Soil Chemistry Analysis and Affects On Corrosion Rate

Soil Chemistry Analysis and
Affects on Corrosion Rate

> AGA Operations Conference
Corrosion Committee
Chicago, IL
April 27, 2005
Daniel Ersoy, GTI
daniel.ersoy@gastechnology.org
Corrosion Rates in General

> When one calculates remaining life (half life) it is inversely
proportional to the corrosion growth rate (GR) assigned.
Life = (constant) (Safety Margin) (Nominal Wall Thickness)/(Growth Rate)
> Therefore the corrosion GR is very important in determining

the reassessment interval based on engineering analysis.
However, corrosion growth rates are difficult to predict and
measure and should be done with caution.
> Actual rates may be obtained from direct measurement of
wall thickness as a function of time (excavations, ILI runs,
etc.). However, this is the exception rather than the rule.
AGA Operations Conference Corrosion Committee Meeting April 27, 2005 Chicago, IL
Corrosion Initiation Time

> Assuming external corrosion started at the time of
installation may result in a non-conservative rate estimate
since a coating system may delay onset of corrosion.
> On the other hand, corrosion rates often drop with time due
to corrosion film build-up which slows diffusion rates.
> Look for evidence of coating damage from installation.
Rock impingement or backfill damage probably happened
during install. Third party damage along the top of the pipe
may also be easy to identify and assign a date to.
> It is difficult to estimate the time period that a coating
provided an efficient barrier.
Growth Rate Estimation - General

> Time periods when CP systems are out-of-service or not
functioning normally are important to know to estimate
growth rates.
> The more surface are inspected, the more likely a larger pit
may be found leading to a higher growth rate.
> Pitting at a localized coating defect is usually more
aggressive than on bare pipe due to the cathode to anode
ratio.
Growth Rate Estimation - Default

> 16 mils per year (mpy) is the recommended rate (NACE RP
0502) for re-inspection intervals. This rate represents the:
80% confidence level of
Maximum pitting rates for
Long-term exposure (17 yr) for
Underground corrosion test of
Bare steel pipe coupons
Without CP
In a variety of soils.
Growth Rate Estimation - Default

> The RP states that 16 mpy can be reduced to 12 mpy if one
can show that CP levels of the pipeline had at least 40 mV
of polarization (considering the IR drop) since installation.
> The RP also allow statistically valid methods based on data
to be used for corrosion rate estimation.
Soil Analysis and Default Rate Modification

> It is therefore very important to understand why certain soil
characteristics or properties are measured at each dig site.
> Corrosion Rates may be justifiably developed by:
Collecting all the important soil parameters and comparing
them to historical/pre-assessment data on the pipeline; and
Comparing the soil/pipe environment to already published/peer
reviewed data for underground/soil corrosion of steel.
> The operator can then make an informed decision as to an

appropriate corrosion rate and state the reasoning behind
the decision.
Corrosion in Soils
> Metal corrosion in undisturbed soils is generally very low
regardless of the soil composition, e.g. metal piles driven
into the soil.
> Corrosion of metal (steel) in disturbed soils (e.g., buried
pipelines that are backfilled) is strongly affected by soil
conditions as noted earlier.
> Soil changes its chemical and physical nature continuously
over time and seasonally.
> Factors contributing to the changes include precipitation,
plant growth and decay, roads, power lines, farming factors,
road salting, etc.
Soil Characteristics to Consider

> Consider the following soil characteristics and environment
variables to assist in estimating corrosion rates:
Chloride level
Moisture content
Oxygen content/Redox potential
Soil permeability/texture
pH/Acidity
Temperature
Soil resistivity
Drainage characteristics
Sulfate and Sulfite ion concentrations
Microbiological activity
Stray currents
Spillage of corrosive substance/pollution
Soil Classification/Texture
> There are numerous ways to classify soils.
> Broad classifications by material are:
Mineral Soils (<15% organic matter)
Organic Soils
> Muck: 15-50% organic Matter
> Peat: >50% organic Matter
> Particle size classes include sands, clays, gravels and

