Water Treatment Handbook Guide

Water Treatment Handbook
Contents
CHAPTER 1: INTRODUCTION ............................ 1-1

BACKGROUND ................................................................... 1-3
Existing Systems Designed for Old Waterfloods......... 1-3
A New System To Be Installed for a New Waterflood
or EOR Project ......................................................... 1-4
OILFIELD WATER REQUIRING TREATMENT ................... 1-4
Water Sources ................................................................. 1-4
Characteristics of Waters That Affect Their
Handling and Treatment .......................................... 1-5
Produced Waters: ........................................................ 1-5
Source Well Waters: .................................................... 1-6
Open Waters: ............................................................... 1-6
WATER TREATMENT OBJECTIVES .................................. 1-7
POSSIBLE TREATMENTS REQUIRED TO ACHIEVE
OBJECTIVES ................................................................ 1-8
Treatment Objective — Injection ................................... 1-9
Filtration ....................................................................... 1-9
Removal of Free Oil from Water ............................... 1-10
Effective Corrosion, Scale, and
Biological Control ............................................... 1-11
Separate Treatment of Waters .................................. 1-11
EOR Treatment Considerations in Addition to
Those Listed Above ........................................... 1-12
Treatment Objective — Surface Disposal ................... 1-12
Additional Water Treatment Objectives ...................... 1-13
Corrosion, Scale, and Biological Control ................ 1-13
Recovery of Free Oil in Water and Lost Revenue ... 1-14
Special Treatment for EOR Requirements .............. 1-14
Nonroutine Treatments of “Special”
Oilfield Waters ..................................................... 1-15
OILFIELD TREATMENT METHODS AND EQUIPMENT .. 1-15
GLOSSARY ....................................................................... 1-19
Water Treatment Handbook i

CHAPTER 2: ANALYTICAL AND
TEST METHODS .............................................. 2-1
WATER ANALYSIS.............................................................. 2-3
Reasons for Water Analysis ........................................... 2-3
Constituents Determined and Properties Measured ... 2-4
Significance of Components or Properties .................. 2-5
Cations ......................................................................... 2-5
Sodium, Na+ .............................................................. 2-5
Potassium, K+ ........................................................... 2-5
Calcium, Ca2+ ........................................................... 2-5
Magnesium, Mg2+ ..................................................... 2-7
Barium, Ba2+ ............................................................. 2-7
Strontium, Sr2+ ......................................................... 2-7
Iron, Fe ...................................................................... 2-7
Hardness ................................................................... 2-8
Anions .......................................................................... 2-8
Chloride, Cl- .............................................................. 2-8
Salinity, Chlorinity, and Chlorisity ........................... 2-9
Salinity ....................................................................... 2-9
Chlorinity ................................................................... 2-9
Chlorisity ................................................................. 2-10
“Organic Acids” ...................................................... 2-10
Alkalinity.................................................................. 2-11
Dissolved Gases ........................................................ 2-11
Oxygen, O2 .............................................................. 2-11
Carbon Dioxide, CO2 .............................................. 2-12
Hydrogen Sulfide, H2S ........................................... 2-12
Neutral Components ................................................. 2-12
Silica ........................................................................ 2-12
Bacterial Content .................................................... 2-12
Oil-in-Water Content ............................................... 2-13
Total Residue .......................................................... 2-13
Suspended Solids................................................... 2-13
Total Dissolved Solids ............................................ 2-14
Properties ................................................................... 2-15
pH............................................................................. 2-15
Temperature ............................................................ 2-15
Turbidity .................................................................. 2-15
Color ........................................................................ 2-16
Density .................................................................... 2-16
Conductivity ............................................................ 2-16
Sampling ........................................................................ 2-16
Sample and System Identification ........................... 2-17
Sampling Procedures ................................................ 2-17
Field Measurements .................................................. 2-19
Preserved Samples.................................................... 2-20
Unpreserved Sample ................................................. 2-21
Oil-in-Water Content .................................................. 2-21
Analytical Methods ....................................................... 2-22
Chemical Properties .................................................. 2-22
ii Water Treatment Handbook

Physical Properties ................................................... 2-29
Standard Analytical Methods ................................... 2-29
Analytical Report .......................................................... 2-30
Sample Identification ................................................ 2-31
Methods of Presentation of Components ............... 2-31
Units of Measurement ............................................... 2-34
Concentration Units Based Upon
Physical Properties .......................................... 2-37
Concentration Units Based On
Chemical Properties......................................... 2-38
Units Used for Properties ...................................... 2-41
Hypothetical Salt Combinations .............................. 2-45
Solubility Calculations .............................................. 2-46
Composition Diagrams ............................................. 2-47
Quality Control .............................................................. 2-47
Anion/Cation Balance ............................................... 2-47
Calculated vs. Measured TDS ................................... 2-48
Calculated vs. Measured Specific Gravity ............... 2-49
Methods Using Electrolytic Conductivity ................ 2-50
Regions of pH and Carbonate Species.................... 2-53
Solubility Calculations .............................................. 2-54
Replicates, Standards, and Spiked Samples .......... 2-54
OIL-IN-WATER ANALYSIS................................................ 2-54
Free Oil vs. Dissolved Oil ............................................. 2-55
Dissolved Oil .............................................................. 2-55
Free Oil ....................................................................... 2-57
Sampling ........................................................................ 2-58
Analytical Procedures .................................................. 2-59
EPA Method 413.1. Oil and Grease. Total,
Recoverable (Gravimetric, Separator Funnel
Extraction) ........................................................... 2-60
EPA Method 413.2. Oil and Grease. Total
Recoverable (Spectrophotometric, Infrared) .... 2-60
EPA Method 418.1 Petroleum Hydrocarbons. Total
Recoverable (Spectrophotometric, Infrared) 2-61
API Recommended Practice for Analysis of
Oilfield Waters, API RP 45 .................................. 2-62
Quality Control .............................................................. 2-62
SUSPENDED SOLIDS ...................................................... 2-64
Sampling and Analytical Procedures .......................... 2-64
National Association of Corrosion Engineers
Standard Test Method TM 0173-84 .................... 2-65
X-Ray Diffraction Analysis ........................................ 2-66
X-Ray Fluorescence Analysis ................................... 2-66
Scanning Electron Microscopy ................................ 2-67
Other Procedures ...................................................... 2-67
Quality Control .............................................................. 2-67
REFERENCES................................................................... 2-69
GLOSSARY ....................................................................... 2-71
Water Treatment Handbook iii

