 75.8 99.3
(main camshaft)
(0.d. -8 cm)
Bearing C 87.0 6.8 3.6 0.9 99.3
(main engine journal)
(0.d. -20 cm)
Bearing D 88.0 7.0 3.5 0.7 99.2
(thrust pad assembly)
(Area -10 cm2)

(A)Nominaloutside diameter

sharp-sided pits, several millimeters in diameter
and with depths from 1 to 60 mm (the former be-
ing the nominal lining thickness). The interface
between the white metal and the steel shell ap-
peared to be regular and well defined. Etching and
metallographic analysis revealed well-dispersed
SbSn cuboids and Cu6Sn5 strands within a
tin-based matrix. No selective corrosion or degra-
dation of the intermetallic phases was ob-
served. A detailed SEM survey showed the pres-
ence of many pits containing intact corrosion
products. EDXA studies showed the presence of

FIGURE 11.10 FIGURE 11.11

A journal bearing, showing pitting and scoring due to Close-up of the surface of a white metal bearing, show-
the formation of hard tin oxide particles (which appear ing the formation of pits containing dark particles of tin
as darkened areas on the surface). (See color plates.) oxides. (See color plates.)
Marine Microbial Corrosion
FIGURE 11.12
A camshaft bearing, showing pitting and mechanical
damage to the white metal lining. (See color plates.)
high sulphur levels in the bottom of many of the
pits. In several cases, fracture cracks were seen
emanating radially from pit recesses, as shown in
Figure 11.10. Several of the larger pits were
scraped and the wear products were analysed by
XRD. The results showed the presence of SnO and
Sn02 in addition to the usual phases of the lin-
ing material (b-Sn, SbSn, and Cu~Sns).The pres-
ence of significant amounts of tin oxides in the
FIGURE 11.1 3
A scanning electron micrograph of the surface of a pitted
region on the bearing shown in Figure 11.1 2, showing
fatigue cracks around the pit recesses.
smallest pits was confirmed by electron diffraction
(ED) measurements on fragments.
Strategic sampling of the lubricating oil system
in areas such as tank bottoms, U-tube sec-
tions, filters, and purifier bowls showed the pres-
ence of sludges and seawater-contaminated water
phases, both of these having high levels of anaer-
obic and aerobic bacteria. Both XRD and ED re-
vealed significant levels of SnO and Sn02 within
the corrosion pits.
Summary
The results are consistent with failure due
to the localized formation of tin oxides via elec-
trochemical c o r r o ~ i o n . ~This
~ - ~type
~ of degra-
dation requires a conductive electrolyte phase
and a suitable cathodic reactant. In the case of
bearings C and D, seawater contamination and
emulsification (assisted by the microbial presence)
provided an efficient electrolyte. Localized pock-
ets of water (arising from leakage into the en-
gine) became emulsified and conductive via ther-
mal breakdown of the oil during service. In all
cases, the most obvious cathodic reactant is dis-
solved oxygen, although the reduction of iron ox-
ides embedded into the surface may also have
played a part. The formation of hard particles of
Sn02 results in scratching and scoring as the
bearing surface loses its essential conformabil-
ity and embedability properties. Localized stress
concentration at pit bottoms may lead to stress
cracking.
Remedial Work
For all the ships involved, steps were taken
to prevent water ingress into the lubricating oil
by leakage or condensation. Following thorough
cleaning, the bearings were relined and carefully
refitted. In the case of vessels showing signif-
icant water phases, sludge formation, and the
presence of microorganisms in the oil system,
cleaning was followed by biocide treatment, im-
proved purification procedures, and oil monitoring
programs.
11.12 Marine Microbial Corrosion

Case # 4: Extensive Pitting of the

External Surface of a Ship’s Hull
Bottom Plate

Background
The immersed part of a ship’s hull on a float-
ing oil storage tanker, anchored in tropical waters,
was examined by divers and was found to be heav-
ily fouled to a thickness of up to 60 cm. The ves-
sel showed some leakage of its oil cargo and was
taken into dry dock for inspection. The hull was
cleaned and subjected to an extensive visual ob-
servation. The bottom was found to be severely FIGURE 11.15
corroded with tens of thousands of pits, each A welded region of the ship’s hull plate, showing a row
pit being approximately hemispherical in shape, of pits along the weld seam. (See color plates.)
20-25 mm deep, and filled with black material. Re-
moval of outer corrosion products and macrofoul-
ing exposed an underlying shiny metallic surface. external hull plate. Oil leakage into the sea sig-
Figure 11.14 shows a section of the hull plate when nified damage and a diver was sent down to in-
the ship was inspected in dry dock after removal spect the hull. Videos showed a comparable pat-
of all marine growth and corrosion. Figure 11-15 tern of damage to that on the first tanker but no
shows the distribution of pits along a welded seam large-scale perforations were detected. The ship’s
hull was covered with barnacles and other types
and Figure 11.16 provides an example of a perfo-
rated section of hull plate. of macrofouling such as seaweed. After clean-
A second (400,000 tonne) oil storage tanker ing, some pitting of the hull was found. A diver
was also found to show pitting corrosion of the found a macrofouled area containing 10-20 oys-
ters. Removal of these revealed some damage to

FIGURE 11.1 4 FIGURE 11.16

General view of ship’s hull, showing the extensive distri- A Perforated zone of ship’s hull Plate, showing leakage of
bution of pits over the surface. (See color plates.) seawater from the interior of the vessel. (See color plates.)
Marine Microbial Corrosion
the underlying steel but no perforations. When dis-
lodged, some of the oysters took the paint coat-
ing with them. Holes were typically found to be
18-20 mm in depth in the 25-30 mm hull plate. The
damaged zone was filled with black (magnetite-
containing) deposits and the underlying metal was
very dark in appearance, with some areas being
covered by corrosion products. The following re-
sults refer to the second vessel.
Findings
A sample from a pit, containing water and
sludge, was allowed to settle and these samples
were analyzed for the presence of sulphates and
sulphides. The water was found to contain traces of
hydrogen sulphide and 2.28 g/dm3 sulphate (c.f.,
2.26 g dm-3 for seawater). The sludge contained
0.25% SO:- and 0.92% S2-. The water was in-
fected with extremely high levels (on the order
of 1O8 cells ~ m - of ~ sulphate-reducing
) bacteria.
Aerobic bacteria were also present at a concen-
tration of 1o3 cells ~ m - ~ .
Summary
Both vessels provide examples in which a very
aggressive local environment, caused by macro-
fouling, resulted in extensive pitting damage to
a ship’s hull plate. The presence of high lev-
els of sulphide ions in the sludge found in the
pit, together with the extremely high numbers of
sulphate-reducing bacteria present in the sam-
ples taken from beneath the macrofouling layer,
is indicative of active microbiological corrosion in
this region. The presence of aerobic bacteria in
the sample may have resulted in even more ag-
gressive conditions due to accumulation of cor-
rosive metabolic products such as exopolymers
and organic and inorganic acids8 The attachment
of oysters appeared to create an extremely favor-
able environment for the growth of SRB, as almost
pure cultures of these bacteria were isolated from
the pit underneath the oyster.
Subsequent laboratory trials of the purified cul-
tures showed this SRB strain to be highly corro-
sive to mild steel with measured corrosion rates of
0.5 mm y-l in batch cultures. Additional studies
showed a very high activity of the hydrogenase
enzyme, which has been implicated in microbial
corrosion of steel by SRB.15
Remedial Action
Extensive cleaning and replating of the hull
plate was necessary. Regular inspection and me-
chanical cleaning of the macrofouled hull plate
to remove biofilms, followed by coating with an
appropriate antifouling paint, was recommended.
Cathodic protection was used in the case of the
second vessel, but excessive anode wear oc-
curred and no beneficial effects on the corrosion
rate were noted.
Closure
During the investigation of microbial corro-
sion problems, on-site observation and sampling
should be followed by a wide range of chemical and
surface analysis whenever feasible. The materials
analysed may include water phases, oils, sludges,
emulsions, and scale in addition to corrosion prod-
ucts. The application of SEM, EDXA, XRD, and
ED techniques to localized corrosion products is
seen to be particularly important in diagnosing the
type of attack via a knowledge of phase compo-
sition. The importance of X-ray techniques in this
context has been emphasised elsewhere.16 Docu-
mentation of corrosion failures provides a critically
important source of information for the following
reasons:
Design engineers may recognize the
dangers and take remedial action.
Inspection and maintenance personnel
may be alerted to the possibility of corro-
sion and hence aggressive conditions in
similar environments on vessels may be
treated early, avoiding severe damage.
Personnel involved in inspection and
consultancy services can be made more
aware of the likelihood of microbial
11,14
corrosion and the attendant possibility
of accelerated, localized attack on metal
components and structures.
Research workers may be stimulated
to investigate the complex mechanisms
and interrelated factors involved in prac-
tical cases of corrosion.
Acknowledgments
The authors are grateful for technical assis-
tance rendered by Dr. A.H. Nahle and Dr. R.A.
Scannell (University of Southampton) and collab-
orations with Dr. T. Baker (Imperial College of Sci-
ence and Technology), Dr. W.T. Chao, K. Johnson
(British Steel Technical), and Prof. D.J. Schiffrin
(University of Liverpool). Scanning electron mi-
croscopy and energy dispersive X-ray analysis
benefited from the expertise of Dr. S. Moss and
P. Bond. X-ray diffraction facilities were kindly pro-
vided by R. Mortlock and Dr. M. Weller (University
of Southampton).
References
1. S.A. Campbell and F.C. Walsh, Bull. Electrochem.
8(1992):311-317.
2. H.A. Humble, Corrosion 5(1949): 292-302.
3. M. Schumacher, Seawater Corrosion Handbook
(Park Ridge, NJ: Noyels Data Corp., 1979).
Marine Microbial Corrosion
4. E. Marsh and D. Dulieu, British Steel Technical
Report, SUS/R/S/952/1/92/D, 1992.
5. N.J.E. Dowling, J. Guezennec, and D.C. White, in
Microbial Problems in the Offshore Oil Industry,
eds. E.C. Hill, J.L. Shennan, and R.J. Watkinson
(Chichester, England: Wiley, 1987), pp. 27-38.
6. C.C. Gaylarde and J.M. Johnston, Int. Biodeterior.
Bull. 18(1982):111-116.
7. C.C. Gaylarde and H. Videla, Int. Biodeterior.
23(1987): 91-1 04.
8. I.B. Beech, C.W.S.Cheung, C.S.P. Chan, M.A. Hill,
R. Franco, and A.R. Lino, Int. Biodeterior. Biodeg.
34(1994) 289-303.
9. F.C. Walsh, W.T. Chao, S.A. Campbell, and I.B.
Beech, Int. Biodeterior. Biodeg. 34(1994): 259-
274.
10. S.A. Campbell, R.A. Scannell, and F.C. Walsh,
“Microbially-Assisted Pitting Corrosion of Ships’
Hull Plate,” Indust. Corros. December (1989):
7-1 4.
11. J.B. Bryce and T.G. Roehner, Trans. I. Mar. E.
73(1961): 377-385.
12. J.F.C. Brown and E.E. Goundry, “Bearing White
Metal Corrosion: An Electrochemical Explanation,”
BSRA Report NS 153,1967.
13. K.A. Lloyd and R.W. Wilson, “Formation of Tin
Oxide on White Metal Bearings,” Proc. I. Mech. E.,
7th Tribology Conference, 1969.
14. R.W. Hiley, Trans. I. Mar. E. 91(1979):52-57.
15. C.W.S. Cheung and I.B. Beech, Biofouling 9(1996):
231-249.
16. F.C. Walsh and A.H. Nahle, “The Application of
X-ray Techniques to Studies of Corrosion and
Protection,” Arab. J. Sci. Eng. 20(1995): 315-
341.
CASE HISTORY CS-4
The Detection and Mitigation of MIC
By If,Cloete, PJ. Allison, and WI.J,Poulton
Summary
The present trend in industrial water systems is
to minimize both water consumption and water dis-
charge by recirculation. This results in the concen-
tration of dissolved and suspended substances,
promoting growth of waterborne microbes, and
shifting the microbial community to a more copi-
otrophic state. The accumulation of undesirable
organic materials on any surface, either natural
or man-made, is generally referred to as biofoul-
ing with subsequent macrofouling of the system
and concomitant microbially induced corrosion
(MIC).
Tubercles of iron hydroxide or iron oxide
caused by the growth of aerobic iron-precipitating
bacteria and anaerobic sulphate-reducing bacte-
ria were removed to prevent excessive underde-
posit corrosion. It is important to note that most
of the commonly used corrosion inhibitors cannot
penetrate through the tubercles to passivate the
active anodic sites.
A number of MIC mitigation strategies were
employed, depending on various factors includ-
ing the system configuration, extent of pitting, and
treatment economics.
Chemical cleaning using a combination of an-
ionic copolymer dispersants and organic pene-
trants was an effective mitigation program that
was conducted on-line. Gradual loosening and dis-
solution of iron corrosion by-products occurred,
and the metal beneath the softened and dis-
persed nodules was chemically passivated and
sanitized.
Mechanical cleaning (pigging) was also em-
ployed as a means of removing MIC nodules.
Introduction
Both water consumption and discharge in
industrial water systems are currently minimized.
The circulation of such water results in concen-
tration of dissolved and suspended substances,
promoting the growth of waterborne microbes,
biofouling, and subsequent macrofouling of the
system and concomitant microbially induced
corrosion.
A number of reviews have been published
on the mechanisms of microbially induced corro-
sion and the organisms involved.’ The subject of
biofilm formation has also been well covered in the
literature.
A lack of information on practical control strate-
gies and case studies is appararent.
Owing to the inaccessibility of sulphur-
reducing bacteria (SRB) beneath biofilms and tu-
bercles, many microbiocide treatment programs
fail to control microbiologically influenced corro-
sion in industrial water systems2
Recognition of the inability of most microbio-
cides to penetrate slime masses and tubercles
stimulated interest in compounds capable of pen-
etrating and dispersing such deposit^.^ Biodis-
persants have been used on a continuous or in-
termittent basis to enhance the effectiveness of
microbi~cides.~ Sessile bacterial biofilm popula-
tions are dispersed or loosened from the surface
into the bulk water, thereby exposing the under-
deposit corrosion sites (pits) to biocide-containing
circulating watera4
Removal of iron oxide tubercles, which har-
bor sulphate-reducing bacteria (SRB), can be
achieved by a number of methods, including
11.16
physical removal by “pigging,” the more aggres-
sive acid cleaning techniques, or the passivating
on-line cleaning approach using a combination of
surfactants and biocides.
The case histories presented demonstrate
successful strategies for the detection and mit-
igation of microbial corrosion in industrial water
systems.
Case Study 1 : Mechanical
Removal of MIC Tubercles by
Means of Pigging Operations
Severe MIC was prevalent in a 450-mm diam-
eter 17-km long mild steel pipeline used to trans-
port water at ambient temperatures between two
mines. The sulphate concentration of 1015 mg/l,
neutral pH of 7.60, and intermittent operation of
the pipeline provided conditions favorable for the
growth of SRB.
Figure 11.17 shows the density of tubercles
within the pipeline. Removal of the tubercles ex-
posed typical pitting corrosion caused by SRB
(Figure 11.18).
Since chemical cleaning was not an option
for this system (because of excessive costs)
FIGURE 11.1 7
High density of tuberculation before mechanical clean-
ing. (See color plates.)
The Detection and Mitigation of MIC
FIGURE 11.18
Pitting corrosion beneath a tubercle. (See color plates.)
a series of mechanical pigging operations was
undertaken at regular intervals over an eight-
month period. The pigs comprised a flexible cellu-
lar polyurethane, coated with an abrasion resistant
polyurethane polymer. The flexible interior allowed
for contraction and expansion of the pig cylinder
with variations in the pipe interior. Wire brushes
on the exterior of the pig facilitated easier removal
of harder corrosion by-products.
Microbiological analyses were performed on
water samples taken before and after passage
of the pig through the pipe. A marked increase
in numbers of total aerobic bacteria (TAB) (from
bacterial biofilm) and SRB was detected after the
mechanical cleaning action. Counts of TAB in the
bulk water increased from 1O4 to 1O8 colony form-
ing units/ml, and those of SRB from 2 to greater
than 100 cfu/ml after pigging.
Incorporation of a biodispersant and broad
spectrum microbiocide (comprising two different
“quick-kill” active ingredients) into the flush water
following the pig served to reduce the SRB popu-
lation and eventually resulted in a 100°/o kill of the
bacteria.
Visual inspection of the pipe interior after the
pigging operations showed that efficient removal of
the nodules and corrosion by-products had been
achieved. Figure 11.19 shows the cleaned metal
surface with “scars” where the tubercles had been
removed.
The Detection and Mitigation of MiC
FIGURE 11.19
Scars on the metal surface after mechanical cleaning
(pigging) operations. (See color plates.)
Case Study 2: Mitigation of MIC
Using an Organic Wetting Agent
and an Anionic Iron-Dispersing
Copolymer
MIC mitigation was required to prevent serious
impairment of a fire water system integrity caused
by leaking pipes.
FIGURE 11.20
Ferric hydroxide ribbons filtered from the fire hydrant
water (400X magnification). (See color plates.)
FIGURE 11.21
Gallionella ferric hydroxide ribbon and bacterial cell
(1 OOOX magnification). (See color plates.)
Samples of water were collected from the
pipes and filtered through 0.22-pm cellulose ac-
etate filters and examined using light and scan-
ning electron microscopy. The appearance of
bean-shaped bacterial cells of the iron bacterium
Gallionella was evident.
Figures 11.20 and 11.21 show light micro-
scopy photographs of the twisted iron hydroxide
ribbons at a magnification of 400X and 1OOOX re-
spectively. The SEM appearance is illustrated in
Figure 11.22.
FIGURE 11.22
Scanning electron micrograph of twisted ferric hydro-
xide (SOOOX magnification).
11.18
FIGURE 11.23
Biofouling deposits on cooling tower packing before
biodispersandbiocide treatment (A) and packing clear of
biofouling deposits after three weeks of treatment (B).
(See color plates.)
Bacterial swabs taken from the fouled metal
surface were cultured in a synthetic agar medium
selective for Gallionella ferrugines and positive
growth was detected. Similarly, the presence of
viable SRB was confirmed by culturing swabs
from the pitted areas in a modified Postgate/SABS
The results from the microbial investigation
showed that the concentration of 3-4 mg/l soluble
iron (Fe2+) in the water, caused by electrochemi-
cal corrosion, stimulated the growth of Gallionella
in the aerated system water. Tuberculation or
induced precipitation of iron hydroxide in turn pro-
vided the anaerobic environment required for the
growth of SRB.
The Detection a n d Mitiaation of MIC
FIGURE 11.24
Slight algal regrowth in the spray area of a cooling tower
after nine months of biodispersanVbiocide treatment.
(See color plates.)
The mitigation strategy involved application
of an organic wetting agent and an anionic
iron-dispersing copolymer to gradually dissolve
and disperse the bacterial nodules. Caution was
required with this approach, since too rapid a rate
of chemical dispersion might lead to dislodgment
of large pieces of corrosion by-products.
Although chemical dispersion was applied
successfully, replacement of some of the piping
was necessary, since some of the pits had
penetrated through the pipe wall and removal of
the nodules removed the “protective caps” and
led to water leaks.
A controlled maintenance program incorporat-
ing a microbiocide, biodispersant, and scale and
corrosion inhibitor was recommended for ongoing
treatment of the fire water system.
The Detection and Mitigation of MIC
Case Study 3: MIC Control
by Biocide and Biodispersant
Treatment in Power Station
Open Recirculating Cooling
Water Systems
Cooling water treatment programs were mon-
itored in the open recirculating cooling water
systems at four fossil-fired power station^.^ Combi-
nations of three biodispersants and four biocides
were evaluated. Visual system inspections were
carried out where possible. All of the dispersants
resulted in increases in the numbers of planktonic
A
B
FIGURE 11.25
Strainer box before the initiation of biodispersantlbiocide
treatment showing hard nodules on surface (A) and un-
derlying pits filled with black liquid (B). (See color plates.)
bacteria. Biocides resulted in percentage kills of
planktonic bacteria between 83.2% and 1OO%,
with only one exception, where no change in
the number of anaerobic bacteria occurred. The
biodispersants resulted in a decrease in sessile
aerobic bacteria numbers in 80% of the cases
and the biocides resulted in decrease in all of the
systems evaluated. Inspections revealed that the
biodispersant/biocide combination removed ses-
sile microbiological deposits and aided in the pen-
etration of the biocide into inorganic deposits by
softening the overlying nodules. The use of combi-
nations of biodispersants and biocides effectively
controlled microbiological growth in all the cooling
A
B
FIGURE 11.26
Strainer box after three weeks of biodispersanVbiocide
treatment showing softened nodules on surface (A) and
loss of black coloration in underlying pits (B). (See color
plates.)
11,20
FIGURE 11.27
Strainer box after nine months of biodispersant/biocide
treatment showing almost complete removal of nodules.
(See color plates.)
water systems. However, the treatment products
did not produce the same effects in different sys-
tems; therefore treatment products had to be se-
lected for each individual system.
The visual inspections confirmed that a combi-
nation of a biodispersant and biocides was effec-
tive in removing biofilms, biofouling deposits, and
nodules of iron oxide, thus assisting in the miti-
gation of MIC. After three weeks, the biofouling
deposits on the cooling water packing and clari-
fiers were either removed or had lost their green
coloration, indicating cell death (Figure 11-23).
In addition, little regrowth of algae occurred over
the nine-month observation period (Figure 11-24).
Thus the biodispersant/biocide program was effec-
tive not only in the removal of biofouling deposits
but also in preventing any reattachment.
The softening and removal of the nodules in
the strainer boxes occurred over a longer time
The Detection a n d Mitigation of MIC
period (Figures 11.25A, B). After three weeks of
treatment, the nodules had been softened and only
half of them contained SRB (Figures 11.26A, B).
However, it was only after nine months that al-
most complete removal of the nodules and thus
mitigation of MIC occurred (Figure 11-27). This
indicated that the biodispersant was responsible
for biofouling deposit removal and mitigation of
MIC, and not the biocide. However, the use of
biocides, particularly in the “clean-up” phase of
treatment, can assist with the control of those
microorganisms dispersed into the bulk water,
where they are more susceptible to the action of
biocides.
References
1. T. Ford and R. Mitchell, “The Ecology of Microbial
Corrosion,” Adv. Microb. Ecol. 11(1990): 231-252.
2. T.E. Cloete, V.S. Brozel, and A. Von Holy, “Practi-
cal Aspects of Biofouling Control in Industrial Water
Systems,” Int. Biodeterior. Biodeg. 29(1992): 299-
341.
3. L. Jacobs, “Anionic and Nonionic Surfactants for the
Controlling of Attached F! aeruginosa to Glass and
3CRIZ Metal Surfaces,” MSc. Thesis, University of
Pretoria, Pretoria, South Africa, 1996.
4. W.I.J. Poulton, “Monitoring and Control of Biofoul-
ing in Power Utility Open Recirculating Cooling Wa-
ter Systems,” MSc. Thesis, University of Pretoria,
Pretoria, South Africa, 1993.
5. Standard Methods for the Examination of Water
and Wastewater, 15th ed. (Washington, DC: Amer-
ican Public Health Association, American Water
Works Association, Water Pollution Control Feder-
ation; 1981).
6. SABS, “Media and Reagents for Microbiological
Tests,” Test Method 563 (South African Bureau of
Standards, Pretoria, Transvaal, 1975).
 Next Page