stones, silts, loams, etc.
> By particle size:
Gravel and Stones > 2 mm

Fine Gravel 1-2 mm
Sand 0.05-1 mm
Silt 0.002-0.05 mm
Loams (friable)
Clay <0.002 mm
Soil Classification/Texture
> Clay has the finest particle size which reduces movement of air
(oxygen) and water, i.e. low aeration when wet. This may lead to
very low general corrosion, but increase local (pitting) corrosion by
setting up differential aeration cells.
> However the high plasticity (stickiness) of clay during shrink-swell
of the soil can pull off susceptible coatings.
> Clay also is susceptible to cracking during wet-dry cycling which
can help transport air and moisture down to the pipe surface.
> Sand promotes aeration and moisture distribution. Soluble salts
and gases (air/oxygen) can are more easily transported to the
metal surface. This may lead to greater general corrosion but also
produce less pitting.
Soil Classification/Drainage
> Drainage can be affected by the soil texture, lay of the
land/inclination, seasonal precipitation, and the water table
height and variation.
> The affect of drainage on general corrosion and maximum
pitting rates has been studied for buried steel and is presented
below:
Drainage Class
(relative level)
Very Poor
Poor
Fair
Good
General Crsn
(mil/yr)
2.3
1.5
2.5
0.86
Max Pitting Rate

(mil/yr)
> 17.7
9.1
12.2
7.1
[Romanoff, M., Underground Corrosion, NIST 1957]
Soil pH
>
For most soils, the acidity or alkalinity is generally stable due

to the buffering nature of the soluble minerals.
>
Soils range in pH in the U.S. from pH 5 to 10. Surprisingly the

pH has a relatively small effect on pitting and general
corrosion compared to other variables.
pH of Soil
< 5.5
5.5-6.5
6.5-7.5
> 7.5
Corrosivity
Severe
Moderate
Neutral (low)
None (low)
Acid/Alkaline
Acidic Soil
Slightly Acidic
Neutral
Alkaline Soil
>
Alkali Soils refer Alkaline soils with sodium and potassium

ions.
>
Calcareous Soils refer to Alkaline soils due to calcium

carbonate.
Soil pH
>
A study looked at 7590 underground sites and for pH found:
pH
< 4.0
4.1-6.0
6.1-7.0
7.1-8.1
8.1-10.0
> 10.0
% Occurrence
0.1
5
10
27
55
3
[Kroon, D.H., Integrity Assurance Program for Underground Storage Tank Systems, NACE Conf. Paper CP-13, California, 1987]
Soil Electrical Resistivity

> Soil electrical resistivity is a function of nature (class of soil),
amount of soluble salts, and moisture content.
> Ions (e.g., hydrogen, hydroxyl, and soluble salt cations and
anions) must migrate in the soil (the electrolyte) to permit the
completion of the corrosion reaction.
> Soil resistivity measures how easily ions move through the soil.
> Therefore a high soil resistivity suggests a low corrosion rate
because the rate of ion diffusion is low.
Soil Res. (ohm-cm)
> 20,000
10,000-20,000
5,000-10,000
3,000-5,000
1,000-3,000
<1,000
Corrosivity Rating of Buried Steel

Non-corrosive
Mildly corrosive
Moderately Corrosive
Corrosive
Highly Corrosive
Extremely Corrosive
[Roberge, P.R., Handbook of Corrosion Eng. McGraw-Hill, 1999]

> A second and third study are presented below:
Soil Res. (ohm-cm)

> 10,000
5,000-10,000
2,000-5,000
1,000-2,000
<1,000
Corrosivity Rating of Buried Steel

Very Low
Low
Moderate
High
Very High
[Miller, Foss, and Wolf, ASTM STP 74, 1981]
Soil Res.
(ohm-cm)
> 12,000
5,000-12,000
1,000-5,000
<1,000
General Crsn
(mil/yr)
1.4
1.3
2.3
2.48
Max Pitting Rate

(mil/yr)
10.2
9.1
> 17.7
12.2

> A fourth study looked at 7590 underground sites:
Soil Res. (ohm-cm)

< 3,000
3,000-9,990
10,000-19,900
20,000-49,900
>50,000
% Occurrence
16.1
37.1
20.7
16.5
9.6
Soil Conductivity
> Soil Conductivity is another measure of the electrical resistance
of the soil. It is measured in a solution of water.
> A high conductivity suggests a high corrosion rate (efficient
electrolyte).
> It is measured in Siemens/centimeter (S/cm), sometimes S is
referred to as mho since 1S = 1(Ohm)-1, and sometimes the
/cm is dropped.
Soil Conductivity (millimho/cm) Soil Corrosivity