CHAPTER 3: OIL/WATER SEPARATION ............ 3-1
PREFACE ............................................................................ 3-3
WATER QUALITY REQUIREMENTS .................................. 3-3
Injection Requirements .................................................. 3-3
Disposal Requirements .................................................. 3-5
Discharge Requirements................................................ 3-6
EOR Requirements ......................................................... 3-6
OILY WATER TREATING EQUIPMENT .............................. 3-8
General ............................................................................ 3-8
DEHYDRATION SEPARATORS ........................................ 3-10
SETTLING SKIM TANKS .................................................. 3-11
COALESCERS .................................................................. 3-12
Loose-Media Coalescers .............................................. 3-12
Fixed-Media Coalescers ............................................... 3-13
PLATE PACKS (INCLUDING SP-PACK AND
VERTICAL TUBE COALESCER) ............................... 3-15
FLOTATION ....................................................................... 3-16
Dissolved Gas Flotation ............................................... 3-17
Induced or Dispersed Gas Flotation ........................... 3-18
Mechanical IGF Units ................................................ 3-19
IGF Selection ................................................................. 3-20
Eductor IGF Units ......................................................... 3-20
Dissolved Gas Flotation Units vs. IGF’s .................. 3-21
Factors Influencing Flotation Cell Performance ..... 3-21
Gas Concentration ................................................. 3-22
Salinity of Produced Water .................................... 3-22
Inlet Oil Concentration ........................................... 3-23
Temperature ............................................................ 3-23
Flotation Aids and Surface Chemistry .................. 3-24
HYDROCYCLONES .......................................................... 3-24
Design and Principle of Operation .............................. 3-25
Static Hydrocyclones ................................................ 3-25
Dynamic Hydrocyclones ........................................... 3-26
Factors Influencing Performance .......................... 3-26
Typical Performance ..................................................... 3-28
Static Hydrocyclones ................................................ 3-28
Dynamic Hydrocyclones ........................................... 3-29
Applications to Date ..................................................... 3-29
Hydrocyclone Selection ............................................... 3-30
FILTERS ............................................................................ 3-31
Downflow Sand/Multimedia Filters ............................. 3-31
Nutshell Filters .............................................................. 3-31
THE INTEGRATED TREATMENT SYSTEMS APPROACH
TO COST-EFFECTIVE WATER TREATMENT ........... 3-32
PROCESS/EQUIPMENT SELECTION .............................. 3-35
MONITORING AND MEASUREMENT .............................. 3-37
General .......................................................................... 3-37
On-Line Methods .......................................................... 3-37
Infrared Light Scattering ........................................... 3-37
Infrared Light Absorption ......................................... 3-38
iv Water Treatment Handbook

Direct Absorption ................................................... 3-38
Solvent Extraction/Infrared Absorption ................... 3-39
Ultraviolet Absorption ............................................... 3-39
Laboratory Methods ..................................................... 3-40
REFERENCES................................................................... 3-41
GLOSSARY ....................................................................... 3-43
APPENDIX ......................................................................... 3-45
CHAPTER 4: FILTRATION ................................... 4-1
CHAPTER 5: SCALING AND
WATER FORMED SOLIDS .............................. 5-1
INTRODUCTION ................................................................. 5-3
SCALES AND THEIR PREDICTION ................................... 5-3
Common Scales .............................................................. 5-4
Calcium Carbonate ...................................................... 5-4
Calcium Sulfate............................................................ 5-4
Barium Sulfate ............................................................. 5-7
Strontium Sulfate......................................................... 5-8
Iron Compounds .......................................................... 5-8
Predicting Scale Formation ........................................... 5-9
Solubility Calculations ................................................ 5-9
Saturation Index .......................................................... 5-9
Calcium Carbonate Scaling Calculation .................. 5-10
Calculations of Sulfate Scaling Tendencies ............ 5-11
Computer Programs for Scaling Tendency
Calculations ......................................................... 5-11
SCALE PREVENTION....................................................... 5-12
Avoid Mixing Incompatible Waters .............................. 5-12
Adjusting Brine Chemistry .......................................... 5-13
Water Dilution ............................................................ 5-13
pH Control .................................................................. 5-13
Removal of Scale-Forming Gases............................ 5-13
Removal of Scale-Forming Ions ............................... 5-13
Addition of Chelators ................................................ 5-14
Environmental Controls ............................................... 5-14
SCALE INHIBITORS ......................................................... 5-14
Principle of Use............................................................. 5-14
Types of Scale Inhibitors.............................................. 5-15
Selection of Scale Inhibitors for Further Evaluation . 5-17
Scale Inhibitor Evaluation — Laboratory Performance
Tests ........................................................................ 5-18
Scale Inhibitor Testing — Field Performance
Monitoring ............................................................... 5-19
Application of Scale Inhibitors .................................... 5-20
Batch Treatments ...................................................... 5-20
Continuous Recirculation ......................................... 5-21
Scale Inhibitor Squeeze — Product Selection ........ 5-22
Squeeze Treatment Design ....................................... 5-24
SCALE REMOVAL ............................................................ 5-28
Scale Identification ....................................................... 5-28
Water Treatment Handbook v

Chemical Removal ........................................................ 5-29
General Comments .................................................... 5-29
Calcium Carbonate .................................................... 5-30
Calcium Sulfate.......................................................... 5-31
Barium Sulfate ........................................................... 5-32
Iron Compounds ........................................................ 5-33
Mechanical Removal ..................................................... 5-34
Scale Removal From Surface Lines ......................... 5-34
Downhole Cleanout ................................................... 5-34
REFERENCES................................................................... 5-37
GLOSSARY ....................................................................... 5-43
APPENDIX ......................................................................... 5-47
CHAPTER 6: CORROSION EFFECTS ................ 6-1
INTRODUCTION ................................................................. 6-3
CORROSION AFFECTS WATER QUALITY ....................... 6-3
GENERAL CORROSION .................................................... 6-4
LOCALIZED CORROSION ................................................. 6-5
Pitting............................................................................... 6-5
Crevice Corrosion ........................................................... 6-6
Galvanic Corrosion ......................................................... 6-6
CORROSION RATE ............................................................ 6-7
Effect of Dissolved Gases .............................................. 6-7
Effect of Dissolved Solids .............................................. 6-9
Effect of Oil and Grease ................................................. 6-9
Effect of Flow and Suspended Solids ......................... 6-10
Effect of Water Treating Chemicals ............................. 6-10
Effect of pH.................................................................... 6-11
Effect of Temperature ................................................... 6-11
Effect of Deposits ......................................................... 6-12
MONITORING .................................................................... 6-12
Inspection ...................................................................... 6-13
Coupons and Spools .................................................... 6-13
Iron Counts.................................................................... 6-14
Electrical Resistance .................................................... 6-14
Linear Polarization........................................................ 6-15
Galvanic Probes ............................................................ 6-15
Hydrogen Monitors ....................................................... 6-16
Ultrasonic Surveys ....................................................... 6-16
CORROSION PREVENTION............................................. 6-16
Inhibitors ....................................................................... 6-18
Alloys ............................................................................. 6-18
Plastics and FRP’s ........................................................ 6-21
Cathodic Protection ...................................................... 6-21
Removal of Dissolved Gases ....................................... 6-22
Coatings ........................................................................ 6-24
Linings ........................................................................... 6-24
Pigging and Scraping ................................................... 6-25
GENERAL REFERENCES ................................................ 6-27
NACE Publications ....................................................... 6-27
Books ............................................................................. 6-27
vi Water Treatment Handbook