CASE HISTORY MM-3

Microbiologically Influenced Corrosion

in Geothermal Fields in Mexico
By B. Valdez Salas, L. Rioseco de la Pefia, G. Hernandez-Duque Delgadillo,
and N. Rosas Gonzalez

Introduction fiberglass structures. The temperature range was

from 40 to 98°C. Cooling towers with MIC problems
had a maximum temperature of 45"C, and at steam
In Mexico, 5% of generated electricity is
purges temperatures were above 70°C.
produced by geothermal power plants (700
Figure 11.28 shows bacterial attack on a
megawatts). The main Mexican geothermal field
stainless steel joint. Microbiological activity took
is located at Cerro Prieto, 20 km from Mexicali in
place on wooden and reinforced fiberglass
the state of Baja California.
(Figure 1129). These composite materials show
Geothermal power plants have cooling towers
a higher degree of biodeterioration.
that process large quantities of water and steam.
Our aim is to report the experimental results
This fluid commonly contains hydrogen sulfide;
of the study conducted on the inductive effect of
thus, when it enters the cooling system and con-
anaerobic bacteria on the corrosion process of
denses, optimum conditions exist to initiate local-
carbon steel supports of the cooling towers. Such
ized corrosion. Not only does the cooling water
supports are immersed in a dense sludge, which
contain dissolved inorganic salts and elemental
promotes biocorrosion.' This sludge is generated
sulfur, it also promotes the growth of bacterial
by chemical transformation of hydrogen sulfide in
colonies, which produce metabolites capable of
oxygenated waters into the inorganic sulfur inside
corroding metallic structures.
cooling towers.

Background Experimental Results

Microbiologically induced corrosion (MIC)
problems in the Cerro Prieto geothermal field oc-
cur in three different zones:
the exploitation zone,
the power generation zone (mainly in
condensers), and
the cooling tower zone.
Materials that were deteriorated include car-
bon steel, stainless steel, wooden, and reinforced
The strains used in the study were isolated
from natural media. Samples of sludge and wa-
ter were taken from the bottom part of the cooling
tower of Cerro Prieto I in clean plastic 1 L bottles.
To obtain a more representative sample of anaer-
obic microorganisms, the sampler was immersed
1 m deep, and the bottle was filled with sludge at
40°C. Microbial cultures as well as isolation tech-
niques were carried out to identify the species. The
production of hydrogen sulfide and the decrease of
pH values were considered indicators of bacterial
metabolic processes.
Previous Page
11.22 Microbiologically Influenced Corrosion in Geothermal Fields in Mexico
FIGURE 11.28
Microbial growth on wooden and stainless steel joints
in the internal structure of a cooling tower. (See color
p Iates.)
The bacterial species identified from the
sludge were Desulfovibrio sp., Citrobacter sp.,
Pseudomonas aeruginosa, and other species of
the genus Bacillus. sp. Algal and Rhizopus sp.
growths also were observed on wood surfaces
(Figure 11.28).
The bacteria isolated from the cooling water
were Desulfuromonas acetoxidans and Desul-
fobacter latus, which also show halophilic and
thermophilic properties. Other bacterial species,
FIGURE 11.29
Biodeterioration induced by microbial growths, which
cause failure of a screen made of reinforced fiberglass.
(See color plates.)
FIGURE 11.30
SEM microphotograph of the biofilm formed by Desul-
foromonas acetoxidans on carbon steel surface showing
a localized rupture zone (scale: 100 ,urn).
Desulfovibrio sp., Pseudomonas sp., Thiobacillus
sp., algae, and Rhizopus sp., were identified, but
only the bacteria mentioned above were used for
the corrosion studies because of their capacity for
anaerobic growth at high temperatures (>7OoC).
The inductive effect of bacteria in carbon steel
corrosion was studied by scanning electron
microscopy (SEM).
Figure 11.30 shows a SEM microphotograph
of the film developed on carbon steel surfaces ex-
posed to sterilized natural media inoculated with
Desulfuromonas acetoxidans. The film is formed
by a mixture of corrosion and metabolic products.
A rupture zone (Figure 11.30) was studied micro-
scopically in detail. A growth of Desulfuromonas
acetoxidans was found under the biofilm. Sim-
ilar behavior was observed when the sterilized
natural media was inoculated with Desulfobac-
ter latus (Figure 11.31). In both cases when the
biofilms were removed from the carbon steel sur-
faces, a localized attack appeared under the bac-
terial growths. This result is in agreement with
other studies in marine and brackish hydrothermal
sediments.* The results are indicative of the influ-
ence of the anaerobic microorganisms in the cor-
rosion process, and it is important to add that their
halophilic and thermophilic properties give them
the ability to attack nonmetallic materials, such as
epoxy fiberglass, as well as metallic ones.
MicrobiologicallyInfluenced Corrosion in Geothermal Fields in Mexico
FIGURE 11.31
SEM microphotograph of the biofilm formed by Desul-
fobacter latus on carbon steel surface showing a local-
ized rupture zone (scale: 10 pm).
Conclusions
The corrosion detected in cooling towers
was the result of chemical and microbiological
processes. Results indicate that microorganisms
present in the cooling water play an important
role in the localized corrosion of the carbon steel
as well as the nonmetallic materials in the geother-
mal field installations. Corrosion has caused eco-
nomical losses by operational failure and repa-
ration and replacement expenses. Therefore, a
maintenance program should include treatment of
cooling waters by adding corrosion inhibitors and
bactericides.
Acknowledgment
This work was supported by CONACyT under
project 4047-A.
References
1. M. Navarrete, M. Ballesteros, J. Sanchez, B. Valdez,
and G. Hernandez, “Biocorrosion in a Geothermal
Power Plant,” Materials Performance, April 1999,
VOI. 38, NO.4, pp. 52-56.
2. L. Elsgaard, D. Prieur, G. Mukwaya, and B.
Jorgensen, Appl. Env. Microbiol. May, 60(1994):
1473-1 480.
3. Laanbrock and N. Pfennig, Arch. Microbiol. 128
(1981): 330.
CASE HISTORY S-1
Microbial Corrosion of Cultural
Heritage Stoneworks
By C. Saiz-Jimenez and X. Aritjo
Abstract
Microbial corrosion is one of the major causes
of weathering of stones and artificial materials
used in monuments and historic buildings. The
most conspicuous attacks are by phototrophic
organisms, mainly cyanobacteria, algae, and
lichens. Techniques currently used for determin-
ing attack include optical and scanning electron
microscopy (SEM) of samples, although in situ
sampling, culture growth, and reproduction of the
weathering processes in the laboratory, using
probe samples, can also be performed. Optical
and SEM images of selected samples are pre-
sented to illustrate the identification of microbial
corrosion patterns.
Introduction
Monuments, sculptures, and objects of art ex-
posed to open air have, over the centuries, de-
teriorated from natural causes. Sun, frost, wind,
rain, etc. contribute to the gradual process of
weathering, in which biological activity plays a key
role. The interactions of biological and physico-
chemical mechanisms are considered central to
the understanding of long-term deterioration.
Although atmospheric pollution is generally
recognized as a significant factor in the deteri-
oration of cultural properties, stone biodeteriora-
tion deserves more attention than it has received.
A great variety of microorganisms (e.g., bacte-
ria, fungi, algae, lichens) colonizing stones and
man-made materials have been They
can be found both on and beneath surfaces.
Colonization and growth of most phototrophic or-
ganisms results in the dissolution of and/or miner-
alogical changes in the substratrum. Some case
histories involving different materials and organ-
isms are described.
Case 1 : Deteriorationof
Roman Mosaics
This case involved the deterioration of mo-
saics (2nd century AD) exhumed during the sec-
ond decade of the 20th century in the Roman
city of Italica, near present-day Seville, Spain
(Figure 11.32). In about 70 years of exposure to
the ravages of nature the original mosaics (com-
posed of stone and vitreous and ceramic tesserae
stuck together by a lime mortar) present different
degrees of deterioration from slight attack (mainly
because it was covered with sand for some years)
to complete d e s t r ~ c t i o nMosaic
.~ colonization and
biodeterioration are usually linked to environmen-
tal conditions. The most significant parameters
affecting microbial growth are physical factors,
mainly moisture, temperature, and light, and the
chemical nature of the substratum.
Only water and a minimal supply of mineral
salts are required for colonization by cyanobacte-
ria and algae. It is the duration of the period of
wetness that is crucial, rather than the frequency
of wetting, in predisposing a surface to coloniza-
tion. Colonization is more rapid where there is
11.26 Microbial Corrosion of Cultural Heritage Stoneworks