< 0.1
Very Low
Low
0.1-0.2
0.2-0.4
Moderate
0.4-1.0
High
> 1.0
Very High
[Miller, Foss, and Wolf, ASTM STP 74, 1981]
Soil Conductivity
> Another study looked at 7590 underground sites and found:
Conductivity (millimho/cm)
< 0.020
0.020-0.049
0.050-0.099
0.100-0.999
> 0.999
% Occurrence
0.1
2.6
10.7
21.2
6.9
Soil Chemistry - General

> Mineral soils are a group of primarily inert
combinations of oxygen, aluminum, silicon, and
iron (and other metals).
> The primary constituents of over 80% of soils are:
Poly silicates: (Si3O84-) + K, Al, or Na
Orthosilicates: (SiO44-) + K,H,AL,Ca, Fe, or O
Metasilictes: (SiO32-) + Ca, Mg, or H
Oxides: (SiO2, Fe2O3, Fe3O4)
Calcite: (CaCO3)
Hydrous Aluminum Silicates (Clays): (AlxOHy) (SixOy)
> Organic matter is another constituent
Soil Chemistry - General

> In well aerated soils the iron compounds are
generally in the Fe3+ state and produce red,
yellow, and brown colors.
> In poorly aerated soils the oxygen content is low
and the soils are gray in color due to the reduced
state of the Fe.
> Organic matter is usually limited to humid regions.
> For corrosion one is interested in the constituents
that are soluble in water:
Basic forming elements: Na, K, Ca, Mg (raise pH).
Acid forming elements: Carbonate, Bicarbonate,
Chloride ion, Nitrate, and Sulfate (lower pH).
Soil Chemistry - Chlorides

> Chlorides are of great concern for several reasons.
> Iron chloride is soluble and its formation promotes anodic
dissolution of iron or steel.
> The chloride ion can act as a catalyst and participate in the
corrosion process many times.
> Chlorides are known to also breakdown protective oxide
layers and they are a cathodic depolarizer.
Chloride (ppm)
>5,000
1,500-5,000
500-1,500
100-500
Corrosivity
Severe
Considerable
Corrosive
Threshold
[modified ACI-318 Building Code]
Soil Chemistry - Chlorides

> A study looked at 7590 underground sites and found:
Chloride Conc. (ppm)

0-9
10-19
20-49
50-99
>100
% Occurrence
43.4
19.9
16.3
7.8
12.6
Soil Chemistry Sulfates/Sulfide

> FeSO4 corrosion product is soluble but less aggressive than
the chloride iron for steel corrosion.
Sulfate (ppm)
>10,000
1,500-10,000
150-1,500
0-150
Soil Corrosivity
Severe
Considerable
Detectible
Negligible
[modified ACI-318 Building Code]
Sulfate is tied to the presence of Sulfate Reducing Bacteria

(SRB). This anaerobic bacteria reduces the sulfate:
SO42- + 8 Hads S2- + 4H2O
Depolarizes
Cathode
Combines with Fe
and forms FeS
Soil Chemistry Sulfates/Sulfide

> Unaerated soils with high SO42- and neutral pH breed SRB.
> Sulfide presence indicates possible FeS and SRB.
> A study looked at 7590 underground sites and found:
Sulfide Conc. (ppm)

0.000
0.001-0.999
1.000-4.999
>5.000
% Occurrence
66.2
23.9
8.0
1.9
Soil Chemistry Moisture Content

> Moisture content contributes to the amount of soluble ions in
solution, resistivity, conductivity, etc.
> Generally, >20% moisture content is considered more
aggressive.
> A study looked at 7590 underground sites and for moisture
content found:
% Moisture Content
< 5.0
5.0-9.9
10.0-14.9
15.0-19.9
20.0-24.9
>25
% Occurrence
15.2
48.3
27.0
7.6
1.2
0.7
Soil Chemistry Redox Potential

> Oxygen content in soils is important because:
SRB require anaerobic conditions to thrive.
Differential oxygen content in adjacent sections of soils can create
oxygen concentration cells and localized corrosion.
> Soil Redox (reduction-oxidation) potential [also called ORP or

oxidation-reduction potential) is measured with a probe that
contains a Pt electrode and a standard calomel electrode
(Hg/Hg2Cl2/KCl).
> The potential difference between the electrodes indicates the soils
dissolved oxygen.
> A more positive Redox potential (standard H scale) indicates more
aeration.
Soil Chemistry Redox Potential