APPENDIX A
INDEX TO CHEVRON
CORROSION PROTECTION MANUAL ..................... 6-29
APPENDIX B
INDEX TO CHEVRON COATINGS MANUAL............. 6-31
APPENDIX C
INDEX TO CHEVRON PIPELINE MANUAL ............... 6-33
CHAPTER 7: MICROBIOLOGICAL PROBLEMS
IN PRODUCTION OPERATIONS ..................... 7-1
INTRODUCTION ................................................................. 7-3
MICROBIOLOGICAL ACTIVITY CAUSES PROBLEMS .... 7-3
Plugging and Fouling ..................................................... 7-4
Microbial Reservoir Souring .......................................... 7-4
Microbiologically Influenced Corrosion ....................... 7-5
Environmental Concerns ............................................... 7-6
Chemical Consumption .................................................. 7-7
Water Chemistry ............................................................. 7-7
Formation Damage ......................................................... 7-8
MICROBIOLOGICAL ENERGETICS .................................. 7-8
MICROORGANISMS INVOLVED IN MICROBIAL
PROBLEMS ................................................................ 7-11
Sulfate-Reducing Bacteria — SRB .............................. 7-11
Slime-Forming Bacteria ............................................... 7-16
Acid Producing Bacteria — APB ................................. 7-17
Iron Bacteria .................................................................. 7-17
Sulfur-Oxidizing Bacteria ............................................. 7-18
Planktonic vs. Sessile Bacteria ................................... 7-18
Planktonic Bacteria ................................................... 7-18
Sessile Bacteria ......................................................... 7-19
Bacteria Classified According to Habitat.................... 7-19
DETECTION OF BACTERIA ............................................. 7-20
Sampling Methods for Bacteria ................................... 7-21
Planktonic Bacteria ................................................... 7-22
Sessile Bacteria and Biofilms................................... 7-22
Test Procedures for Bacterial Types ........................... 7-23
Culturing Methods ..................................................... 7-23
Broth Bottles ........................................................... 7-25
Solid Culture Media ................................................ 7-26
Pour-Plate Method .................................................. 7-27
Spread-Plate Method .............................................. 7-27
Melt Agar Tube Method .......................................... 7-27
Direct Methods ........................................................... 7-28
ATP Assay ............................................................... 7-28
Epifluorescence/Cell Surface Antibody Methods. 7-29
APS Reductase Antibodies Method ...................... 7-29
Phospholipid Signature ......................................... 7-30
Radio-Respirometry ............................................... 7-30
Chemical Analysis .................................................. 7-31
Hydrogenase Enzyme Detection ........................... 7-32
Water Treatment Handbook vii

Sulfur Isotope Differentiation Method ..................... 7-32
Comparison of Field Kits for SRB ............................ 7-33
CONTROL OF BACTERIAL ACTIVITY ............................ 7-34
Bacterial Control by Mechanical Design .................... 7-35
Bacterial Control by Physical Cleaning ...................... 7-35
Bacterial Control by Chemical Cleaning..................... 7-36
Bacterial Control by Ultraviolet Radiation .................. 7-38
Bacterial Control by Biocides ...................................... 7-38
Types of Biocides ...................................................... 7-38
Biocide Selection .......................................................... 7-41
Time-Kill Procedure for Biocide Effectiveness .... 7-44
Estimation of Biocide Batch Frequency ............... 7-46
Factors Affecting Biocide Effectiveness ............... 7-47
Sessile Samples for Biocide Testing ....................... 7-49
Laboratory Recirculation Loops............................ 7-50
Field Side-Stream Test Loops ................................ 7-50
Field In-Line Probes ............................................... 7-52
Biocide Treatment Procedures ................................. 7-53
Biocide Toxicity ......................................................... 7-53
MONITORING METHODS FOR MICROBIAL ACTIVITY .. 7-55
REFERENCES................................................................... 7-57
GLOSSARY ....................................................................... 7-59
CHAPTER 8: CHEMICAL INJECTION ................. 8-1
INTRODUCTION ................................................................. 8-3
NATURAL COMPONENTS OF OILFIELD WATERS.......... 8-4
TYPES AND FUNCTIONS OF OILFIELD CHEMICALS ..... 8-5
General ............................................................................ 8-5
Scale Inhibitors ............................................................... 8-6
Corrosion Inhibitors ....................................................... 8-6
Biocides ........................................................................... 8-7
Emulsion Breakers ......................................................... 8-7
Reverse Breakers............................................................ 8-8
Coagulants and Flocculants .......................................... 8-8
Antifoamers ..................................................................... 8-9
Surfactants ...................................................................... 8-9
Paraffin Treating ............................................................. 8-9
Oxygen Scavengers ...................................................... 8-10
Sulfide Scavengers ....................................................... 8-10
Hydrate Inhibitors ......................................................... 8-11
Gas Dehydration Chemicals ........................................ 8-11
Well Stimulation Chemicals ......................................... 8-11
Acids ........................................................................... 8-11
Fracturing Fluids ....................................................... 8-12
Additives .................................................................... 8-12
Workover Fluids ............................................................ 8-13
Weighted Brines ........................................................ 8-13
Corrosion Inhibitors (see list above) ....................... 8-13
Biocides (see list above) ........................................... 8-13
Oxygen Scavengers (see list above) ....................... 8-13
Viscosifiers ................................................................ 8-13
viii Water Treatment Handbook

IONIC CHARACTER OF OILFIELD INJECTED
CHEMICALS ............................................................... 8-14
CHEMICAL INTERACTIONS ............................................ 8-14
Cation/Anion Interactions Resulting in
Scale Formation ..................................................... 8-15
Surfactant Interactions ................................................. 8-18
Demulsifier/Reverse Demulsifier Interactions ........ 8-19
Description of Demulsifier Chemistry ................... 8-19
Treatment Problems and Interactions ................... 8-20
Demulsifiers ......................................................... 8-20
Reverse Demulsifiers .......................................... 8-21
Other Surfactant Interactions ................................... 8-23
Biocide Reactions ......................................................... 8-24
Strong Acid Reactions ................................................. 8-24
SOME DO’S AND DON’TS WITH RESPECT TO
CHEMICAL INTERACTIONS ...................................... 8-25
GLOSSARY ....................................................................... 8-27
CHAPTER 9: WATER/FORMATION
ROCK INTERACTIONS ................................... 9-1
INTRODUCTION ................................................................. 9-3
Mechanisms of Formation Permeability Damage ........ 9-3
Formation Clay Deflocculation and Migration .......... 9-3
Formation Clay Structural Expansion ....................... 9-4
Mica Alteration ................................................................ 9-5
Differential Dissolution .................................................. 9-6
Dissolution and Reprecipitation .................................... 9-7
Precipitation .................................................................... 9-8
Identifying Potential Formation Permeability
Damage ..................................................................... 9-8
Water and Rock Analyses .............................................. 9-9
Proper Salts and Concentrations ................................ 9-10
PREVENTING FORMATION DAMAGE IN THE FIELD .... 9-13
REFERENCES................................................................... 9-15
GLOSSARY ....................................................................... 9-17
APPENDIX ......................................................................... 9-19
CHAPTER 10: HANDLING SEPARATED
WASTES ........................................................ 10-1
INTRODUCTION ............................................................... 10-3
ORIGIN OF WASTE STREAMS ........................................ 10-3
FACTORS IN HANDLING SEPARATED WASTE
STREAMS ................................................................... 10-9
Minimizing Arbitrary Recycling ................................... 10-9
Incorporating Point-Source Treating Into the
System Design...................................................... 10-10
Concentration of Separated Wastes ......................... 10-11
DISPOSAL OF THE SEPARATED WASTES .................. 10-14
Waste Disposal and the Environment ....................... 10-15
Environmental Regulations and Regulators ......... 10-16
Federal ...................................................................... 10-16
Water Treatment Handbook ix