FIGURE 11.33
House of Neptune, Italica, Spain. Mosaic of ceramic
tesserae colonized by algae. (See color plates.)

and the underlying mortar. However, colonization

by epilithic cyanobacteria and algae was only ev-
ident in a few mosaics sheltered by cypresses
that border the paths or in those composed of ce-
ramic tesserae, both resulting in a longer period of
wetness (Figure 11.33). These epilithic organisms
are usually associated with mosses, which pro-
duce a profuse network of rhizoids in the mortar
(Figure 1 1.34). Rhizoids may penetrate the mortar

FIGURE 11.32
View of the House of the Birds, Italica, Spain. (See color
plates.)

adjacent or overhanging vegetation from which

cyanobacteria and algae can be brought by wind
and rain, and development is further accelerated
if bird droppings, agricultural fertilizers, and air
pollutants introduce additional nitrogen and phos-
phorus. Rough or porous surfaces facilitate attach-
ment of airborne propagules and the accumulation
of nutrients. Although cyanobacteria and algae are
phototrophic organisms, obtaining their energy for
FIGURE 11.34
growth from light, they can also live under dim light Mosaic of the Labyrinth, House of Neptune, Italica,
and relatively constant humidity conditions, as en- Spain. Mortars are colonized by moss plants and lichens.
dolithic organisms inside the mosaic. This kind Of F~~~ the mortars the lichens the tesserae (see
growth is observed in the different mosaics but re- margin of Some tesserae with Verrucaria nigrescens).
stricted to the interface between the white lime- Also, some tesserae (see central one) are colonized by
stone tesserae, which permit light transmission, endolithic Caloplaca sp. (See color plates.)
Microbial Corrosion of Cultural Heritage Stoneworks
FIGURE 11.35
Growth of lichens can cover several tesserae. Caloplaca
chalybaea, Aspicilia contorta, and Verrucaria nigrescens
are particularly dominant species in the mosaics of
Italica. (See color plates.)
down to the base allowing easy access of water to
deep levels, but they have not been found pene-
trating t e ~ s e r a e . ~
White tesserae usually have the most abun-
dant colonization and also the most notable lichen
invasion, particularly by Caloplaca chalybaea,
Aspicilia hoffmanii, and Verrucaria nigrescens
(Figure 11.35). Lichen attack of tesserae and
mortars is both mechanical and chemical. It has
FIGURE 11.36
Thin section of a mortar (left) and limestone tessera
(right). It can be observed that the lichen penetrates into
the limestone from the mortar. (See color plates.)
FIGURE 11.37
Epilithic lichens produce pitting and etching in limestone
tesserae.
been observed that lichens colonize and pene-
trate tesserae producing pitting and etching of
the minerals6 (Figures 11.36 and 11.37). Disin-
tegration of mortars and loosening of tesserae
open the way for subsequent vascular plant inva-
sion, which is the final step in the destruction of
mosaics.
Case 2: Deterioration of Marble
The pyramid of Caius Cestius (first century
BC) is located in Rome, Italy (Figure 11.38). It
is made of Carrara marble blocks, some of which
present areas of black stains and holes or macro-
pitting developed in southeastern and southwest-
ern exposures7 (Figure 11.39). From microbio-
logical and chemical data it was concluded that
the surface of the pyramid was colonized mainly
by cyanobacteria and algae. This growth was
superficial as denoted by the removal of the black
patina by simple scraping with a razor blade.
Senescence of cyanobacterial mats leads to a
blackening of the stone surface, mainly as a re-
sult of chemical changes in lipid components such
as chlorophyll and oxidation of unsaturated fatty
acids accumulated in the cells. The most abun-
dant species were flectonema boryanum, fseu-
docapsa dubia, and Synechocystis sp. (cyanobac-
teria) and Klebsormidium flaccidum, Muriella
11.28
FIGURE 11.38
View of the pyramid of Caius Cestius, Rome, Italy, with
black and brown patinas. (See color plates.)
terrestris, and Chlorella saccharophila var. sac-
charophila (algae).
In addition to visible macro- and mesopitting,
SEM showed calcite crystals containing micropit-
ting (Figures 11.40 and 11.41) caused by dissolu-
tion induced by the phototrophic organisms.
Case 3: Deterioration of
Roman Stuccoes
The Roman city of Baelo Claudia was founded
in the second century BC. Its economy was based
Microbial Corrosion of Cultural Heritage Stoneworks
FIGURE 11.39
Detail of the patina formed by colonies of phototrophic
microorganisms. Extensive pitting is also evident. (See
color plates.)
on fishing, especially of tuna from the Strait of
Gibraltar, and its trade made it one of the wealthi-
est cities in the Mediterranean.
Toward the end of the first century AD its pro-
ductivity and prosperity diminished with the gen-
eral decline of the Roman Empire. However, the
city continued its activity and trade until the end
of the fifth century AD when it was abandoned
because of its geographical situation away from
commercial routes. It was discovered in the sec-
ond decade of the 20th century.
FIGURE 11.40
In the pyramid, pitting is also observed at the microscopic
level in calcite crystals. Bar is 200 k m .
Microbial Corrosion of Cultural Heritage Stoneworks
FIGURE 11.41
Detail )f micropitting. Bar is 25 p m .
The forum and the temples of the city, after
excavation in 971, appeared relatively well pre-
served. However, there has been a gradual deteri-
oration of its paving flagstones and stuccoed walls
after 30 years of exposure.8 The deterioration pro-
cesses are exemplified in the stuccoes coating
the walls of the temples (Figure 11.42). The stuc-
coes are made of sand and lime and although the
surface is porous and soft, making the establish-
ment of a lichen community difficult, some thalli of
Verrucaria spp. have been successful colonizers.
FIGURE 11.42
Stuccoed wall of the temple of Jupiter, Baelo Claudia,
Spain. (See color plates.)
FIGURE 11.43
Pitting produced by lichens. (See color plates.)
The stuccoed surface shows an abundant pitting.
The pits range between 0.2 and 0.7 mm in di-
ameter and are about 1 mm depth. Inside the
pits are the lichen fruiting bodies (Figures 11.43
and 11.44).
In northern exposures, cyanobacteria and al-
gae contribute to deterioration as the result of
colonization of fissures and cracks, penetration
to inner layers, and eventual dissolution of lime
(Figure 11.45). The penetration gives rise to the
establishment of a cryptoendolithic community
FIGURE 11.44
Detail of pitting produced by lichens. The lichen fruiting
body is located inside the pit. Bar is 200 p m .
11.30
FIGURE 11.45
Temple of Isis, Baelo Claudia, Spain. Stuccoed wall colo-
nized by cyanobacteria and algae. Surface is weathered
and fragmented. (See color plates.)
(Figure 11-46) developed parallel to the surface
where the temperature and humidity conditions
are suitable for growth. SEM reveals that the com-
munity is composed of numerous cyanobacteria
and algae (Figure 11.47). Heterotrophic bacteria
and fungi that use the extracellular organic matter
excreted by the former are also present. The con-
siderable deterioration of the stuccoes illustrated
the significance of the cryptoendolithic growth.
FIGURE 11.46
Cryptoendolithic community in a stucco from the Jupiter
temple, Baelo Claudia, Spain. (See color plates.)
Microbial Corrosion of Cultural Heritaae Stoneworks
FIGURE 11.47
Cyanobacteria and algae from the cryptoendolithic com-
munity of Figure 11.46. Bar is 25 p m .
Case 4: Deterioration of
Consolidant Resins
In the past decade, consolidants based on
resins were used to protect some stuccoed cap-
itals located in the Forum of Baelo Claudia
(Figure 11.48). In the capitals the growth of five
lichens was observed: Caloplaca lactea, Calo-
placa citrina, Sarcogyne pruinosa, Verrucaria
FIGURE 11.48
Stuccoed capital colonized by lichens at Forum of Baelo
Claudia, Spain. (See color plates.)
Microbial Corrosion of Cultural Heritage Stoneworks
FIGURE 11.49
Caloplaca citrina emerging from a resin layer coating
stuccoed capital of Figure 11.48. (See color plates.)
muralis, and Lecania turicensis (Figure 11.49).
These species are very common in xeric and ni-
trified environments and have often been identi-
fied in stone monuments and man-made substata.
SEM revealed that lichen thalli developed under
the resin coating and fruiting bodies emerged from
the resin layer (Figures 11 5 0 and 11.51). Proba-
bly, a combined mechanical and chemical action
caused the observed phenomenon.
FIGURE 11.50
Detail of lichen structures emerging from the resin layer.
Bar is 50 p m .
FIGURE 11.51
Apotecia of Sarcogyne pruinosa breaking the resin layer.
Bar is 250 b m .
Remedial Measures
In some of the presented cases, colonization
of cyanobacteria, algae, and lichens have been
treated by using simple measures (e.g., clean-
ing and maintenance). Manual cleaning and re-
moval of the lichens, mosses, and vascular plants
was undertaken in order to preserve mosaics. The
medium- and long-term effects of this method are
doubtful, as fragments of the removed lichens and
mosses may be deposited and retained on the
rough mortar, favoring further colonization, or en-
riching the substrate with organic matter and hu-
mus needed for plant invasion.
A better solution is the use of specific algi-
cides and lichenicides that have proven to be ef-
fective. Recently, a long-term effect of the biocide
2,3,5,6-tetrachloro-4-(methylsulfonyl)-pyridine(Al-
gophase) was reported for two monuments in dif-
ferent climatic conditions. In fact, a survey on
the main facade of the small church of Scurano,
near Parma, Italy, treated with Hydrophase, a
water repellent, and the biocides benzalkonium
chloride and Algophase, resulted in the pre-
vention of the colonization and/or recolonization
of the stone by phototrophic organisms for 6
yearsg
11,32
In a further study in the Templete Mudejar,
Monastery of Guadalupe, Spain, the performance
of the water-repellent-biocide treatment was
tested 8 years later. The Templete was sub-
jected to rising dampness, because it was sur-
rounded by a water pond that separates it from
a garden. This very humid environment and the
rising dampness contributed to the thriving of pho-
totrophic organisms up to 40 cm in height, col-
onizing bricks and mortars. In the part of the
walls not affected by rising dampness, the treat-
ment appeared to be effective, as no signifi-
cant colonization by phototrophic organisms was
observed.
It was evident that under normal conditions
the biocide Algophase was able to inhibit re-
colonization of phototrophic organisms for a pe-
riod ranging between 5 and 8 years, but not un-
der continuous rising dampness conditions. In
such a case, the treatment with a water repel-
lent and the subsequent application of a bio-
cide was not a barrier for the colonization and
growth of cyanobacteria, algae, and mosses. It
can be hypothesized that rising dampness and
continuous changes of moisture and salt crys-
tallization inside the bricks affected the perfor-
mance of the silicone layer and could even-
tually induce degradation or peeling off of the
products.
A new formulation involving the joint applica-
tion of the silicone and biocide as a compatible
water emulsion was developed.’’ This formulation,
unlike most frequently used commercial silicones
and biocides, which are dissolved in aromatic or
chlorinated solvents, is environmentally friendly; it
is being testing in the laboratory.12
Conclusions
Phototrophic organisms thriving on marble,
limestones, and lime mortars produce consid-
erable chemical dissolution of calcite crystals,
demonstrated as macropitting, mesopitting, and
micropitting, which proves the corrosive ability of
these organisms.
Microbial Corrosion of Cultural Heritage Stoneworks
Acknowledgment
This work was supported by the European
Commission, project ENV4-CT98-0707.
References
1. C. Saiz-Jimenez, “Biodeterioration of Stone in His-
toric Buildings and Monuments,” in Biodeteriora-
tion Research 4, eds. G.C. Llewellyn, W.V. Dashek,
and C.E. O’Rear (New York, NY: Plenum, 1994),
pp. 587-603.
2. C. Saiz-Jimenez, “Deposition of Anthropogenic
Compounds on Monuments and Their Effect on
Airborne Microorganisms,” Aerobiologia 1 l(1995):
161-175.
3. J.J. Ortega-Calvo, M. Hernandez-Marine, and C.
Saiz-Jimenez, “Cyanobacteria and Algae ,on Histo-
ric Buildings and Monuments,” in Recent Advances
in Biodeterioration and Biodegradation, Vol. I, eds.
K.L. Garg, N. Garg, and K.G. Mukerji (Calcutta,
India: Naya Prokash, 1994),pp. 173-203.
4. C. Saiz-Jimenez, J. Garica-Rowe, and J.M.
Rodriguez-Hidalgo, “Biodeterioration of Polychr-
ome Roman Mosaics,” Int. Biodeterior. 28(1991):
65-79.
5. J.A. Gil and C. Saiz-Jimenez, “Biodeterioration of
Roman mosaics by Bryophytes,” in Proceedings of
the 7th International Congress on Deterioration and
Conservation of Stone, Vol. 1 , eds. J.D. Rodrigues,
F. Henriques, and F.T. Jeremias (Lisbon, Portugal:
L.N.E.C., 1992),pp.511-519.
6. J. Garcia-Rowe and C. Saiz-Jimenez, “A Case
Study of the Corrosion of Stone by Lichens: The
Mosaics of the Roman Remains of ltalica,” in Micro-
bial Corrosion, eds. C.A.C. Sequeira and A.K. Tiller
(London, U.K.: The Institute of Materials, 1992),
pp. 275-281.
7 G. Caneva, M.P. Nugari, S. Ricci, and 0. Salvadori,
“Pitting of Marble Roman Monuments and the Re-
lated Microflora,” in Proceedings of the 7th Inter-
national Congress on Deterioration and Conser-
vation of Stone, Vol. 1 , eds. J.D. Rodrigues, F.
Henriques, and F.T. Jeremias (Lisbon, Portugal:
L.N.E.C., 1992),pp. 521-530.
8 X. Ariiio, J.J. Ortega-Calvo, A. Gomez-Bolea, and
C. Saiz-Jimenez, “Lichen Colonization of the Ro-
man Pavement of Baelo Claudia (Cadiz, Spain):
Microbial Corrosion of Cultural Heritage Stoneworks
Biodeterioration vs Bioprotection,” Sci. Total Envi-
ron. 167(1995): 353-363.
9. A. Gomez-Bolea, X. AriAo, R. Balzarotti, and C.
Saiz-Jimenez, “Surface Treatment of Stones: Con-
sequences on Lichenic Colonisation,” in Of Mi-
crobes and Art (Florence, Italy: Abstracts ICMC’99,
1999), pp. 233-237.
10. X. AriAo, A. Canals, A. Gomez-Bolea, and C.
Saiz-Jimenez, “Re-Colonization of the Templete
Mudejar, Guadalupe Monastery, Caceres, Spain,
after Silicone/Biocide Treatment,” in Protection
and Conservation of the Cultural Heritage of the
Mediterranean Cities, ed. E. Galan, (Seville, Spain:
Departamento de Cristalografia, Mineralogia y
Quimica Agricola, 2000), pp. 69-71.
11. R. Balzarotti-Kammlein, M. Sansoni, and A. Cas-
tronovo, “An Innovative Water-Compatible Formu-
lation of Algophase for Treatment of Mortars,” in
Of Microbes and Art (Florence, Italy: Abstracts
ICMC’99, 1999), pp. 21 7-220.
12. C. Fortes Revilla, Propiedades y Evolucion de
Nuevas Formulaciones de Hidrofugantes y Biocida
Aplicadas a Morteros y Hormigones de Restau-
racion del Patrimonio Cultural (Madrid, Spain:
lnstituto de Ciencias de la Construccion Eduardo
Torroja, 2000).
CASE HISTORY SS-13
Localized Corrosion of Stainless Steel
Milk Sterilizers
By H A Videla
Introduction
Corrosion hazard is one of the major problems
in the dairy industry owing to its economic signifi-
cance and its incidence on the quality of the final
products. Corrosion cases are related both to milk
and its by-products and to cleaning and disinfect-
ing media used daily in the plant. The type of attack
are usually pitting and crevice corrosion, favored
by the high chloride levels generally present in milk
media, and by biological deposits (caseinates and
other proteins) formed during sterilizing and clean-
ing procedures.
Background
The case described here is related to severe
localized corrosion found in (UNS S31600L) type
stainless steel (SS) plates of a new UHT milk
sterilizer, after only six months of use.
When the steel plates were observed by
means of a stereoscopic magnifier, two differ-
ent types of attack were distinguished: (a) cor-
rosion spread uniformly in the major part of the
plate surface and (b) pitting and crevice corrosion
found either in the projecting areas of the plate
or underneath the rubber joints (Figures 11.52
and 11.53). Some areas that appeared as pol-
ished parts of the surface showed an incipient lo-
calized attack when observed by scanning elec-
tron microscopy (SEM) at higher magnification
(Figure 115 4 ) .
Pitting attackwas also observed in the project-
ing parts of the plate rib design, where the local-
ized corrosion was accompanied by gray thread-
like deposits (Figure 1155-1 1.57) that revealed a
protein nature after energy dispersive x-ray analy-
sis (EDXA) and electronic microprobe analysis.
The sterilizer was used at temperatures
around 70°C and the cleaning procedure, made
daily after operation, was performed by washing
with a 1% nitric acid solution and later with al-
kaline solution (with additives) to repassivate the
surface.
In all cases, the attack was enhanced in the
milMmilk contact area of the sterilizer.
Metal and Water Analysis
The chemical composition of the SS is shown
in Table 11.2. The chemical composition of the
water used for washing procedures is shown in
Table 11.3.
Electrochemical Experiments
Potentiodynamic polarization curves in deaer-
ated milk, at a scan rate of 0.020 V/min, using
UNS S31600L type SS electrodes, showed an ac-
tive dissolution region between -0.70 and -0.65 V
followed by the active to passive transition zone.
Passivity extends up to 0.40 V, which corre-
sponds to the breakdown potential (Eb) of the alloy.
At higher anodic potentials passivity breakdown
11.36 Localized Corrosion of Stainless Steel Milk Sterilizers

FIGURE 11.52 FIGURE 11.55

Photograph of the localized attack observed on one of SEM micrograph of threadlike deposits inside the corro-
the projecting areas of the SS plate. sive attack at the surface of one of the SS plates (scale:
100 pm).