Redox Potential
(standard H Scale)
Aeration
Soil Corrosivity
Negative
0 to 100 mV
not aerated
none to weak
Extremely severe
Severe
100 to 200 mV
weakly aerated
Moderate
200 to 400 mV
aerated
Slight
> 400 mV
strongly aerated Noncorrosive

[Bradford, S., CASTI handbook of corrosion in soils, CASTI, 2000]
Some Thumb rules to Help

Determine Growth Rates
> A general set thumb rules from the stated data can be developed:
SOIL CORROSIVITY FOR BURIED STEEL
pH
Resistivity (ohm-cm)
Conductivity (mS/cm)
Chloride (ppm)
Sulfates (ppm)
Sulfides (ppm)
% Moisture (% wt)
Redox (mV Std. H)
Low
>6.5
>20,000
<0.2
<100
<150
Not Detectable
<20%
>200
Moderate
5.5-6.5
5,000-10,000
0.2-0.4
100-1,500
150-1,500
1-5
>20%
100-200
Severe
<5.5
<3,000
>0.4
>1,500
>1,500
>5
>20%
<100
The affects of Soil Classification, Texture, and Drainage are difficult to quantify.
Summary
> It may be possible to combine:
The data in this presentation and the thumb rules stated; with
The direct observations and analysis of the soil conditions and
observed corrosion for a pipeline segment; and
Prehistory from the Pre-Assessment
> And form a reasonable justification for a reduced corrosion rate

below the 16 mpy default rate.
> Recall that the 16 mpy is at a confidence level that indicates that is
is very likely that the value will be between 20% of the stated
value and that the value is the maximum pitting rate for long-term
corrosion of steel samples without CP.
> Therefore if the majority of ones conditions fell in the low area of
the thumb rules and the observed corrosion on the line reinforced
this low growth rate, the assigned rate should be able to be
lowered below the 16 mpy by a justifiable amount based on the
particular situation.
> The more data collected and analyzed, the more reliable the
assigned corrosion rate will be, and the easier to justify.
QUESTIONS ???
Soil Chemistry Analysis and

Affects on Corrosion Rate
> AGA Operations Conference
Corrosion Committee
Chicago, IL
April 27, 2005
Daniel Ersoy, GTI
daniel.ersoy@gastechnology.org

Soil Chemistry Analysis and Affects On Corrosion Rate

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Soil Chemistry Analysis and Affects On Corrosion Rate

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Soil Chemistry Analysis and

Affects on Corrosion Rate

Corrosion Rates in General

> Therefore the corrosion GR is very important in determining

Corrosion Initiation Time

Growth Rate Estimation - General

Growth Rate Estimation - Default

Growth Rate Estimation - Default

Soil Analysis and Default Rate Modification

> The operator can then make an informed decision as to an

Soil Characteristics to Consider

> Particle size classes include sands, clays, gravels and

Gravel and Stones > 2 mm

Max Pitting Rate

For most soils, the acidity or alkalinity is generally stable due

Soils range in pH in the U.S. from pH 5 to 10. Surprisingly the

Alkali Soils refer Alkaline soils with sodium and potassium

Calcareous Soils refer to Alkaline soils due to calcium

A study looked at 7590 underground sites and for pH found:

Soil Electrical Resistivity

Corrosivity Rating of Buried Steel

Soil Electrical Resistivity

Soil Res. (ohm-cm)

Corrosivity Rating of Buried Steel

Max Pitting Rate

Soil Electrical Resistivity

Soil Res. (ohm-cm)

Soil Conductivity (millimho/cm) Soil Corrosivity

Soil Chemistry - General

> Organic matter is another constituent

Soil Chemistry - General

Soil Chemistry - Chlorides

Soil Chemistry - Chlorides

Chloride Conc. (ppm)

Soil Chemistry Sulfates/Sulfide

Sulfate is tied to the presence of Sulfate Reducing Bacteria

Soil Chemistry Sulfates/Sulfide

Sulfide Conc. (ppm)

Soil Chemistry Moisture Content

Soil Chemistry Redox Potential

> Soil Redox (reduction-oxidation) potential [also called ORP or

Soil Chemistry Redox Potential

strongly aerated Noncorrosive

Some Thumb rules to Help

> And form a reasonable justification for a reduced corrosion rate

Soil Chemistry Analysis and

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