State (California) ...................................................... 10-17
Local ......................................................................... 10-17
Federal ...................................................................... 10-17
State (California) ...................................................... 10-17
Classification and Relative Disposal of Wastes ... 10-18
REFERENCE ................................................................... 10-22
GLOSSARY ..................................................................... 10-23
APPENDIX ....................................................................... 10-25
INDEX ...................................................................................... I-1
x Water Treatment Handbook

C H A P T E R
Introduction
Chapter 1: Introduction 1-1

1-2 Water Treatment Handbook
BACKGROUND
Handling and treating of water in an oil field are impor-
tant factors for successful, economical operation of the
field. These factors become especially important as fields
mature and the produced water cuts increase to levels
where the volume of water treated, reinjected, or dis-
posed of can be 10 to 50 times the volume of oil pro-
duced. Even in new, low-water-cut fields, at least as
much water as oil produced may have to be treated and
injected to maintain reservoir pressure and to control
voidage. Enhanced oil recovery (EOR) projects require
good-quality water for injection for three reasons:
1. To raise and maintain reservoir pressure.
2. To act as the carrier for the chemicals designed to free
oil from pore spaces and/or improve the sweep
efficiency.
3. To be converted to steam and transfer heat needed to
lower viscosity and mobilize heavy crudes.
Water treating systems present some special challenges.
The greatest challenge relates to the fact that oilfield Water treating presents
waters change continually in terms of volume and chemi-
special challenges
cal and physical properties. Also, because of its reactivity
(corrosivity, scaling tendency, microbiological activity, because oilfield waters
etc.), water causes the treating system itself to change change continually in
with time. volume and chemical and
The following discussion illustrates some problems physical properties.
involving water treating systems.
Existing Systems Designed for Old

Waterfloods
The system probably was designed and installed long
before the current operating staff became involved.
These persons are not familiar with the details and objec-
tives of the system. The water has changed and the
system has gone through multiple modifications. The
system may not be able to handle the present water
needs. A decision on making further modifications or
designing a new system must be made. Whether the
system is modified or rebuilt, it will probably have to
handle increasing volumes of water. Should the new

design be similar to the existing system? Or should it
incorporate new technology? The problems with the
present system must be diagnosed so that they are not
incorporated into the new design or modifications. The
possibility of a future EOR application may need to be
considered. Input from geologists and from design and
construction, gas and chemical, reservoir, and production
engineers is needed for many of these decisions.
A New System To Be Installed for a New

Waterflood or EOR Project
A decision must be made about using a design that the
operating people are familiar with or trying new technol-
ogy. Again, input from geologists and from design and
construction, gas and chemical, reservoir, and production
engineers is needed to prevent repeating past errors; to
consider capital, operating, and other costs; to anticipate
future requirements; to incorporate reservoir factors; and
to consider environmental concerns.
OILFIELD WATER REQUIRING TREATMENT

Water Sources
The waters handled in producing operations vary from
field to field and during the life of any particular field.
Water sources can be grouped into three general cate-
gories: oil or gas production, source wells, and open
Three categories of water sources. Depending on the life of a waterflood, produced
sources are from oil or gas water is made up of a combination of natural formation
production, source wells, waters and injected water, which itself may be a mixture
of produced water, source well water, and waters from
and open sources.
several open sources. Consequently, the proportions of
these waters change during the life of the field. Likewise,
salinity and other properties of the produced water
change. Water from source wells is generally produced
from aquifer formations separate from the reservoir
being flooded.
Open water sources include oceans and bays, rivers,
canals, and lakes, as well as rain runoff collected on
onshore fields and deck runoff from offshore platforms.
Other sources of open water are waste waters generated
by oilfield operations like filter backwash, induced gas

flotation skimmings, pit water, and tank bottoms. These
waters, although only a small fraction of the total water
used in a field operation, are particularly detrimental to
water handling and treatment because of their chemistry.
Water chemistry is complicated by any chemicals added,
oxygen dissolution, and by-products of scale, corrosion,
etc. They also usually contain high concentrations of
suspended solids, oil, and/or sludge.
Oilfield waters are complex mixtures that change with
time and location. They require specific handling and
treatment according to their intended use.
Characteristics of Waters That Affect Their

Handling and Treatment
The following lists give important characteristics of
waters from the three sources discussed above that must
be considered in their handling and treatment, whether
for injection or for disposal.
Produced Waters:
1. Generally are corrosive as a result of elevated tem-
perature and high salinity. Potential problems from
handling produced waters
2. Usually contain dissolved gases (oxygen, carbon
dioxide, and/or hydrogen sulfide), which increase include their corrosivity,
corrosiveness. variable composition,
3. Will vary in terms of physical and chemical properties tendency to carry or form
with time, location, and field operations (wells shut solids, and oil content.
in, brought on line, being worked over, stimulated,
etc.).
4. Typically contain dissolved iron, which causes the
water to be chemically unstable, leading to scale and/
or precipitate formation and interaction with other
waters or chemical additives.
5. Contain suspended solids, including clays and other
formation fines, iron sulfides, paraffins, and asphal-
tenes that are coated with oil, which causes them to
agglomerate.
6. Contain various amounts of free oil and dissolved
organic compounds.

7. Are or readily become microbiologically active owing
to the presence of dissolved organics, reducible oxy-
gen sources, and other conditions required for bio-
logical growth.
8. Contain sufficient levels of dissolved solid to become
sources of scaling solids caused by commingled
waters or changes in temperature, pressure, or flow
rate or direction.
Source Well Waters:

1. Tend to be less corrosive because they contain little or
no dissolved oxygen.
2. May contain dissolved carbon dioxide or hydrogen
sulfide.
3. Have salinities and temperatures that cover wide
ranges.
4. Generally have a low suspended solids content (with
proper source well completion).
5. Tend not to be microbiologically active.
6. May have scaling tendencies generally caused by
commingling of incompatible waters, affected by
temperature, pressure, or flow changes.
Open Waters:
1. Are very corrosive because of high levels of dissolved
oxygen.
2. Can contain anywhere from low to very high
concentrations of suspended solids that may be or-
ganic or inorganic and can vary seasonally and/or
with the oilfield operation that is the water source.
3. May have variable chemistry, depending on the water
source.
4. Often are microbiologically active and potential
sources of bacterial contamination in surface facilities,
wellbores, and waterflooded formations.
5. May contain significant nutrients and reducible oxy-
gen to facilitate bacterial growth.