FIGURE 11.53
Photograph of the localized attack observed underneath
FIGURE 11.56
the rubber joints. SEM micrograph of one of the areas of attack shown in
Figure 11.55 at higher magnification (scale: 10 p m ) .

FIGURE 11.54 FIGURE 11.57

SEM micrograph of one of the areas of attack of the pro- SEM micrograph of denaturated protein fibers inside the
jecting ribs of the plate (scale: 100 pm). cavity of attack on the SS surface (scale: 10 pm).
~

Localized Corrosion of Stainless Steel Milk Sterilizers

TABLE 11.2
Conclusions
Chemical Composition of Stainless Steel
According to previous polarization results, a
~

Carbon 0.06
Silicon 0.82 passive behavior can be assigned to the SS spec-
Manganese 2.80 imens in contact with deaerated milk at 70°C.
Chromium 16.40 This assumption is supported by the anodic Eb
Nickel 11.oo values obtained with respect to the open cir-
Molybdenum 1.10 cuit potential. In addition, the uniform corrosion
widely observed on the steel plates by the met-
allurgical microscope can be assigned to the
periodic cleaning procedure with 1o/o nitric acid
occurs, and the pitting attack started. Open cir-
solution.
cuit potential versus time measurements showed
Localized corrosion observed on the project-
fairly stable potential values of --0.23 V. After
ing areas of the plates can be explained by
polarization, the microscopic observation of the
the mechanical contact between adjacent plates.
electrodes did not show any corrosive attack on
Thus, fretting effects are able to depassivate the
the surface, in agreement with the passive be-
metal, allowing pitting to start at potential values
havior observed for the SS at those potentials
very close to those of the open circuit potential.
in the polarization scan. Scratching tests were
Current densities at fretting areas, assess-
also made to observe the steel corrosion behav-
ed through polarization tests, showed values of
ior after removal of the passive film upon the
around 1 A/cm2.
surface. After two or three scratching tests, an im-
The severe attack observed under the rubber
portant increase of the current density and pit nu-
joints can be assigned to crevice corrosion, which
cleation over the scratched areas of the surface
is very common in this kind of steel’ when the cor-
was noticed.
rosivity of the electrolyte entrapped underneath
the joints is high. Within these areas, a strong
acidic electrolyte is present, with its composi-
TABLE 11.3 tion resembling that of a ferrous chloride sat-
Chemical Composition of the Water Used for urated solutionn2 In this way, milk proteins en-
Cleaning Procedures trapped in the cavities of the plates are easily
denatured by the acidic pH values and the
PH 7.70 PPm chemical characteristics of the solution present
Alkalinity (free) (as calcium carbonate) 0.00 in those restricted areas3 This denaturation
Alkalinity (total) (as calcium carbonate) 300.00
1917.00
is also enhanced by the high temperature of
Chlorides
Sulfates 1670.00 operation.
Nitrites 0.02 In summary, the severe corrosion attack ob-
Bicarbonate (as calcium carbonate) 300.00 served in SS plates of UHT sterilizers can be as-
Carbonate (as calcium carbonate) 0.00 signed to different causes:
Hydroxides (as calcium carbonate) 0.00
Alkalinity excess (as sodium carbonate) -
Temp. hardness (as calcium carbonate) 300.00 the cleaning procedure made with 1%
Perm. hardness (as calcium carbonate) 20.00 nitric acid solution in the presence of high
Total hardness (as calcium carbonate) 320.00 chloride levels of the plant water (see
Calcium hardness (as calcium carbonate) 155.00 Table 11.3);
Iron 0.30
Silicon (as silicon dioxide) 34.00 the fretting effects and the corrosive
characteristics of the media;
11.38
biological deposits of denatured proteins,
which facilitate crevice corrosion and;
the high temperatures of operation,
which enhance the rate of the corrosion
process.
Remedial measures taken were: a) re-
placement of sterilizer plates with a new
design to avoid fretting effects; b) use of water
with lower chloride content for cleaning proce-
dures.
Localized Corrosion of Stainless Steel Milk Sterilizers
References
1. A.J. Sedriks, Corrosion of Stainless Steel(New York:
Wiley, 1979), p. 88.
2. Z. Szlarska-Smialowska, “Nucleation and Develop-
ment of Pitting Corrosion in Iron and Steel,” in Pro-
ceedings of the 7th International Congress on Metal
Corrosion (Brazil: ABRACO, 1978), p. 14.
3. R.C. Salvarezza, M.F.L. Mele, and H.A. Videla,
“Study of the Biological Films Formed During the
Pitting of Aluminum in Human Plasma,” Life Supp.
Syst. 2(1984): 137.
About the Editor

John G. Stoecker II earned a bachelor of Science Degree in Mechanical

Engineering from the University of Missouri School of Mines and Metal-
lurgy. He is the Principal Consultant for Stoecker & Associates, St. Louis,
Missouri; a Principal Materials Engineering Specialist (retired after 25 years
of service), Monsanto Co.; and a High Temperature Design/Applications
Engineer, Abex Corporation. He is affiliated with ASM International and is
an active member of NACE International, for which he has Chaired Group
Committee T-3, Corrosion Science and Technology; was one of the founders
of Unit Committee T-3J, Microbiologically Influenced Corrosion; and served
on other committees and Task Groups such as T-3J-7, which produced this
book. Stoecker is the author of numerous articles on corrosion.

T-3J-7 Members,
Manual Contributors,
and Reviewers
The scope of Unit Committee T-3J, Microbio-
logically Influenced Corrosion, was to provide a
cooperative mechanism for studies in the area of
corrosion caused by microbiological organisms.
Specific activities included:
Producing reports on the state of the art,
Identifying and publishing case histories,
Sponsoring symposia,
Developing analytical techniques,
Providing practical mechanisms,
Determining basic mechanisms, and
Defining needed research.
Task Group T-3J-7 was formed during
the CORROSION/83 Conference in Anaheim,
California, in April 1983 to write a textbook
on microbiologically influenced corrosion (MIC)
over a five-year period. In a meeting of the
Task Group during CORROSION/85 in Boston,
Massachusetts, in March 1985, the group decided
that a definitive text on MIC was premature, but
that a practical manual might be appropriate. Greg
Kobrin agreed to chair the group with the re-
vised charter in mind. However, the manual con-
cept and format, with author assignments and so
=Unit Committees T-3J and T-3J-7 no longer exist. Please reference current edition of Nace's "Technical Committees Directory" for similar
Committees and Groups.
vii
TASKS AND ACKNOWLEDGMENTS
forth, were not officially developed until the T-3J-7
meeting during Fall Committee Week/86 in
Atlanta, Georgia, in September 1986. Only mi-
nor modifications to the format and contents have
been made since Volume 1 of the manual was pub-
lished in 1993.
John Stoecker agreed to chair T-3J-7 to pro-
duce Volume 2 of the practical manual during a
meeting at CORROSION/95 in Orlando, Florida in
March 1995. The Task Group designed Volume 2
using the same format as Volume 1 with a goal
to present new material that was not included in
Volume 1 plus current developments in the study
of MIC.
These manuals are designed to provide practi-
cal information on: the roles microorganisms such
as bacteria and fungi play in corrosion reactions;
the occurrence of MIC in several industries; how
to go about identifying whether or not a particu-
lar corrosion problem has been influenced by mi-
croorganisms; MIC treatment and prevention tips;
selected case histories from the technical litera-
ture with photographs in color to further assist the
reader in diagnosing potential MIC. Selected ref-
erences are supplied for further study. Authors of
various sections are known internationally as ex-
perts in this field.
We believe this approach to the subject of MIC
is unique and that these manuals will be a valuable
addition to the technical literature.
viii Tasks and Acknowledgments

Task Group T-3J-7

Members During The Work On Volume 2
Peter W. Allison Bruce A. Cookingham Jeffery R. Kearns Brent A. Scott
Joseph Boivin Michael Davies Ernest W. Klechka Alan L. Smith
Susan W. Borenstein Stephen C. Dexter Gregory Kobrin Arthur A. Stein
Thomas C. Breske Scott Farthing Madana M. Kunjapur John G. Stoecker II
John R. Bruce Arthur J. Freedman John J. Kvochak Robert E. Tatnall
Paul A. Burda Edward Freiter George J. Licina Hector A. Videla
James R. Burge Paige A. Herbert Richard W. Lutey Donald P. Wyman
Patricia A. Burke Gary Horacek Rupi Prasad Timothy P. Zintel
John C. Caron Charles F. Jenkins Andrew M. Pritchard Peter S. Zisson
Allen P. Castillo Doug Jones J.H. Schulz

T-3J - 7 Contributors
P.J. Allison J.W. Dusseault Richard W. Lutey J.H. Schulz
X. Arino Scott Farthing* Claude G. Matasa* J.B. Soebbing
I.B. Beech Navor Rojsas Gonzales Leticia Rioseca de la Pena John G. Stoecker II*
Joseph Boivin* Thomas R. Jack Daniel H. Pope Hector A. Videla
S.A. Cambell C. Saiz-Jimenez Rebecca M. Pope Patricia Wagner
T.E. Cloete Thomas M. Laronge* W.I.J. Poulton F.C. Walsh
Guillermo Hernandez- George J. Licina Richard I. Ray Timothy P. Zintel
Duque Delgadillo Brenda J. Little Benjamin Valdez Salas

T-3J-7 Reviewers per TPC Guidelines

Susan W. Borenstein C.F. Jenkins David J. Morgan Robert E. Tatnall
Stephen C. Dexter George J. Licina Rupi Prasad Hector A. Videla
Scott Farthing Brenda J. Little Brent A. Scott Patricia Wagner
Arthur J. Freedman Richard W. Lutey John G. Stoecker II Timothy P. Zintel

Final Review Conducted By:

Editor's Note: Special thank you to the following people for conducting a thorough review and critique on
the eve before printing.
Stephen C. Dexter Gregory Kobrin

'These are authors who submitted papers which were not included in the book
 CP.1

COLOR PLATES

2, Fungal-Influenced Corrosion of Metals

in Humid Environments c P.3-c P.5
3, Biodegradation of Nonmetallic Engineering Materials CPm6-CP,6
4. Biodeterioration of Building Materials CP.7-CP. 10
5 Microbiologically Influenced Corrosion
I

in Fire Protection Sprinkler Systems c P. 1-CP. 1 1

6. Part1
MIC jn Underground Environments: External
Corrosion in the Gas Pipeline Industry c P, 2-CP. 12
Part II
Microbiologically Influenced Corrosion of Internal Aspects
of Natural Gas Industry Pipelines and Associated Equipment:
Mechanisms, Diagnosis, and Mitigation CP.13-CP, 15
Part Ill
A Case Study-Microbially Induced Organic Acid
Attack in a Natural Gas Gathering System CP. 16-CP, 16
7. MIC in the Power lndustry CP.17-CP. 19
8# MIC in the Waste Treatment Industries CP,19-CP.20
9. Treatment for the Mitigation of MIC CP,2 1-CP. 24
11. cs-3
Marine Microbial Corrosion cP,25-c P.27
cs-4
The Detection and Mitigation of MIC CP028-CP,31
CP.2 COLOR PLATES

MM-3
Microbiologically Influenced Corrosion in
Geothermal fields in Mexico CP.31-CP.31
s- 1
Microbial Corrosion of Cultural Heritage Stoneworks CP.32-CPn34
COLOR PLATES - ChaDter 2 CP.3

Fungal- Influenced
Corrosion of
Metals in Humid
Environments

FIGURE 2.2 (a)

Wooden spool on which wire rope was stored.
Pieces of paper are attached to rim edges.

FIGURE 2.1
Growth stages of filamentous fungi.
CP,4 COLOR PLATES - Chapter 2

FIGURE 2.2 (b)

Inside surface of wooden spool. White deposits are
the result of fungal growth. FIGURE 2.4
(a) Wire rope that had been in contact with wood and PDA
inoculated with Aspergillus niger. Rope rolled aside to
show localized corrosion after contact with agar or wood
(3x1. (b) Light micrograph of localized corrosion associated
with fungi (40x1.

FIGURE 2.5
Interior of H-53 helicopter with luxurious fungal growth
on polyurethane paint.
COLOR PLATES - Chapter 2 CP.5

FIGURE 2.6
(a) Aureobasidiurn sp. colonizing polyurethane paint taken from H-53 helicopter. (b) 3 X magnification of (a).
(c) ESEM micrograph of Aureobasidiurn sp. on polyurethane paint. (d) Aureobasidiurn sp. on underside of
polyurethane paint chip (40X).

FIGURE 2.7
Fungal-induced corrosion of bare 2024 T-6 aluminum (40X).
CP.6 COLOR PLATES - Chapter 3

Biodegradation of
Nonmetallic
Engineering Materials

FIGURE 3.9 (a)

Corrosion of rebar in concrete.

FIGURE 3.11
(a) Deterioration of wood due to bacteria and fungi, (b) fungal
colonization (400X), and (c) staining to show bacterial penetration
of wood (1OOOX). (Courtesy of R. Lutey, Buckman Laboratories,
Memphis, TN.)
COLOR PLATES - Chapter 4 CP.7

Biodeterioration of
Building Materials

FIGURE 4.1
Staining of marble on the Certosa of Pavia, Italy.

FIGURE 4.2
Right: Phototrophic microorganisms on the facade of the cathedral
of Salamanca, Spain.

FIGURE 4.4
Limestone tessera from a mosaic of the Roman town of Italica, Spain, covered by epilithic lichens. Before (a) and
after (b) removal of the lichen thalli with hydrogen peroxide. Extensive pitting was observed beneath the thalli.
CP,8 COLOR PLATES - ChaDter 4

FIGURE 4.5
Fruiting bodies of an endolithic lichen
(Caloplaca sp.) emerging between calcite
crystals.