6. Are generally the source of sulfate ion to form sulfate
scales when commingled with waters containing
barium, strontium, or calcium ions.
WATER TREATMENT OBJECTIVES

There usually are two general objectives for treating
water in an oil field. The first is to prepare the water for
injection. This could be in a conventional waterflood, as
a requirement in an EOR project, or for subsurface dis-
posal. In all three cases, filtration may be required to
minimize wellbore plugging caused by suspended solids
in the injected water. In addition, treatment may be
needed to reduce free oil, to remove oxygen or other
dissolved gases to control corrosion, to change the pH or
water chemistry to allow chemicals to be added for EOR
purposes, or to reduce the water hardness to prepare the
water as steam generator feed. Subsurface injection for
disposal may be required because of the imposition of a
“zero discharge” environmental regulation.
The second general objective is to prepare an oilfield
water for surface disposal by discharge to an ocean, a
river, a canal, or a municipal sewer system. As discharge
regulations and questions of liability become increasingly
strict, surface discharge will become less common (al-
most the exception).
There are several additional objectives for treating oil-
field waters. Actually, these objectives are not indepen-
dent of the general objectives.
1. To control the detrimental effects of corrosion, scale
formation, and biological activity on piping, tanks, Two general objectives
other surface equipment and facilities, and downhole for treating water in an oil
well equipment.
field are to prepare the
2. To recover oil and revenue lost because of ineffective water for injection or
oil/water separation.
disposal.
3. To provide the treatment required to use a water for
EOR.
4. To meet the nonroutine treatment requirements for
handling “special” oilfield waters (added to the
injected water or disposed of separately). These
special waters include:

• Tank bottoms, sand dumps, induced gas flotation
skimmings, filter backwash, and pit waters.
• Spent water-softener regeneration brine.
• Glycol/water mixtures from gas dehydration.
• Desalter waste water.
• Water from pipe scraping (pigging) operations.
• Backflow water from wells following stimulation
treatments.
• Field or platform rain runoff.
• Platform deck wash water.
These special waters are best treated as small-volume
“point sources” before being allowed to commingle
together or with the main injection water. When com-
mingled, their associated high solids and chemical load-
ings have an extreme negative impact on water quality.
When handled separately, the special chemical treatment
and solids removal requirements of these waters are met
more effectively to minimize this negative impact. In
addition, flow rates, chemistries, and solids loadings of
these waters fluctuate greatly. Handling them separately
(with special tanks, chemical additions, etc.) tends to
level out the fluctuations before they affect the combined
waters.
POSSIBLE TREATMENTS REQUIRED TO

ACHIEVE OBJECTIVES
A variety of processes are available for treating oilfield
Everything done to the waters to achieve the objectives described above. The
water upstream affects water treating system may be as basic as adding chemi-
cals to change the water chemistry. At the other extreme,
everything that happens
the system could require the combination of chemical
downstream. A total additions, tanks to provide required residence time,
system approach must be water softening, phase separation (filtration, oil removal),
taken. process regeneration (filter backwash, softener regener-
ation), and additional cleanup steps to treat waste
streams (filter backwash, tank or flotation skimmings,
spent regeneration brine, pit water) for disposal. Every-

thing done to the water upstream affects everything that
happens downstream. A total system approach must be
taken.
A total system approach considers the interactions of the
separate parts of the system and their effect on the whole
system. For example, a surfactant chemical added to the
backwash to improve filter-bed cleanup could be an
emulsion stabilizer. If the backwash water is returned to
the system upstream of the oil/water separation equip-
ment, the efficiency of that equipment will be lost. Or
maximizing water removal from crude by adding chemi-
cals may increase the oil content in the water to a level
that fouls the filter media and destroys filter efficiency.
Treatment Objective — Injection
Filtration
1. Economical water injection requires that lives of the
injection wells to be maximized. Economical justifica- Economical justification
tion of filtration must consider more than the capital
for filtration must
and costs of the filters. Filtration costs must be com-
pared with costs for drilling new wells, working over consider its costs versus
or redrilling plugged wells, or stimulating partially the benefits of increased
plugged wells. An effective stimulation treatment injector life and improved
does more than just increase injectivity one time only.
waterflood sweep
The number of times an injector can be stimulated
successfully must also be considered. This includes efficiency.
the detrimental effects of acids on well equipment and
the effect of the treatment on injection profile. There
is also the question of whether permits may be se-
cured from regulatory agencies to drill new wells.
Regulations are becoming more restrictive for dis-
posal wells. A proper decision to install filters must
have input from reservoir, production, gas and chemi-
cal, and design and construction engineers, as well as
from environmental coordinators.
2. The need to maintain profile control (sweep) by
removing the suspended solids that plug tight zones
is another factor to include in considering filtration.

3. As a general rule, a clean water handling system
(with minimum suspended solids) is required to
maintain good water quality for injection throughout
the life of a waterflood.
• Solids that drop out in pipes, tanks, process equip-
ment, injection lines, and tubing hinder corrosion
and scale inhibitor and biocide effectiveness.
Thus, they reduce water quality (further accumu-
lation of scale, corrosion, and biological reaction
products).
• Accumulation of solids in lines also causes water
quality to decline as water flows through the
system and solids are dislodged owing to pressure
surges, flow-rate variations, or water chemistry
changes.
• Poor water quality, caused by ineffective water
treatment in the early life of a waterflood with
resulting accumulations of solids in the injection
lines and tanks, leaves the system so dirty that
subsequent installation of filters and other water
treating equipment often cannot overcome the
deleterious effect that the dirty system has on
water quality. At that point, it is usually too late,
unless special steps are taken to clean up the
injection water lines and/or to install filters at the
wellheads.
• Similarly, a water handling system should be kept
clean in anticipation of later EOR projects where
water- quality requirements may be even more
stringent. These earlier solids accumulations tend
to slough off when they come into contact with
surface-active chemicals (surfactants), carbon
dioxide, miscellars, low-salinity water, and high
temperatures associated with EOR.
Removal of Free Oil from Water

1. Free oil in water often is associated with sludge and
agglomerated solids (iron sulfides, other scales, for-
mation fines, paraffins, and asphaltenes) that plug
injection wells.