FIGURE 4.6
Walls of the cathedral of Salamanca, Spain, with
disperse lichen thalli.
COLOR PLATES - Chapter 4 CP.9

FIGURE 4.10
Vascular plants emerging from terracotta crevices
on the Pardon Gate, cathedral of Seville, Spain.
FIGURE 4.9
Terracotta colonized by cyanobacteria and algae on the
Pardon Gate, cathedral of Seville, Spain.

FIGURE 4.11
Deteriorated mural painting from the chapel of Castle Herberstein, Austria.
CP,lO COLOR PLATES - Chapter 4

FIGURE 4.12
Wall of the cloister of the Jeronimos
monastery, Lisbon, Portugal, colonized
by lichens.

FIGURE 4.13
Wall of the Quadrangular Mausoleum, Necropolis of
Carmona, Spain, colonized by calcifying cyanobacteria.
 Next Page

COLOR PLATES - Chapter 5 CP,ll

Microbiologically Influenced
Corrosion in Fire Protection
Sprinkler Systems

FIGURE 5.1
Examples of MIC in FPS. (a) Discrete deposits (nodules) and deposits in steel wet FPS
pipe. (b) Galvanized steel wet FPS pipe showing heavier deposition and pitting on bottom
of pipe. (c) Pit in copper wet FPS pipe. (d) Deposits in galvanized steel dry FPS pipe.
(e) Pinhole leak in galvanized steel dry FPS pipe.
Previous Page

CP.12 COLOR PLATES - Chapter 6 (Part I)

MIC in Underground
Environments: External
Corrosion in the
Gas Pipeline Industry

FIGURE 6.5
Pressurized bubbles of gas in the adhesive between coating layers on a tape-wrapped pipeline.
COLOR PLATES - Chapter 6 (Part II) CP. 13

Microbiologically Influenced Corro-

sion of Internal Aspects of Natural
Gas Industry Pipelines and Associ-
ated Equipment: Mechanisms,
Diagnosis, and Mitigation

FIGURE 6.9 FIGURE 6.11

FITC-stained MIC community on carbon steel exposed to Internal diameter of gas pipeline showing Phase 2 of a
city water for 8 days. MIC site.
CP.14 COLOR PLATES - Chapter 6 (Parts I l l

Cells prepared on-site in PBS-Formalin

I Small volume spotted onto slide

Stained with FlTC or

fluorescent antibody

Viewed using epifluorescence

FIGURE 6.15 (a)

Procedure for total microscopic count using fluorescent
FIGURE 6.13 (a) stain for biological material and epifluorescent micro-
Phase 3. MIC nodule on a sucker rod from an oil well, show- scope.
ing layers of corrosion product. Layer at bottom of pit is very
rich in chloride.
-
0 non-SRB
Cells from PBS-forrnalin heat
fixed to microscopic slide

,(, 1 A Rabbit anti-SRB antibody

added to slide & allowed to
I, react

A
,I
A
~

I,
1 ,i
Goat anti-rabbit second
antibody labeled with FlTC
allowed to react with rabbit
anti-SRB

LViewed
'using epifluorescence
microscopy

FIGURE 6.15 (b)

Procedure for enumeration of specific bacteria using flu-
orescently labeled antibodies.
FIGURE 6.13 (b)
Copper-nickel (90/10) tubing showing mature discrete de-
posits. Severe pitting was seen under most deposits.

FIGURE 6.13 (c)

Left: 304 Stainless steel piping showing mature nodules
especially at weld and heat-affectedzone. Goblet-shaped
pits were observed under the nodules.
COLOR PLATES - Chapter 6 (Parts II) CP.15

FIGURE 6.22
Internal diameter of a natural gas pipeline showing corrosion at 6 o’clock position,
immediately downstream of low point in pipeline.

FIGURE 6.23
Internal diameter of a liquid hydrocarbon pipeline at low point where water and
debris accumulated. Note severe pitting principally at 5-7 o’clock portions of pipe.
CP.16 COLOR PLATES - Chapter 6 (Part 111)

A Case Study-Microbially
Induced Organic Acid Attack in
a Natural Gas Gathering System

FIGURE 6.24 FIGURE 6.25

Example of isolated pitting as seen in the examined Example of acid type of attack in the examined south-
southeastern Alberta, Canada shallow gas production eastern Alberta, Canada shallow gas production system.
system.

FIGURE 6.26 FIGURE 6.28

MIC pitting in conjunction with an O2type of attack. Biofilm spool locations (red dots) at this southeastern
Alberta, Canada shallow gas production system.
COLOR PLATES - Chapter 7 CP.17

MIC in the Power Industry

FIGURE 7.3
FIGURE 7.2 Attack at carbon steel welds on service water piping
MIC of carbon steel fire protection system piping. from a nuclear plant.
(Photograph provided courtesty of Buckman Laboratories
International, Inc.)

FIGURE 7.5 FIGURE 7.6

MIC of carbon steel at a nuclear plant. MIC of carbon steel at a nuclear plant.
rP 18 COLOR PLATES - Chapter 7

FIGURE 7.7
MIC of 90-10 copper-nickel stator cooler.

FIGURE 7.8
MIC of stainless steel weldments, showing pre-service
failure from a fossil-fired plant.

FIGURE 7.9
MIC of stainless steel weldments, showing pre-service FIGURE 7.12
failure from a fossil-fired plant. MIC in stainless steel weldments. (From Chung et a1.28)

FIGURE 7.18
FIGURE 7.13 MIC attack at heat-affected zone of a stainless steel
MIC in stainless steel weldments. (From Chung et al.28) weldment in a fossil plant.
COLOR PLATES - Chapters 7 and 8 CP,19

MIC in the Waste

Treatment Industries

FIGURE 8.1
Flocculating and settling activated sludge with
FIGURE 7.20 heterotrophic bacteria and protozoa (2000X).
MIC attack on heat exchanger tube.

FIGURE 8.2
Bacillus subtilis and Sphaerotilis natans in
activated sludge (200OX).
 Next Page

c P.20 COLOR PLATES - Chapter 8

FIGURE 8.3 FIGURE 8.4

Tubercles beneath the biofilm appear as mounds at Deep, rounded pit identified beneath a removed tubercle.
approximately 3 and 5 o’clock on the pipe wall.

FIGURE 8.5 FIGURE 8.6

Thick biofilm on the interior of RAS piping. Small pinhole-type pit and nonuniform coal tar epoxy
lining on the interior of the pipe sample.
Previous Page
COLOR PLATES - Chapter 9
FIGURE 9.1
Internal surface of carbon steel pipe that has been
colonized by iron-oxidizingbacteria formingtubercles.
This condition can be mitigated by mechanical/chemical
cleaning before pipe failure occurs.
FIGURE 9.3
Internal surface of carbon steel pipe and face of a gate
valve located in a fire protection system. Note the "old"
tubercles formed by iron-oxidizing bacteria and the "new"
growth on the surface of the tubercles demonstrated by
the orange-colored deposits. (Courtesy Russ Green)
CP.21
Treatment for the
Mitigation of MIC
FIGURE 9.2
Internal surface of carbon steel pipe showing extensive
tuberculation caused by iron-oxidizing bacteria. The
tubercles could be removed by mechanical/chemical
cleaning, but there may be significant pitting corrosion
underneath the tubercles.
FIGURE 9.4
Internal surface of a carbon steel elbow covered with
corrosion products and tubercles formed by iron-
oxidizing bacteria. Note the aggressive attack of the
weldment at the socket welds covered by tubercles.
CP.22 COLOR PLATES - Chapter 9

FIGURE 9.7 FIGURE 9.8

Internal surface of carbon steel pipe at a welded flange Exterior surface of pipe shown in Figure 9.7 showing the
colonized by iron-oxidizing becteria. Note the black de- through-wall penetrations of pits caused by growth of
posits on the metal surface where the tubercle has been sulfate-reducing bacteria underneath tubercles seen in
removed. Figure 9.7.
COLOR PLATES - Chapter 9 CP.23

FIGURE 9.9 FIGURE 9.10

Cross section of carbon steel pipe with a large tubercle Close-up view of the anaerobic pit area underneath the
on the interior surface. Note the stratification of layers of tubercle shown in Figure 9.9. Note the through-wall
deposited iron products that formed as the tubercle grew penetration.
in size. Note also the large pit and through-wall pene-
tration caused by sulfate-reducing bacteria growing in
the anaerobic environment underneath the tubercle.

FIGURE 9.12
View of heat exchanger tube sheet and tubes with
tuberculation caused by iron-oxidizing bacteria.

FIGURE 9.11
View of heat exchanger tube sheet covered with biomass
and corrosion product. Note the tuberculation on the
inner surfaces of the tubes. Unless removed by cleaning,
these will provide sites for pitting and reduce flow rate
through the tubes.

FIGURE 9.13
View of heat exchanger tuber sheet and tubes fouled by
biomass and corrosion product.
C P.24
FIGURE 9.14
View of 304 stainless steel welded tank wall showing
attack by microorganisms. Note the rust streaks coming
from corrosion sites at the welds and the numerous small
corrosion sites scattered over the tank wall.
FIGURE 9.16
View of the internal surface of a 90/10 copper-nickel
heat exchanger tube showing pits into the base metal
and surface covered with biofilm.
COLOR PLATES - Chapter 9
FIGURE 9.15
Close-up view of the corrosion site at the weld on the
tank wall shown in Figure 9.14.
FIGURE 9.17
Close-up view of a pit and deposition of corrosion prod-
uct on the surface of a 90/10 copper-nickel heat ex-
changer tube. This corrosion is caused by slime-forming
metal-oxidizing bacteria.
FIGURE 9.18
Close-up view of a pit into the base metal of an admiralty
brass heat exchanger tube. Note the absence of corrosion
product and the deposition of elemental copper in the pit.
Note also the surrounding surface of the tube covered with
dehydrated biofilm. This corrosion is caused by slime-
forming metal-oxidizing bacteria.
COLOR PLATES - Chapter 1 1 (CS-3) CP.25

Marine Microbial Corrosion

FIGURE 11.1
General view of steel piling, showing zones affected by
low water corrosion.

FIGURE 11.5
View of the underside of a ship’s hull bottom plate in a
dry dock, with a corroded section removed for analysis
and repair.

FIGURE 11.2
A close-up of a particular section of steel piling, show-
ing severe perforation at the low water level.
CP.26 COLOR PLATES - Chapter 1 1 (CS-3)

FIGURE 11.8
Cross section of the hull plate, showing the reduction in
normal thickness (12 mm) due to microbial attack
resulting in severe pitting.

FIGURE 11.6
Photograph of the inside surface of a ship’s bottom plate
removed from the vessel, showing pitting of the steel
revealed by clearing away the mud film.

FIGURE 11.10
A journal bearing, showing pitting and scoring due to
the formation of hard tin oxide particles (which appear
as darkened areas on the surface).

FIGURE 11.7
General view of the inside surface of a section of hull plate,
showing extensive pitting corrosion and crater formation.
COLOR PLATES - Chapter 1 1 (CS-3) CP.27

FIGURE 11.11 FIGURE 1 1 .I 5

Close-up view of the surface of a white metal bearing, A welded region of the ship’s hull plate, showing a row
showing the formation of pits containing dark particles of of pits along the weld seam.
tin oxides.

FIGURE 11.1 2
A camshaft bearing, showing pitting and mechanical FIGURE 11.16
damage to the white metal lining. A perforated zone of ship’s hull plate, showing leakage of
seawater from the interior of the vessel.

FIGURE 11.1 4
General view of ship’s hull, showing the extensive
distribution of pits over the surface.
 Next Page

CP.28 COLOR PLATES - Chapter 1 1 (CS-4)

The Detection and

Mitigation of MIC

FIGURE 11.17 FIGURE 11.I 8

High density of tuberculation before mechanical cleaning. Pitting corrosion beneath a tubercle.

FIGURE 11.19 FIGURE 11.20

Scars on the metal surface after mechanical cleaning Ferric hydroxide ribbons filtered from the fire hydrant
(pigging) operations. water (400X magnification).
Previous Page

COLOR PLATES - Chapter 1 1 (CS-4) CP.29

FIGURE 11.21
1OOOX magnification of Gallionella ferric hydroxide
ribbon and bacterial cell.

FIGURE 11.23
Biofouling deposits on cooling tower packing before biodis-
persantibiocide treatment (A) and packing clear of biofouling
deposits after three weeks of treatment (B).

FIGURE 11.24
Slight algal regrowth in the spray area of a cooling
tower after nine months of biodispersantibiocide
treatment.
CP.30 COLOR PLATES - Chapter 1 1 (CS-4)

FIGURE 11.25 FIGURE 11.26

Strainer box before the initiation of biodispersantl Strainer box after three weeks of biodispersantbiocide
biocide treatment showing hard nodules on surface (A) treatment showing softened nodules on surface (A) and loss
and underlying pits filled with black liquid (B). of black coloration in underlying pits (B).
 -
COLOR PLATES Chapter 11 (CS-4 and MM-3) CP.3 1

Microbiologically
Influenced Corrosion
in Geothermal
Fields in Mexico

FIGURE 11.27
Strainer box after nine months of biodispersant/biocide
treatment showing almost complete removal of nodules.

FIGURE 11.28
Microbial growth on wooden and stainless steel joints
in the internal structure of a cooling tower.

FIGURE 11.29
Biodeterioration induced by microbial growths, which
cause failure of a screen made of reinforced fiberglass.
CP,32 COLOR PLATES - Chapter 1 1 (S-1)

Microbial Corrosion of Cultural

Heritage Stoneworks

FIGURE 11.33
House of Neptune, Italica, Spain. Mosaic of ceramic
tesserae colonized by algae.

FIGURE 11.32
View of the House of the Birds, Italica, Spain.

FIGURE 11.34
Mosaic of the Labyrinth, House of Neptune, Italica,
Spain. Mortars are colonized by moss plants and
lichens. From the mortars the lichens colonize the
tesserae (see margin of some tesserae with Verrucaria
nigrescens). Also, some tesserae (see central one) are
colonized by endolithic Caloplaca sp.
COLOR PLATES - Chapter 1 1 6 1 ) CP.33

FIGURE 11.36
FIGURE 11.35
Thin section of a mortar (left) and limestone tessera
Growth of lichens can cover several tesserae. Caloplaca
(right). It can be observed that the lichen penetrates
chalybaea, Aspicilia contotfa, and Verrucaria nigrescens
into the limestone from the mortar.
are particularly dominant species in the mosaics of Italica.

FIGURE 11.39
Detail of the patina formed by colonies of phototrophic
microorganisms. Extensive pitting is also evident.

FIGURE 11.38 FIGURE 11.42

View of the pyramid of Caius Cestius, Rome, Italy, Stuccoed wall of the temple of Jupiter, Baelo Claudia,
with black and brown patinas. Spain.
cP.34 COLOR PLATES - Chapter 1 1 ($1)

FIGURE 11.43 FIGURE 11.45

Pitting produced by lichens. Temple of Isis, Baelo Claudia, Spain. Stuccoed wall col-
onized by cyanobacteria and algae. Surface i s weath-
ered and fragmented.

FIGURE 11.46
Cryptoendolithic community in a stucco from the Jupiter
temple, Baelo Claudia, Spain.

FIGURE 11.48
Stuccoed capital colonized by lichens at Forum of Baelo
Claudia, Spain.

FIGURE 11.49
Caloplaca citrina emerging from a resin layer coating
stuccoed capital of Figure 11.48.

Aerobe: An organism that requires oxygen to live.
Aerobic: Exposed to oxygen,
Algae: A heterogeneous group of photosynthetic
plants, ranging from microscopic single-cell forms
to multicellular very large forms such as seaweed.
Anaerobe: An organism that lives without oxygen.
Anode: The electrode of an electrolyte cell at
which oxidation occurs. Electrons flow away from
the anode in the external circuit. Corrosion occurs
at this electrode, and metal ions enter the solution.
Bacteria (Bacterium): Any of a large group of
microscopic organisms that are often aggregated
into colonies, are enclosed by a cell wall or mem-
brane (procaryotes), and lack fully differentiated
nuclei. Bacteria may exist as free-living organisms
in soil, water, or organic matter, or as parasites in
the live bodies of plants and animals.
Biocide: A compound toxic to any living thing.
Biomass: Organic matter grown by the photosyn-
thetic conversion of solar energy.
Cathode: The electrode of an electrolytic cell at
which reduction takes place. Electrons flow toward
the cathode in the external circuit. Typical cathodic
processes are cations taking up electrons and be-
ing discharged, oxygen being reduced, and the re-
duction of a metallic element or group of elements
from a higher to a lower valence state.
Cathodic Polarization: The change of the elec-
trode potential in the active (negative) direction
caused by current flow (see Polarization).
ix
GLOSSARY
Cathodic Protection: Reduction of corrosion rate
by shifting the potential of the corroding metal to-
ward a less oxidizing potential with application of
an external electromotive force, such as with a less
noble metal (galvanic) anode or an impressed di-
rect current.
Colony: A visible growth of microorganisms on a
medium.
Concentration Cell: A corrosion cell in which the
driving force is caused by a difference in concen-
tration of a component in the electrolyte.
Contaminant: Any unwanted or undesired mate-
rial in an environment.
Corrosion Potential (Ecorr): The potential of a
corroding surface in an electrolyte relative to a ref-
erence electrode. Also called rest potential, open
circuit potential, freely corroding potential.
Corrosion Rate: The rate at which corrosion pro-
ceeds, expressed as either weight loss or penetra-
tion per unit time.
Corrosion Resistance: Ability of a metal to with-
stand corrosion in an environment.
Corrosion: The deterioration of a material, usually
a metal, by reaction with its environment.
Corrosiveness, Corrosivity: The tendency of
an environment to cause corrosion in a given
corrosion system.
Crevice Corrosion: A form of localized corro-
sion occurring at locations where easy access to
the bulk environment is prevented, such as at the
Y Glossarv
mating surfaces of metals or assemblies of metals
and nonmetals (see Concentration Cell).
Critical Pitting Potential (Ecp,E,, E,,): The Iow-
est value of oxidizing potential at which pits nucle-
ate and grow.
Culture Medium: Any nutrient system for the ar-
tificial cultivation of bacteria or other microorgan-
isms, usually a mixture of organic and inorganic
materials.
Depolarization: The removal of factors resisting
the flow of current in an electrochemical cell.
Deposit Attack: Corrosion occurring under or
around a deposit on a metallic surface (also called
poultice corrosion).
Desulfovibrio: A genus of bacteria that reduces
sulfate to H2S and obtains energy by oxidation of
H2S or organic molecules.
Differential Aeration Cell: A corrosion cell
caused by differences in oxygen concentration in
an electrolyte.
Electrochemical Cell: An electrochemical system
consisting of an anode and a cathode in electrical
contact and immersed in an electrolyte. The anode
and cathode may be different metals or dissimilar
areas on the same metal surface.
Electrolyte: A chemical substance or mixture,
usually liquid, containing ions that migrate in an
electric field.
Environmental Cracking: Fracture of normally
ductile metal in which the corrosive effect of the
environment is a causative factor. Environmental
cracking is a general term that includes all of the
following terms:
Corrosion Fatigue
High Temperature Hydrogen Attack
Hydrogen Blistering
Hydrogen Embrittlement
Hydrogen-Induced Cracking
Liquid Metal Cracking
Stress Corrosion Cracking
Sulfide Stress Cracking
Enzyme: Organic catalyst of biochemical reac-
tions in a bacterial cell; composed of protein.
Erosion: Destruction of materials by the abrasive
action of moving fluids, usually accelerated by the
presence of solid particles.
Exopolymer: An extracellular material, frequently
sticky, that defines the shape of organisms and
serves to trap particulate matter.
Facultative Cells: Bacterial cells that can live ei-
ther in the presence or absence of oxygen.
Ferrobacteria: Any of a group of bacteria that ox-
idize iron as a source of energy. The oxidized iron,
in the form of Fe(OH)3, is then deposited in the
environment by secretion from the bacterium. The
energy obtained from these reactions is used to
carry on processes in which the basic substances
needed by the bacterium are manufactured. These
bacteria, also known as iron bacteria, are com-
monly found, for example, in seepage waters of
coal and iron mining areas where iron compounds
abound.
Fouling: An accumulation of deposits on a sur-
face. This term includes accumulation and growth
of marine organisms on a submerged metal
surface and also includes the accumulation of
deposits (usually inorganic) on heat exchanger
tubing.
Fungus (Fungi): Any of a major group of para-
sitic plants that lack chlorophyll, including molds,
mildews, smuts, mushrooms, and yeasts.
Galvanic Anode: A metal that, because of its
relative position in the galvanic series, provides
GIossary
sacrificial protection to metals that are more noble
in the series when coupled in an electrolyte.
Galvanic Corrosion: Accelerated corrosion asso-
ciated with current resulting from electrical cou-
pling of dissimilar metals in an electrolyte.
General Corrosion: A form of deterioration that is
distributed more or less uniformly over a surface.
Habitat: The natural environment of an organism.
Iron Bacteria: See Ferrobacteria.
Medium: A substance used to provide nutrients
for cell growth. It may be liquid (broth) or solid
(agar).
Metabolism: The entire set of enzyme-catalyzed
transformations of organic nutrient molecules in
living cells.
Metabolite: A chemical intermediate in the
enzyme-catalyzed reactions of metabolism.
Microbe: A microscopic organism; applied partic-
ularly to bacteria.
Microbiocide: Any chemical that will kill microor-
ganisms. Used synonymously with biocide and
bacteriocide.
Microbiology: The science dealing with the struc-
ture, classification, physiology, and distribution of
microorganisms, and with their technical and med-
ical significance. The term microorganism is ap-
plied to the unicellular and structurally closely
related simple representatives of the plant and
animal kingdoms. With few exceptions, unicellular
organisms are invisible to the naked eye and gen-
erally have dimensions between a fraction of a
micron and 200 microns.
Microorganism: Any organism of microscopic
size that requires a microscope to be seen.
Obligate: A term used to describe a metabolism
restricted to a similar type, as in the expression,
obligate anaerobe.
xi
Passivation: A reduction of the corrosion rate of a
metal due to formation of a protective film, usually
an oxide, on its surface.
Pits, Pitting: Localized corrosion of a metal sur-
face that is confined to a small area and takes the
form of cavities.
Plankton (Planktonic): Microorganisms floating
or drifting in a body of water.
Polarization: The deviation from the open circuit
potential of an electrode resulting from the pas-
sage of current.
Rust: Corrosion product consisting primarily of hy-
drated iron oxide; a term properly applied only to
iron and ferrous alloys.
Scaling: The deposition of water-insoluble con-
stituents on a metal surface.
Sessile: Attached to a surface.
Slime: An extracellular material produced by some
microorganisms, characterized by a slimy consis-
tency of varied chemical composition.
Sterile: Free of any living organisms.
Strain: Microorganisms of the same species but
with distinctive characteristics and not usually con-
sidered a different breed or variety.
Sulfate-Reducing Bacterium (SRB): Any organ-
ism that metabolically reduces sulfate to H2S;
includes a variety of microorganisms (see
Desulfovibrio).
Thermophile (Thermophilic): An organism that
grows best at temperatures greater than 50°C
(122°F).
Tuberculation: The formation of localized corro-
sion products scattered over the surface in the
form of knoblike mounds called tubercles.
Underfilm Corrosion: Corrosion that occurs
xii Glossary

under organic films in the form of randomly dis- Bibliography

tributed threadlike filaments or spots.
Yeast: A fungus of the family Saccharomyc-
etaceae used especially in the making Of alcoholic
liquors and as leavening in baking.
1. NACE Corrosion Engineer’s Reference Book
(Houston, TX: NACE, 1991).
2. “The Language of Biotechnology-A Glossary”
(Phillips Petroleum Co. Research Center, 1984).
INDEX

Index Terms Links

Aachen cathedral, Germany 4.8

Abrasive particles 9.22
Acidity. see pH
Acid-producing bacteria (APB)
asphalt degradation 6.3
biocides and 6.22
in fire protection sprinkler systems 5.5
in gas gathering system study 6.35
growth assays 10.4
testing for 6.28 6.31
Acid rain 4.7
Acinetobacter 3.8
Acinetobacter calcoaceticus 3.3
Acinetobacter Iwoffi 4.11
Acoustic emission (AE) 3.3
Actinomycetes 4.11
Activated sludge 8.1 CP.19
Adenosine triphosphate (ATP) assays 10.5
Adhesives degradation 6.4 CP.12
Aerobic/anaerobic alternating conditions 6.8
Aerobic biofilms 1.2 6.31 CP.16
Alcaligenes 3.8
Algae
consolidant resins 11.30
marble 11.27
mortars 4.14
mosaics 11.26 CP.32
organic resins 4.15
stonework deterioration 4.5 4.8 4.10 CP.9

This page has been reformatted by Knovel to provide easier navigation.

Index Terms Links

Algae (cont.)
stuccoes 11.28 CP.34
ultraviolet radiation treatment 4.15
Algophase 11.31
Alloys
copper 1.5 6.16 7.5 9.12
9.16 9.19 CP.18
nickel-based 7.10
nonferrous 9.19
pH and 9.12
in wastewater treatment systems 8.6
Alternaria 3.6
Alternating current (AC) impedance
techniques 10.14
Aluminum 1.6 2.5 CP.5
Anaerobic conditions 6.7
Anionic polyelectrolytes 9.27 11.18
Anodic pitting corrosion cells 9.18
Anodic polarizations 1.6
Antimony 11.10
APB. See Acid-producing bacteria
APS reductase test 6.31
Archaea 4.12
Arthrobacter globiformis 4.11
Aspergillus 4.3
Aspergillus niger 2.3 3.6 4.3 CP.4
Aspergillus versicolor 3.3 3.5 4.12
Asphalt degradation 3.8 6.2 6.6 8.5
Aspicilia 4.10
Aspicilia contorta 11.27 CP.33
Aspicilia hoffmanii 11.27
Aureobasidium sp. 2.4 3.6 CP.5
Austenite phase 7.6 7.9 9.19
Autotrophic bacteria 3.1 4.6
Azole-based inhibitors 9.14

This page has been reformatted by Knovel to provide easier navigation.

Index Terms Links

Bacillariophyta 4.10
Bacillus 4.11 8.2
Bacillus sp. Algal 11.22
Bacillus subtilis 8.2 CP.19
Bacteria. See also Acid-producing bacteria; names
of individual bacteria; Sulfate- reducing bacteria
aerobic 1.2 5.4 6.31
autotrophic 3.1 4.1 4.6
in fire protection sprinkler systems 5.4
heterotrophic vs. autotrophic 3.1 4.6
iron-oxidizing 9.15 9.20 11.17 CP.21
CP.22 CP.23
iron-related 5.5
Iow-nutrient 5.4
manganese-reducing 1.5
nitrifying 1.2 4.6
wood degradation 3.8 CP.6
Baelo Claudia, Cadiz, Spain 4.13 11.28 CP.33 CP.34
Balegem calcarenite 4.1
Ballast tanks 11.6
Basidiomycetes 3.8
Basilica of Tongeren, Belgium 4.4
Bearings, white metal 11.8 CP.26 CP.27
Benzalkonium chloride 11.31
Benzothiazoles 9.9
Biocalcarenite 4.8
Biocatalyzed leaching from waste ores 8.3 8.7
Biocides
application 6.31
bioassay evaluation of 6.28
biological wastes 8.8
case studies 6.31 11.19
during chemical cIeaning 9.25

This page has been reformatted by Knovel to provide easier navigation.

Index Terms Links

Biocides (cont.)
combined with biodispersants 11.16 CP.29 CP.30 CP.31
compatibility with scale inhibitors 6.19
costs 10.2
effluent discharge limitations 9.8
failure of 6.27 6.30
foaming of 6.30
in gas gathering system study 6.33
glutaraldehyde 6.21
half-lives of 9.11
in hydrostatic testing water 9.14
isopropyl alcohol 6.21
for lichens and algae 11.31
maintenance 9.6
during mechanical cleaning 11.16
nonoxidizing 9.7 9.25
during outages and wet lay-up periods 9.11
pH and 9.12
power plants 7.10
quaternary amines 6.21
residual testing 6.33 6.38
stoneworks 4.15
2,3,5,6-tetrachloro-4-(methylsulfonyl)-pyridine 4.15
toxicity concerns 10.1
Biocorrosion. See Microbial-induced corrosion
Biodispersants 7.11 9.27 11.15 11.18
CP.29 CP.30
Biofilms
concentration profiles in 1.4
conceptual models 1.2
copper alloys 1.5
corrosion cells under mud films 11.9
deposition accumulation monitors 10.7
direct inspection 10.3
electrochemical monitoring 10.9 10.12

This page has been reformatted by Knovel to provide easier navigation.

Index Terms Links

Biofilms (cont.)
fluid velocity and 8.4
hydrogen sulfide accumulation 1.4
methanogenic 1.2
pH within 1.5
sampling devices 10.7 10.12
Spools 6.30 CP.16
in waste treatment equipment 8.4 CP.20
Biofilm spools 6.30 CP.16
Biomineralization 1.2
Bioreceptivity 4.1
Bioremediation of hazardous wastes 8.2 8.7
Biostats 9.7 9.14
Biotite 4.9
Bird droppings 4.8
Bismaleimide, carbon-reinforced 3.3
Blue-green algae. See Cyanobacteria
Borate salts 9.12 9.14
Borobudur temple, Indonesia 4.4
Brazilian sandstone churches 4.8
Bricks 4.10
Bromine treatment 9.7
Bryophytes 4.6 4.9
See also Mosses
Building materials. See also Stonework corrosion
bioreceptivity 4.1
bricks and terracotta 4.10 CP.9
granites 4.9
limestones 4.2 11.26 CP.7 CP.32
CP.33
marble 4.1 11.27 CP.7
mortars 1.5 4.1 4.9 8.5
sandstones 4.6
treatment and restoration 4.14

This page has been reformatted by Knovel to provide easier navigation.