2. Free oil interferes with scale and corrosion inhibitors
and biocides, resulting in poor water quality.
3. Oil and sludge damage the efficiency of filtering.
4. Oil and sludge around an injector wellbore reduce
relative permeability to water.
Effective Corrosion, Scale, and Biological

Control
1. The by-products of poor control of corrosion, scale,
and biological activity reduce water quality (both
chemistry and suspended solids) and cause injector
plugging by solids and interactions between the
water and the formation rock.
Separate Treatment of Waters

1. The following are general rules for treating different
oilfield waters:
• Waters of different qualities (in terms of both
chemistry and suspended solids) should not be Waters of different
mixed before treatment (or before potential inter- qualities should be
actions are identified). The quality of the resulting
treated separately as a
combined water will be no better than that of the
worst water in the mixture. “point source.”
• Treat each water separately as a “point source” of
suspended solids, corrosion, scale, and bacteria.
• If following the above steps is impossible and the
waters are mixed before treatment, sufficient
residence time must be provided (1) to allow the
mixed water to come to chemical equilibrium for
all interactions to occur and (2) to stabilize the
water to maximize particulate formation before
filtration.
• Once treated by chemical or mechanical processes,
waters must not be allowed to come into contact
with air (oxygen). Contact with oxygen causes
additional particulates (iron compounds particu-
larly) to form. This is especially a problem with
produced water. Benefits of corrosion control and
filtration are nullified if contact with oxygen
occurs downstream from the filters (from

unblanketed tanks, influx of oxygenated water,
leaking pump seals, use of air to scour filter me-
dia, etc.).
EOR Treatment Considerations in Addition to

Those Listed Above
1. Added chemicals or changes made in water chemistry
to meet an EOR objective may interfere or interact
with chemicals added for other purposes. The result
is a loss of water quality at a time when an improve-
ment in water quality is needed for a successful EOR
project. Such interferences include but are not limited
to:
• Surfactants counteracting (e.g., a wetting agent
stripping off a filming corrosion inhibitor).
• Polymers and surfactants interacting.
• Biocides (aldehyde type) reacting with a polymer.
• Scale and corrosion inhibitors and biocides becom-
ing ineffective at low-pH (CO2 injection) condi-
tions.
Note that other state and federal regulations must be
met, in addition to considerations for treating a water for
injection. In fact, the regulations themselves may be the
motivation for injection.
Treatment Objective — Surface Disposal

Surface disposal is controlled by the conditions specified
in a discharge permit obtained from a state or federal
regulatory agency. The permit sets the environmental
discharge standards and/or limits including but not
limited by:
1. The “oil and grease” content (defined by the method
specified for measuring the concentration of hydro-
carbons/organics in the water).
2. The “toxicity” (in turn defined by the toxic effect of
the water on the mortality of one or more biological
species based on a test method acceptable to the state
or federal agency and specified in the discharge
permit).

3. A list of effluent components with maximum allow-
able concentrations (absolute or relative to ambient).
• Effluent components include (in addition to oil
and grease content and toxicity) suspended solids,
oxygen demand, sulfides, chlorine, pH, ammonia,
radioactivity, metals, and organics.
4. Temperature.
5. Volume of water discharged.
Meeting these standards may require additional oil
removal and other equipment besides that needed for
injection. In some cases, special processes, such as acti-
vated carbon adsorption, have been required to remove
organics (e.g., phenols). Drinking water standards,
groundwater protection, and air pollution controls are
becoming more important in state and federal surface
discharge permitting processes.
Additional Water Treatment Objectives
Corrosion, Scale, and Biological Control

1. An effective water treating program to control prob-
lems caused by corrosion, scale, and bacteria must be It is important to control
based on two equally important perspectives. Both corrosion, scale, and
the equipment and the water must be considered.
bacteria growth both to
First, all the field equipment — including system
piping, pumps, tanks, process equipment (separators, protect equipment and
filters, deaerators, flotation units, filters, etc.), well- maintain good water
heads, and tubing — need to be protected from the quality.
deleterious effects of all three problems. Second, the
interrelated effects of corrosion, scale, and bacteria on
the quality of water flowing through the system must
be considered. For example, a corrosion rate that is
acceptable in terms of equipment life may be
unacceptable in terms of its effect on water quality.
Dissolved iron released by corrosion reactions comes
out of solution to form particulates and scale when it
comes into contact with air or H2S. Suspended solids
content also is increased by scale formation and
biological activity.

2. The chemicals added to the water to control corro-
sion, scale, or biological activity may not be compat-
ible. Included are surfactants of all types, polymers,
reducing agents, and oxidizing agents. The combina-
tion of chemicals used and the points where they are
added must be evaluated carefully.
Recovery of Free Oil in Water and Lost

Revenue
1. The value of crude oil is an important factor in the
The value of the crude oil economics of recovering additional free oil from
recovered can more than produced water. The increased revenue from the oil is
compared with the costs of installing additional oil/
pay for the recovery
water separation equipment or improving existing
equipment, plus improve separation equipment through design or chemical
the water quality. changes. Even the choice of a filter design can be
affected by the filter ’s ability to recover oil and to
remove suspended solids.
2. Some equipment or operation changes to improve oil
separation include the use of coalescers, improved
tank design to increase residence time for better oil/
water separation, increased gas flotation capacity, a
change in coalescing or coagulation chemical type or
point of addition, and use of other types of separa-
tors.
Special Treatment for EOR Requirements

1. To add special EOR chemicals to the injection water or
to use the water for steam generation, softening,
reducing the alkalinity, or raising the pH of the water
may be necessary.
2. Softening the water may require the oil and sus-
pended solids content of the water to be reduced
further to prevent fouling of the softener resin bed
and solids deposition on steam generator tubes.
3. The added EOR chemicals may affect water chemistry
and pH so much that the corrosion and scale inhibi-
tors must be changed to be effective at the new condi-
tions. Similarly, the biocide (particularly an oxidizing
type) will no longer be usable in the presence of

polymers added for EOR. Also, polymers will in-
crease the biological activity of the system, requiring
re-evaluation of biocides.
4. Finally, added surfactants and pH changes for EOR
will dislodge scales and other deposits from pipes
and vessels. Secondary filtration or filter modifica-
tions will be needed.
Nonroutine Treatments of “Special” Oilfield

Waters
1. As stated earlier, these “special” waters (tank bot-
toms, flotation skimmings, pit waters, spent softener
regeneration brine, etc.) are best treated as small-
volume “point sources.” As such, the treatment of
each water must be tailored to its specific chemical
and physical properties and destination (handled
separately or mixed with other waters for injection or
open discharge). Consequently, a complete spectrum
of mechanical and chemical treatment procedures can
be involved.
OILFIELD TREATMENT METHODS AND

EQUIPMENT
The following outlines mechanical and chemical methods
and equipment used to treat oilfield waters to achieve the
objectives discussed above. The length of the list illus-
trates the large number of options available. Details are
given in succeeding chapters.
1. Mechanical (Physical) Methods With or Without
Chemicals and Heat Added
A. Oil/Water Separation
1. Free-water knock-out vessels
2. Two- and three-phase separators
3. Skimmer tanks and vessels
4. Pits
5. Coalescers
6. Combinations of coalescers and skimmers

7. Precipitators
8. Flotation units
a. Dissolved gas
b. Dispersed gas
9. Disposal piles (on platforms)
10. Hydrocyclones — liquid/liquid
a. Static
b. Dynamic
B. Filtration (suspended solids)
1. “Sand” filters
a. Upflow
b. Downflow
c. Duoflow
d. High and low rate
e. Single and multimedia
f. Coalescing
g. Horizontal and vertical
2. Precoat filters (diatomaceous earth)
3. Cartridge filters
a. Disposable cartridge
b. Backwashable
4. Fluidized bed, regeneration-type filters
a. Walnut-shell media
b. Pecan-shell media
5. Hydrocyclones — solid/liquid
6. Flotation units (see Item A-1-h)
7. Dry cake filters
a. Precoat and body feed on wire-wrap screen
1. Diatomaceous earth
2. Pearlite
3. Walnut and pecan shells
b. Rotary drum filters
c. Plate-and-frame filters
C. De-aeration (oxygen removal)

1. Gas stripping
a. Nitrogen
b. Fuel gas
c. Flue gas
d. With or without packing or plates
2. Vacuum
D. Gas Stripping to Remove H2S
2. Chemical Methods (Involve Changes in Water Chem-
istry)
A. Surfactant Addition
1. Emulsion breakers for oil/water separation
2. Filter cleaners in backwash water
3. Relative permeability modifiers to improve
water injectivity
4. De-aerator antifoamers and defoamers
5. Some biocides
6. Corrosion inhibitors
7. Scale inhibitors
8. Oil-coalescing surfactants
B. Oxygen Scavenging
1. Various sulfides ( SO 2 , HSO −32 , SO −3 2 )

C. Biocide Addition
1. Oxidizers
a. Chlorine
b. Chlorine dioxide
2. Aldehydes
3. Quaternary amines
4. Mixed aldehyde/amines
D. Corrosion-Inhibitor Addition
1. Filming amines
2. Water dispersible or soluble

E. Scale-Inhibitor Addition
1. Phosphates
2. Phosphonates
3. Mixtures
F. Changing pH
1. Decrease
a. Adding SO2 to control scale
b. CO2 flooding (EOR)
c. Reducing alkalinity
d. Decreasing solubility of dissolved organic
compounds
2. Increase
a. Neutralizing weak acid softener spent
regenerant
b. Removing of H2S or CO2 from water
c. Neutralizing water for discharge
d. Caustic flooding (EOR)
G. Controlling Cation Concentration
1. Softening
a. Exchange divalent ions for monovalent ions
b. Lime soda
2. Direct addition of salts
a. Increase potassium concentration
b. Increase salinity
3. Mixing waters of different salinities
H. Adsorption of Dissolved Organics on Activated
Charcoal
I. Addition of Polymers
1. Filteraids
2. Coagulants
3. Polymer flood (EOR)

GLOSSARY
incompatible waters — waters when mixed form solid
precipitates.
total system approach — considering effects in the entire
treatment system.

C H A P T E R
Analytical and Test Methods
Chapter 2: Analytical and Test Methods 2-1

WATER ANALYSIS
Reasons for Water Analysis

Chevron produces roughly 10 times as much water as
crude oil. This water causes many problems in produc-
ing operations and in treating for use or disposal. Water-
related problems include:
• Bacterial activity.
• Corrosion.
• Emulsions.
• Formation damage.
• Environmental restrictions.
• Equipment fouling.
• Formation plugging.
• Scale and precipitate formation.
• Incompatibility.
In water sampling and analysis, we determine the type
and amount of dissolved and suspended material in the Critical components:
water and the physical, chemical and microbiological
dissolved solids,
properties of the water. Water analysis is a first step in a
diagnostic procedure (1) to ascertain the possibility of suspended solids,
problems, (2) to determine the existence of problems, physical, chemical, and
(3) to test possible physical and chemical remedial treat- microbiological
ments, and (4) to measure the effectiveness of these
properties.
treatments.
Water is a major component of all EOR projects. In caus-
tic and steamfloods, we must know the types and
amounts of hardness and alkalinity and the total salinity
to determine the type and extent of softening required to
minimize the formation of plugging precipitates and
fouling scale deposits in steam generators. Knowledge of
hardness, alkalinity, and total salinity is necessary to
predict the effectiveness and compatibility of chemical
floods with surfactants or foams. With CO2 floods,
knowing the changing chemistry of CO2-acidified injec-
tion water (as it moves through and reacts with the
producing formation) helps us identify formation rock

dissolution reactions and potential corrosion and scaling
problems in producing wells and surface treating equip-
ment.
The composition of produced water can sometimes
indicate the source sand or formation for the produced
fluids. When compared with the compositions of injec-
tion and connate waters, produced-water composition
can indicate the time and extent of injection-water break-
through.
Composition changes across a facility for production,
separation, treating, and injection can pinpoint locations
and types of problems. Chemical analysis can help
diagnose the problems and determine the effectiveness of
treatment schemes. Dissolved oxygen measurements can
indicate the need for and effectiveness of mechanical and
chemical de-aeration. Monitoring oil-in-water content or
the types and amounts of suspended solids mirrors the
performance of the chemical treatment or process equip-
ment. It also confirms whether environmental discharge
requirements are met.
Because of the importance of oil-in-water concentration
and suspended solids in fouling equipment and plugging
injection or disposal wells, the sampling for and analysis
of these two items are treated separately in this chapter.
Bacteria and bacterial fouling problems are discussed
Chapter 7.
Constituents Determined and Properties

Measured
This chapter focuses on those major components and
properties of water that are important in recognizing and
treating of water-related problems in producing opera-
tions. Characterizing waters for trace elements, as in an
extensive geochemical analysis, is not covered. Simpler
procedures and techniques are used; major components
are determined; fewer properties are measured; and the
emphasis is on rapid, reproducible, relatively accurate
procedures and methods for “sampling” and analysis.
Table 1 lists the components determined and properties
measured for the purposes of problem solving. Not all
components are determined nor all properties measured

in each analysis. Emphasis is on those components
pertinent to the system or problem under study. Those
factors of importance for each type of situation are dis-
cussed next.
Significance of Components or Properties
Cations
Sodium, Na+
• Is the principal monovalent cation in most waters. Cations are positively
• All commonly occurring sodium compounds are charged ions that moved
soluble, although sodium chloride may precipitate towards the cathode in an
from highly concentrated, nearly saturated brines.
electrolysis cell.
• Should be determined analytically, not calculated by
difference, as was common in many “older” analyses.
• Is the primary cation contributor to total dissolved
solids (TDS) and ionic strength. Sodium ions are the
• Used in cation/anion balance as a quality-control major cations in normal
check. produced or connate
waters.
Potassium, K+
• Is usually present at lower concentrations than so-
dium.
• High levels may indicate sample contamination from
drilling or completion fluids.
• All commonly occurring potassium compounds are
soluble.
• May be combined with and reported as equivalent
amount of sodium ions.
Calcium, Ca2+
• Usually is the principal divalent cation.
• Contributes to and may be reported as water hard-
Calcium and magnesium
ness.
are the principal
• Combines with sulfate or carbonate ions to form
suspended solids or adherent scale deposits. “hardness ions” in
produced waters.