Index Terms Links

Caius Cestius pyramid 11.27 CP.33

Calcarenite 4.1
Calcite 4.3 4.6 4.14 11.28
CP.8
Caloplaca 4.6 11.26 CP.8 CP.32
Caloplaca aurantia 4.8
Caloplaca chalybaea 11.27 CP.33
Caloplaca citrina 11.30 CP.34
Caloplaca lactea 11.30
Camshaft bearings 11.11 CP.27
Candelariella 4.10
Carbon dioxide corrosion 6.27
Carbon fibers 3.2 8.6
Carbon steel
cooling tower supports 11.21 CP.31
gas pipelines 6.1 6.15 CP.13
internal surface of corroded piping 7.5 9.15 CP.17 CP.21
CP.22
pit shape 6.18
return activated sludge 8.2
rupture zones 11.22
type 43A 11.3
type 50A 11.3
wastewater piping 8.2 8.5 8.7 CP.20
weight-loss coupons 10.11
Carrara marble 4.1 11.27
Case studies
consolidant resins 11.30
constructional steel pilings 11.3 CP.25
geothermal fields in Mexico 11.21
marble 11.27
milk sterilizers 11.35
natural gas gathering system 6.27

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Case studies (cont.)

organic wetting agents and anionic copolymers 11.17
pigging operations 11.16
power station cooling water 11.19 CP.30 CP.31
Roman mosaics 11.25 CP.32 CP.33
Roman stuccoes 11.28 CP.34
ships' ballast tanks 11.6
ships' hull bottom plate 11.6 11.12 CP.25 CP.26
CP.27
tin-oxide corrosion of white metal bearing surfaces 11.8 CP.26 CP.27
Castle Herberstein, Austria 4.11 CP.9
Cathodic polarizations 1.7
Cathodic protection (CP)
changes in electrical properties 6.3
gas pipelines 6.1 6.10
non-metallic linings 9.9
pH changes 6.3
waste treatment processes 8.7
water conductivity 6.8
Cell components assays 10.5
Cell numbers, limited interpretation of 1.6
Cement mortar 8.5
Cerro Prieto geothermal field 11.21
Certosa of Pavia, Italy 4.2 CP.7
Cestia pyramid, Rome, Italy 4.4
Chaetomium 3.3
Chelating agents, for cleaning 9.4 9.24
Chemautotrophic bacteria 4.1
Chemical cleaning. See Cleaning, chemical
Chlorella homosphaera 4.9
Chlorella saccharophila var.saccharophila, 11.27
Chlorinated polyvinyl chloride (CPVC) 8.6
Chlorine treatments 7.10 9.7 9.25
Chlorophyta 4.10
Chromates 9.9

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Citrobacter sp. 11.22

Cladosporium 2.5 4.3 4.7
Cladosporium sphaerospermum 4.12
Clays 4.10 4.11
Cleaning
biocides during 9.25 11.16
chemical
of carbon steel piping 9.15
long-term, on-line, nonaggressive 9.4 9.26
materials of construction and 9.23
procedures 9.22
selection of chemicals 9.4 9.23
short-term, shutdown, aggressive 9.25
short-term, shutdown, nonaggressive 9.25
effluent discharge 9.20 9.24
maintenance 8.8 9.3 9.10
mechanical 6.19 6.22 9.3 9.15
9.22 11.16 CP.28
Closed-loop systems 7.2 9.2 9.5 9.10
11.19
Clostridium 4.11
Clostridium acetobutylicum, ATCC #824 3.2
Coal tar 6.2 8.5 8.7 CP.20
Coatings
cement mortar 8.5
coal tar 6.2
epoxy resin 2.1 3.2 8.5 CP.20
latex 3.5
new 6.10
plastic tape 6.2 6.4 CP.12
polymeric 3.4 8.6
Cologne cathedral, Germany 4.7
Colonization 4.1
Concrete 3.6 4.6 8.7 CP.6
Conductive caulk 3.4

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Consolidant resins 11.30

Control of MIC. See also Biocides; Mitigation of MIC
cathodic protection 6.1 6.8 6.10 8.7
9.9
corrosion inhibitors 6.20 6.30 9.9 9.14
environmental conditions control 4.15
fabrication, installation, and testing 8.6
fire protection sprinkler systems 5.4
fluid velocity 8.4 9.1 9.12
gas pipelines 6.19
maintenance and system design changes 9.28
microorganism control 9.6
postmitigation chemical treatment 9.29
prevention costs 7.11
source water 7.4 9.1 9.5 9.10
9.14
stoneworks 4.14 11.31
surfactants 6.40
system design 8.4 9.1 9.13 9.19
ultraviolet radiation 4.15
utilization of resistant materials 8.4 9.2 9.20
ventilation 2.4
welding seams 8.4
Cooling waters
bacterial species in 11.21
biocide/biodispersant treatment 11.19 CP.30 CP.31
monitoring 10.3 10.12
packing material 11.18 11.20 CP.29
recirculating systems 7.2 9.3 9.5 9.10
11.19 CP.30 CP.31
tower supports 11.22 CP.31
typical designs 7.2
Copper 5.1 9.19 11.10 CP.11
Copper alloys 1.5 6.16 7.5 9.12
9.16 9.19

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Copper-nickel tubing 6.16 CP.14 CP.24

Corrosion cells 6.7 11.9
Corrosion inhibitors 6.20 6.30 9.9 9.14
Corrosion potential 1.3
Corrosion products
analysis 6.8 6.18
austenite phase 7.6 7.9 9.19
as fingerprints for MIC 1.6 6.9
organic acid diagnosis from 6.28 CP.16
Costs of MIC 7.1 7.11 9.21 10.1
Coupon examination 10.6 10.10
CP. See Cathodic protection
Crevice corrosion 6.15 9.19 11.37
Cryptoendolithic communities 11.29
Cumulative corrosion loss (INT) 3.7
Cyanobacteria
bioreceptivity 4.1
consolidant resins 11.30
frescoes and mortars 4.13
light intensity and 4.4 4.13
mosaics 11.26
stonework deterioration 4.3 4.7 CP.9 CP.10
stuccoes 11.29 CP.34
ultraviolet radiation treatment 4.15

Delta ferrite 9.19

Denaturing gradient gel electrophoresis (DGGE) 4.11
Denickelfication 6.18
Deposition accumulation monitors 10.7
Design factors 8.4 9.1 9.13 9.19
Desulfobacter latus 11.22
Desulfovibrio 11.22
Desulfovibrio desulfuricans 4.2
Desulfovibrio vulgaris var. vulgaris NClB 8303 6.4

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Desulfuromonas acetoxidans 11.22

Diagnosis of MIC
cathodic protection current demand 6.4
chemical characterization of products 6.18
commercial assay kits 6.1
culturing 6.17 6.31
DNA probe techniques 6.1
in fire protection sprinkler systems 5.5
fluorescently labeled antibody probes 6.17 10.4 CP.18
in gas pipelines 6.13 6.16
In Line Inspection 6.10
microscopic examination 6.17 10.4 CP.14
Most Probable Number technique 6.3
Dichlorophene 4.15
Didymodon fallax 4.6
Direct current (DC) impedance techniques 10.14
Dirina massiliensis 4.8 4.12
Dispersants 7.11 9.27 11.15 11.18
CP.29
Djurelite 1.5
DNA genome assays 4.11 10.6
Dolomite 4.3

Effluent discharge 9.8 9.20 9.24

EHMW-HDPE (extra high molecular weight,
high-density polyethylene) 8.6
Electric coupons 10.13
Electrical resistance (ER) probes 10.13
Electrochemical biofilm monitoring 10.9 10.12 11.35
Electrochemical corrosion inhibitors 9.28
Electrochemical impedance spectroscopy (EIS) 3.3 10.14
Electrochemical noise (ECN) 3.5 10.15
Electron microscopy. See Scanning electron
microscopy; Transmission electron microscopy

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Energy dispersive X-ray analysis (EDXA) 6.8 10.6 11.5 11.6

11.8 11.10 11.35
Engyodontium album 4.12
Environmental scanning electron microscopy
(ESEM) 2.4 3.6 10.6
Enzymatic attack 3.2
Enzyme assays 10.5
Epicoccum 2.5 3.6
Epoxy resin coatings
bacterial degradation 3.2
fungal deterioration 2.1
polyamide-cured 8.5
in wastewater treatment piping 8.5 CP.20
Epsomite 4.12
Exophiala 4.7
Extra high molecular weight, high-density
polyethylene (EHMW-HDPE) 8.6
Extruded polyethylene 6.5

Fatty acid methyl ester (FAME) profiles 10.5

Feldspars 4.9
Fiber-reinforced plastic (FRP) 8.6
Fiber-reinforced polymeric composites (FRPCs) 3.2
Filtration of source water 9.2 9.5 9.10
Fire protection sprinkler systems (FPS)
components 5.1 5.3
diagnosis of MIC 5.5
maintenance cleaning 9.9 9.15
in power plants 7.2 7.5 CP.17
questionnaire 5.7
source water 9.2 9.10
summary of MIC cases 5.3
treatment and monitoring of MIC 5.6 9.11 11.17 CP.28
Flavirnonas 3.8

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Flavobacteriurn 3.8
Fluid velocity 8.4 9.1 9.12 9.23
Fluorescently labeled antibody probes 6.17 10.4 CP.14
Fluorinated polyimide composites 3.3
Foam application 9.24
Foaming 6.30
Forum of Baelo Claudia (Spain) 11.30 CP.34
FPS. See Fire protection sprinkler systems
Frankia 4.11
Frescoes 4.11
Frost-thaw cycles 4.1
Fuel tanks 3.4
Fungi
acidity 2.4
humid environments 2.1
military he1icopters 2.4
polymeric coatings 3.5 4.15
ship holds 2.5
stonework 4.3 4.10
structure and growth 2.1 3.1 CP.3
stuccoes 11.30
water activity and 2.1
wire rope 2.2 CP.4
Wood 3.8 CP.6
Fusariurn 4.7
Fusion bond epoxy 6.5

Gallionella 9.20 11.17 CP.29

Gallionella ferruginea 11 .18
Galvanic probes 10.12
Gas gathering systems 6.27
baseline monitoring 6.30
bioassay of potential biocides 6.28

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Gas gathering systems (cont.)

biocide application 6.31
biocide residual testing 6.33
conclusions 6.40
monitoring results 6.33
Gas pipelines, external corrosion in
coating degradation 6.3
corrosion scenarios 6.9
future needs 6.11
integrity management 6.10
modes of coating failure 6.1
newer coatings 6.10
protected steel 6.8
shielding disbondments 6.4 6.10
unprotected steel 6.6
Gas pipelines, internal corrosion in
detection 6.16
mechanisms 6.14
microbes involved 6.14
mitigation 6.19
monitoring 6.18
photographs 6.15 6.23 6.24 CP.13
CP.15
Geitleria calcarea 4.13
Gene probes 10.5
Geothermal power plants 11.21
Glass fibers 3.2 8.6
Gloeothece sp. 4.1 4.5 4.7
Glossary of terms ix
Glutaraldehyde 6.21 9.11
Goethite 6.9
Gold ore 8.3
Granites 4.9
Graphite fibers 3.3
Greigite 6.9

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Growth assays 6.3 6.31 10.4

Gymnostomum calcareum 4.6
Gypsum crusts 4.2

Haematoccus pluvialis 4.4

Halite 4.12
Halobacterium 4.12
Halococcus 4.12
Halomonas 4.11
Halophilic microorganisms 4.12
Hazardous waste bioremediation 8.2
Heat exchangers
corrosion monitoring 10.9 10.11
mechanical cleaning 9.4
photos of corrosion on 9.17 CP.23 CP.24
in the power industry 7.5 7.9 CP.19
Hematite 6.9
Heterotrophic bacteria 3.1 4.1 4.7 4.11
High-pressure water lancing 9.10
Hormodendrum 2.5 3.6
House of Neptune (Italica, Spain) 11.26 CP.32
House of the Birds (Italica, Spain) 11.26 CP.32
Hull plate corrosion 11.12 CP.25 CP.26 CP.27
Humid environments, fungal-influenced corrosion 2.1
Hydraulic fluid 2.5
Hydrazine 9.9
Hydrocarbon fuels 2.1 4.7 6.24 8.2
Hydrocarbon wastes 8.2
Hydrogenase assays 10.5 11.13
Hydrogen peroxide 4.15 9.7 9.11 9.25
Hydrogen sulfide accumulation 1.3 8.6
Hydrolazing 9.22
Hydrolysis of biocides 9.11
Hydrolysis reactions by metal-depositing bacteria 1.4

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Hydrophase 11.31
Hydrostatic testing, MIC from 7.3 8.6 9.6 9.9
9.13
Hyella fontana 4.4
Hyphae 3.1 4.9
Hypochlorite treatments 4.15 9.25

In-line filtration 9.2

In Line Inspection (ILI) 6.10
Inoculation 4.1
In situ bioremediation 8.2 8.7
INT (cumulative corrosion loss) 3.7
Iron 1.6 8.7
Iron hydroxide ribbons 11.17 CP.28 CP.29
Iron oxide deposition 1.3 1.4 9.15
Iron-oxidizing bacteria 9.15 9.20 11.17 CP.21
CP.22 CP.23
Iron-related bacteria (IRB) 5.5
Iron sulfides 6.5 10.5 10.13
See also Sulfides
lsoelectric points 1.7
lsopropyl alcohol 6.21
Italica, Spain 4.5 4.13 11.26 CP.7
CP.32

Jeronimos monastery, Lisbon, Portugal 4.13 CP.10

Jetting 9.22
Journal bearings 11.8 11.10 CP.26 CP.27

Kerosene 4.7
Ketoglutaric acid 4.9
Klebsormidium flaccidum 4.9 4.10 11.27

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Lactococcus lactis subsp. lactis, ATCC #19435 3.2

Lancing, high-pressure water 9.1
Land farming 8.2
Lanolin 2.5
Lateral corrosion 9.18
Latex coatings 3.5
LCO (limiting condition of operation) 7.4
Lead 4.2 11.10
Leak testing water. see Hydrostatic testing, MIC from
Lecania erysibe 4.8
Lecania turicensis 11.31
Lecanora 4.10
Lecanora pruinosa 4.8
Lecanoric acid 4.6
Lepidocrosite 6.9
Lichen acids 4.6 4.13
Lichens
building stone 4.5 4.8 4.14 CP.7
CP.8 CP.9
endolithic 4.5 4.14 CP.8
epilithic 4.5
frescoes and mortars 4.12 CP.10
on limestone 4.5 11.26 CP.7 CP.8
CP.32 CP.33
organic acids from 4.6 4.13
ornithocoprophilous 4.8
polyester resins 4.15
on stuccoes 11.29 CP.34
Limestones 4.2 11.26 CP.7 CP.8
CP.32
Limiting condition of operation (LCO) 7.4
Linear polarization resistance (LPR) probes 10.13 11.5
Low-nutrient bacteria (LNB) 5.4
Lubricating oils 11.9 11.11

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Mackinawite 1.6 6.9

Maghemite 6.9
Magnetite 6.9
Makeup water 9.5 9.10
See also Source water
Manganese oxide deposition 1.3
Manganese-reducing bacteria (MRB) 1.5
Marble 4.1 11.27 CP.7
Marcasite 6.9
Marine microbial corrosion
constructional steel pilings 11.3 CP.25
ships’ ballast tanks 11.6
ships’ hull bottom plate 11.6 11.12 CP.25 CP.26
CP.27
tin-oxide corrosion of white metal bearing surfaces 11.8 CP.26 CP.27
Mayan Great Jaguar Pyramid 4.6
Mechanical cleaning 9.3 9.15 9.22
Medical uses of biodegradation 3.8
Mesopitting 4.14
Metabolites 10.5
Metals. See also names of individual metals
biocatalyzed leaching from waste ores 8.3 8.7
biomineralization 1.2
chemical cleaning agents 9.4
fungal-influenced corrosion 2.1
reprecipitation 9.4
Methanogenic films 1.2
Mica 4.9
Microbial-induced corrosion (MIC)
assessment of 9.17
(See also Diagnosis of MIC)
beneficial uses 3.8
Costs of 7.1 9.21 10.1

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Microbial-induced corrosion (MIC) (cont.)

definition 5.1
mechanisms 6.14
monitoring (See Monitoring of MIC)
overview 6.13
pitting, general, and crevice 6.15 9.18 11.37
rate-limiting step 6.14
Microbiology influenced corrosion 6.13
See also Microbial-induced corrosion
Micrococcus 4.11
Microcolonies 1.3
Micropitting 4.14
Microscopic examination 6.17 10.4 CP.14
Mildew 3.2
Military helicopters 2.4 3.5 CP.4 CP.5
Milk sterilizers 11.35
Mineral generation 4.10
Minium 4.2
Mitigation of MIC. See also Biocides; Cleaning
Control of MIC
chemical treatments 8.8 9.3 9.6
chlorine treatments 4.15 7.10 9.7 9.25
control of microorganisms 9.6
deciding viability of 9.14
effluent discharge 9.8 9.20
evaluation of 9.14
during hydrostatic testing 7.3 8.6 9.6 9.9
9.13
identification of limitations 9.19
maintenance cleaning 8.8 9.3 9.10
microorganism control 9.6
off-line vs. on-line 9.3 9.20
during outages and wet lay-up 9.11
pigging 6.19 6.22 11.16
postmitigation chemical treatments 9.29

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Mitigation of MIC. See also Biocides; Cleaning

Control of MIC (cont.)
during preoperational construction phase 9.12
preprogram planning 9.16
during pretreatment phase 9.13
stagnant vs. flowing water 9.12
suspended solids control 9.8
use of resistant materials 8.4 9.2 9.20 CP.20
waste treatment systems 8.8
water treatment 7.10 8.8 9.3 9.5
Monitoring of MIC
assessment of severity and extent 9.17
baseline 6.30
cell components 10.5
coupon examinations 10.6
deposition accumulation monitors 10.7
direct inspection 10.3
electrical resistance probes 10.13
electrochemical impedance spectroscopy 3.3 10.14
electrochemical methods 10.9 10.12
electrochemical noise methods 10.15
enzyme assays 10.5
in fire protection sprinkler systems 5.6
galvanic probes 10.12
in gas gathering system study 6.33
gas pipelines 6.18
growth assays 10.4
linear polarization resistance probes 10.13
metabolites 10.5
method requirements 10.2
of microbes 10.3 10.13
sampling devices 10.7 10.12
Monuments. See Stonework corrosion
Mortars 1.5 4.1 4.9 8.5
Mosaics deterioration 4.13 11.25 CP.32

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Mosses 4.6 4.9 4.14 11.26

11.32 CP.32
Most Probable Number (MPN) 6.3 6.31 10.4
Muriella terrestris 4.9 4.10 11.27
Mycelia 3.1
Mycelia sterila 3.6

Natrococcus 4.12
Natronobacterium 4.12
Necropolis of Carmona, Spain 4.13 CP.10
Nickel-based alloys 7.10
Nitrifying bacteria 1.2 4.6
Nitrite borate inhibitors 9.9
Nitrobacter 4.7
Nitrobacter vulgaris 4.7
Nitrosomonas 4.7
Nitrosospira 4.7
Nitrosovibrio 4.7
Nitrous oxides 4.7
Nocardia 4.11
Nodules. See Tubercles
Nonferrous alloys 9.19
Nostoc punctiforme 4.10
Nuclear power plants. See also Power stations
competing requirements 7.1
copper alloys 7.5 CP.18
costs of repairs 7.1 10.1
mitigation 7.10
nickel-based alloys 7.10
redundancy requirements 7.2
stainless steels 7.6
steels and cast irons 7.4 7.6 CP.17
Nuclear waste storage containers 2.1 3.6
Nucleic acid assays 10.5
Nutrients, from air pollution 4.2

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Oceanospirillum 1.7
Offshore production systems 6.19
Open-loop systems 7.2 9.3 9.5
Orcinol depsides and depsidones 4.6
Organic acids
analysis of 6.31
bacterial 5.5
concrete degradation 3.6
diagnosis of 6.28
free acid forms 6.31
fungal 2.1 3.6 4.3 4.9
in gas gathering system study 6.37
lichen acids 4.6 4.13
as microbial nutrients 6.15
Organic deposits, cleaning of 9.5
Organic wetting agents 11.18
Orsellinic acid 4.6
Outages 9.11
Oxalic acid 4.5 4.8 4.13
Oxidizing agents 9.7 9.10
Oxygen
alternating aerobic/anaerobic conditions 6.8
copper sulfide corrosion 1.5
gas gathering pipe corrosion 6.28 CP.16
scavengers 9.10
stainless steels 7.8 7.1
Oysters 11.13
Ozone treatment 9.7

Palazzo Farnese, Caprarola, Italy 4.13

Pardon Gate, Seville, Spain 4.10 CP.9
Parmelia conspersa 4.10
PCR (polymerase chain reaction) 10.6

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Penetrant-biodispersants 9.8 9.14

Penicillium sp. 2.3 2.5 3.6 4.3
4.7
Pentachlorophenol 4.15
Pestalotia 2.5 3.6
Petroff Hauser Counting Chamber 10.4
Petrographic studies 4.5
pH
in biofilms 1.5
cathodic protection and 6.3
cement mortars 1.5 8.5
corrosion rates 6.7
in frescoes and mortars 4.12
hydrolysis reactions and 1.4
during hydrostatic testing 9.14
organic acid production 6.15
Phenanthrene 4.2
Phoma 2.5 3.6 4.7
Phormidium sp. 4.7
Phormidium tenue 4.9 4.10
Phosphonic acid derivatives 9.9
Phototrophic microorganisms 4.4 4.10 CP.7 CP.33
Phthalates 6.6
Physcia 4.10
Pigging 6.19 6.22 9.22 11.16
Piling corrosion, case history 11.3 CP.25
Piping systems. See also Gas pipelines, external
corrosion in; Gas pipelines,
internal corrosion in
internal surfaces of 7.5 9.15 CP.17 CP.21
CP.22 CP.23
mechanical cleaning 9.4 9.15 9.22
in nuclear plants 7.3 CP.17
steel 6.6 8.2 CP.20
sulfate-reducing bacteria 9.16
in wastewater treatment 8.2 8.5 CP.20

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Pitting
anodic corrosion cells 9.18 11.9
assessment of 9.17
ballast tanks 11.6
bearing surfaces 11.10 CP.26 CP.27
beneath tubercles 6.15 9.15 9.20
11.16 CP.14 CP.28
fire protection systems 5.2 CP.11
formation process 6.15
gas gathering systems 6.28 CP.16
heat exchangers 9.17 CP.24
hyphae penetration 4.9
mesopitting/micropitting 4.14
nuclear power plants 7.4 CP.17
pit shape 6.18
ships’hulls 11.12 CP.26 CP.27
in stonework 11.27 CP.33 CP.34
Planktonic organisms 10.3 11.19
Plasticizers 6.6
Plastics degradation 8.6
Plastic tape coatings 6.2 6.4 CP.12
Plectonema 4.9
Plectonema boryanum 4.9 4.10 11.27
Polarization resistance (LPR) probes 10.13 11.5 11.35
Polyamide-cured epoxies 8.5
Polycyclic aromatic hydrocarbons (PAHs) 4.2
Polyester polyurethanes 3.2 3.4
Polyethylene 6.5 8.6
Polyimide films 3.5
Polymerase chain reaction (PCR) 10.6
Polymeric coatings 3.4 8.6
PoIymeric materials
cross-linking in 8.6
fiber-reinforced polymeric composites 3.2
medical uses of biodegradation 3.8

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PoIymeric materials (cont.)

polymeric coatings 3.4 8.6
for treatment and restoration 4.15
Polymeric quaternary nitrogen 9.11
Polyolefin tape 6.4
Polypropylene tape 6.6
PoIyt hioet h er conductive cauIk 3.4
Polyurethane cable sheathing 2.1
Polyurethane paint 2.4 3.5 CP.4 CP.5
Polyvinyl chloride (PVC) 6.6 8.6
Portsmouth Harbour pilings 11.3
Power stations. See also Nuclear power plants
biocide and biodispersant case study 11.19 CP.30 CP.31
cleaning 7.11
copper alloys 7.5 CP.18
Costs of MIC 7.1
fire protection systems 7.2
hydrotesting 7.3
mitigation approaches 7.10
piping systems 7.3
stainless steel 7.6 CP.18
Pozzolana 4.1
A Practical Manual on Microbiologically Influenced
Corrosion 7.1
Preoperational construction phase 9.12
Pretreatment phase 9.13
Prevention of MIC. see Control of MIC
“Primer on the AC Impedance Technique” 10.14
Protozoa 8.2 CP.19
Pseudoanabaena sp. 4.10
Pseudocapsa dubia 11.27
Pseudomonas 1.7 3.8 4.11 8.2
11.5 11.22
Pseudomonas aeruginosa 1.2 3.3 11.22
Pseudomonas fluorescens 3.2

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Pseudonocardiaceae 4.11
Pyrite 6.9

Quartzite 4.9
See also Sandstones
Quaternary amines (QA) 6.21
Quaternary ammonium compounds 4.15

Ramalina capitata 4.8

Ramalina digitellata 4.8
Rate-limiting step 6.14
Rebar 3.7 CP.6
Recirculating systems 7.2 9.3 9.5 9.10
11.19 CP.30 CP.31
Redox potential 1.4 6.7
Reinforced fiberglass 11.22 CP.31
Resins
consolidant 11.30
epoxy 2.1 3.2 8.5 CP.20
organic 4.15
polyester 4.15
for treatment and restoration 4.15
Restoration, of stoneworks 4.14
Return activated sludge (RAS) 8.1 8.4 8.7
Reverse Sample Genome Probing (RSGP) 10.6
Rhizocarpon geographicum 4.9
Rhizopus sp. 11.22
Roman mosaics 4.5 11.25 CP.32 CP.33
Roman stuccoes 11.28 CP.34
Rupture zones 11.22

Salamanca, Spain 4.4 4.8 CP.7 CP.8

Salinity 4.12 6.7

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Sampling devices l0.7 10.12

Sandblasting 9.22
Sandstones 4.6
Santa Maria degli Alemanni, Messina, Italy 4.6
Santa Maria de la Rabida, Huelva, Spain 4.11
Sarcogyne pruinosa 11.30
Scale inhibitors 6.19 9.5 9.8
Scanning electron microscopy (SEM)
biofilms 11.22
building materials 4.5 4.9 4.14
copper alloys 1.5
cyanobacteria 4.5
environmental 2.4 3.6 10.6 CP.5
fatigue cracks 11.11
ferric hydroxide 11.17
fungi 2.3 CP.5
iron hydroxide ribbons 11.17 CP.29
lichens 11.29
stainless steel milk sterilizers 11.36
weldments 7.8
Schleswig Cathedral, Germany 4.10
Scytonema julianum 4.13
Secondary treatment 8.1
Selinunte, Italy 4.8
Sessile organisms, monitoring of 10.3
Seville, Spain 4.7
Sewage collection systems 3.7 3.9
Ships' holds 2.1 2.5 3.4 11.6
Ships' hull bottom plates 11.6 11.12 CP.25 CP.26
CP.27
Siderite 6.9
Side-stream filtration 9.2 9.10
Soapstone 4.8
Sodium hypochlorite 4.15 9.25
Sodium sulfite 9.11

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Soil, clay content in 6.7

Soil aggressivity model 6.7
Soil organisms 6.5
Soil resistivity 6.7
Source water 7.4 9.1 9.5 9.10
9.14
Sphaerotilis natans 8.2 CP.19
Sponge-ball cleaning systems 9.22
Spores 2.1
SRB. See Sulfate-reducing bacteria
Stability diagram, mackinawite 1.6
Stainless steel
chemical composition 11.37
high molybdenum 7.10
manganese oxide deposition 1.3
milk sterilizers 11.35
nickel content of corrosion products 6.18
pit shapes 6.18
polymeric coatings on 3.4
return activated sludge 8.2
sulfides and 1.4
tanks 9.16 9.18
two-phase welds 9.19
type 303 8.6
type 304 6.16 8.2 8.6
9.18 10.16 CP.24
type 316 8.7
wastewater treatment systems 8.6
weldment corrosion 7.6 CP.18 CP.24
wrought 7.8
Steel. See also Carbon steel; Stainless steel
embedded in concrete 3.7
in fire protection sprinkler systems 5.1 CP.11
galvanized 5.2 CP.11
iron sulfide galvanic couples 6.7

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Steel. See also Carbon steel; Stainless steel (cont.)

pilings 11.3 CP.25
piping 6.6 8.2 CP.20
rebar 3.7 CP.6
steel/FeS/SRB corrosion cells 6.7
Stemphylium 2.5 3.6
Stichococcus bacillaris 4.9
Stonework corrosion
bricks and terracotta 4.10 CP.9
consolidant resins 11.30
frescoes 4.11
granites 4.9
limestone 4.2 11.26 CP.7 CP.8
CP.33
marble 4.2 11.27 CP.7
mortars 4.1 4.9
remedial measures 4.14 11.31
Roman mosaics 4.5 11.25 CP.32 CP.33
Roman stuccoes 11.28 CP.34
sandstones 4.6
soapstone 4.8
Streamers 1.2
Streptomyces 4.11
Streptomyces griseus 4.11
Stuccoes deterioration 11.28 CP.34
Suffield shallow gas gathering system 6.27
Sulfate-reducing bacteria (SRB)
cathode depolarization 6.14
cement mortar coatings 8.5
concrete degradation 3.7
diagnosis 6.27 6.31 10.6
in gas gathering system study 6.35
gas pipeline degradation 6.3 6.7
growth assays 10.4
hydrogen sulfide accumulation 1.3

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Sulfate-reducing bacteria (SRB) (cont.)

limited interpretation of cell numbers 1.6
marine pilings degradation 11.5
in piping 9.16
poIymeric materials 3.2 3.4
ships' ballast tanks 11.6
Sulfate reductase 10.5
Sulfides
accumulation 1.3 8.6
bioprecipitated 1.4
black iron sulfide precipitates 6.7
detection and analysis of 6.8
iron 6.5 10.5 10.13
in wastewater treatment systems 8.6
Sulfur, elemental 6.9
Sulfuric acid, in wastewater treatment systems 8.6
Surfactants 6.40 8.6 11.18
Suspended solids control 9.8 9.10
Synechococcus sp. 4.10
Synechocystis sp. 11.27

Tanks
ballast 11.6
fuel 3.4
mechanical cleaning 9.4
stainless steel 9.16 9.18
Tape wrap coatings 6.2 6.4 CP.12
Temperature 7.9 9.1 9.23
Temple of lsis (Baelo Claudia, Spain) 11.30
Temple of Jupiter (Baelo Claudia, Spain) 11.29 CP.33 CP.34
Templete Mudejar (Spain) 11.32
Terracotta 4.10 CP.9
Tesserae deterioration 4.2 11.26 CP.7 CP.32
CP.33

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2,3,5,6- TetrachIoro-4-( methylsuIfonyl)-pyridine 4.15

Thermonatrite 6.4
Thiobacillus 4.6 8.6
Thiobacillus ferroxidans 3.2 8.3
Thiobacillus intermedius 4.6
Thiobacillus novellus 4.6
Tidal zones 11.3 CP.25
Tin-oxide corrosion of white metal bearing surfaces 11.8 CP.26 CP.27
Titanium corrosion 1.7
Toledo, Spain 4.9
Tortula muralis 4.6
Total residual oxidant (TRO) 9.7
Transmission electron microscopy (TEM) 10.6
Treatment. See Biocides; Control of MIC; Mitigation
of MIC
trichoderma 2.5 3.6 4.7
trichotecium sp. 4.3
Tubercles
carbon steel piping 9.15 CP.21 CP.22 CP.23
effects on fluid-carrying capacity 7.4
formation of 6.15
heat exchangers 9.20
nuclear power plants 7.4
pipelines 11.16 CP.28
reactions under 1.4 7.4 CP.14
removal of 11.15
Turbidity inspections 9.10 10.4
Turbulence-induced corrosion 1.5

Ultraviolet radiation 4.15

Underdeposit acid attack 6.16 6.30

Vascular plants 4.11 CP.9

Verrucaria muralis 11.31

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Verrucaria nigrescens 4.8 11.26 11.29 CP.33

Vibrio 11.5
Vibrio parahaemolyticus 1.2
Vinyl ester composites 3.2

Waste ores, biocatalyzed leaching 8.3 8.7

Waste treatment
biological waste treatment processes 8.1
cathodic protection 8.7
fabrication, intalIation, and testing 8.6
hazardous waste bioremediation 8.2
resistant materials 8.4 CP.20
system design 8.4
wastewater 3.6 3.9 8.1
Wastewater treatment systems 3.6 3.9 8.1
Water
activity 2.1
conductivity 6.7 6.10
hydrostatic testing 8.6 9.6
lancing 9.10
makeup 9.5 9.10
source 7.4 9.1 9.5 9.10
9.14
velocity 8.4 9.1 9.12 9.23
Water systems, high purity 9.10
Water treatment 9.5
Weight-loss coupons 10.6 10.10
Welded seams 7.5 8.4 8.6 9.2
9.18 CP.18 CP.24
Wet lay-up 9.11
Wetting agents 11.18
White metal, tin-oxide corrosion of 11.8 CP.26 CP.27
Wire rope corrosion 2.2 CP-4
Wood degradation 3.8 CP.6
Wooden spools 2.2 CP.3 CP.4

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Xanthophyta 4.10
X-ray diffraction (XRD) 6.8 11.5 11.6 11.11
11.13

Yeasts. 2.1

Zero resistance ammeter (ZRA) 10.15

Zinc chromate 3.4
Zinc phosphate 3.4

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