Table 1 Primary Components and Properties of Oil
Field Waters
+
Cations Sodium, Na
+
Potassium, K
2+
Calcium, Ca
2+
Magnesium, Mg
2+
Barium, Ba
2+
Strontium, Sr
2+
Iron, Fe
Hardness, as CaCO3
-
Anions Chloride, Cl
Salinity, Chlorinity, and
Chlorosity
Carbonate, CO 2-3 and
Bicarbonate, HCO −3
Sulfate, SO 24−
Organic Acids, as Acetate
Alkalinity, as CaCO3
Dissolved Gases Oxygen, O2
Carbon Dioxide, CO2
Hydrogen Sulfide, H2S
Neutral Silica
Components Bacterial Content
Oil-in-Water
Total Residue
Total Dissolved Solids
Suspended Solids
Amount
Type
Particle Size Analysis
Properties pH (field and lab)

Temperature
Turbidity
Color
Density (or Specific Gravity)
Conductivity (or Resistivity)

Magnesium, Mg2+
• Frequently is present in smaller amounts than calcium
except in seawater or connate waters derived from
seawater.
• Contributes to and may be reported as water hard-
ness.
• May form insoluble magnesium hydroxide at high
pH.
• Readily forms ion pairs with sulfate ions, thereby
decreasing the activity of free sulfate ions and increas-
ing the apparent solubility of sulfate scales and pre-
cipitates.
Barium, Ba2+
• Is frequently found in produced waters but at a lower
concentration than calcium or magnesium.
• Combines with sulfate ions to form extremely in-
soluble barium sulfate deposits that are difficult to
remove.
• May indicate the presence of other radioactive alka-
line earth cations (e.g., radium).
Strontium, Sr2+
NORM (naturally
• Usually is associated with but at lower concentrations
than barium. occurring radioactive
material) is usually
• Forms insoluble strontium sulfate or mixed
strontium/barium sulfate precipitates. radioactive divalent
cations included in
Iron, Fe sulfate scales.
• Usually is determined and reported as soluble iron
and total iron (soluble + insoluble).
• May occur naturally in some waters and formations
but frequently indicates corrosion of producing and
treating equipment.
Soluble iron may be an
• Is present initially in the reduced form, Fe2+ or Fe(II), indication of corrosion.
in produced water.
• Reduced iron, Fe2+ or Fe(II), is more soluble than
oxidized iron, Fe3+ or Fe(III).

• Reduced iron oxidizes easily by contact with air or
other oxidants.
• “Iron counts” are useful in detecting and monitoring
corrosion only in “sulfide-free” waters.
• “Red water” — suspended iron oxide and hydrox-
ides, usually found in oxidizing environments.
• “Black water” — suspended iron sulfides, usually
found in reducing environments with measurable
sulfide levels.
• Iron sulfides and oxides cause severe formation
plugging and may be difficult to remove by acidizing.
• Iron sulfides are readily oxidized upon exposure to
air or an oxidizing environment.
Hardness
• Originally named for and determined by reaction
with soap solution to form scum or “bathtub ring.”
• Reported as parts per million (ppm) or milligrams per
liter (mg/L) as calcium carbonate.
• Composed primarily of calcium and magnesium ions
Calcium and magnesium but includes any other di- and trivalent cations.
are the principal hardness • Indicates relative carbonate scale formation potential.
ions and form an
• Frequently precipitated in boilers, steam generators,
insoluble scum with and highly alkaline waters.
soaps. • May be determined directly by titrimetric chemical
analysis or calculated by conversion of di- and tri-
valent cation concentrations to chemically equivalent
amounts of calcium carbonate (CaCO3).
Anions
Chloride, Cl-
• Major anion in many waters.
Anions are negatively • High concentrations increase water corrosivity.
charged ions that move
• Stable anion, useful for identifying and tracing water
towards the anode in an flow.
electrolysis cell.

Salinity, Chlorinity, and Chlorisity
• Terms frequently used to describe the amount of
dissolved solids, in terms of Cl- or Cl- equivalents, in
seawater or waters derived from seawater by dilution
or concentration.
• Should not be used for waters with anion composi-
tion ratios differing from those of seawater, e.g., Salinity, chlorinity, and
waters with high ratios. chlorisity are used only
for waters similar in
Salinity
composition to seawater.
• Total solids after all carbonate and bicarbonate have
been converted to oxide, all bromide and iodide have
been replaced by the equivalent amount of chloride,
and all organic matter has been oxidized.
• Usually reported as grams per kilogram (g/kg) of
solution or parts per thousand (ppt, ‰)
• Calculated from chlorinity only for seawater and
seawater-like waters by the following empirical
relationship:1
salinity, ‰ = 0.03 + 1.805 x (chlorinity, ‰).
• Calculated from measured chlorisity by using Table
210:IV of Ref. 2 (1980) (Pages 109-20).
• Experimentally determined by measuring
temperature-corrected specific gravity with a hy-
drometer and converting to salinity by means of
density/salinity tables [Table 210:II, Ref. 2 (1980),
Pages 105-06].
Chlorinity
• Now defined in parts per thousand (ppt, ‰) as the
number of grams of silver necessary to precipitate
the Cl- and Br- in 328.5233 g of seawater.3
• Usually determined by titration with silver nitrate.
• Can be calculated from ionic concentrations by
− −
Cl(‰)= 0.9996∗ (Cl + 0.4437∗ Br + 0.2794∗ I )
-

Chlorisity
• Obtained by multiplying chlorinity by the density of
water at 20°C.
• Similar to chlorinity except chlorisity is a weight-per-
volume concentration term.
Carbonate and Bicarbonate, CO 32 - and

HCO3−
• Major component (along with organic acids) of alka-
linity.
• Forms scale deposits with calcium ions.
Alkalinity is a measure of
the capacity of a water to • Relative proportions of CO 23 − − HCO −3 − CO 2 are pH-
react with acids. dependent.
Bicarbonate and • Decomposes at high temperatures to yield carbon
carbonate are the major dioxide in the vapor (steam) phase and hydroxide
components of alkalinity ions in the liquid phase.
in many produced waters. • Carbonates are sometimes referred to as phenolphtha-
lein alkalinity; bicarbonates as methyl orange alkalin-
ity.
Sulfate, SO 42 −
• Forms insoluble deposits with calcium, barium,
strontium, and other alkaline earth cations.
• Electron acceptor (oxidizing agent) in the biogenic or
thermal production of hydrogen sulfide.
• Barium sulfate (barite) is a common component of
drilling muds and may appear as a contaminant in
produced water.
“Organic Acids”
• Major component (along with carbonates and bicar-
Organic acids can be a bonates) of alkalinity in some produced waters.
carbon and energy source • Generally are low-molecular-weight (C2 to C4) ali-
for bacterial activity. phatic acids or naphthenic acids (saturated acids with
five- and six-membered rings of carbon atoms).

• Low-molecular-weight aliphatic acids are readily
soluble in moderately basic waters.
• Acetic acid (or acetate ions) is the most commonly
occurring organic acid in produced water and may be
present in concentrations as high as thousands of
milligrams per liter.
• Naphthenic acids have low water solubilities, espe-
cially at pH less than 4 to 5.
• May have been formed by bacterial action or by
thermal decomposition of more complex organic
material in crude oil or crude oil precursors.
• Carbon and energy sources used by many bacteria,
including sulfate-reducing bacteria (SRB).
Alkalinity
• Measure of ability to combine with or consume hy-
drogen ions from an acid.
• Made up primarily of carbonate, bicarbonate,
and organic acid anions, with minor contributions
from other acid anions (e.g., bisulfide, borate, phos-
phate) and weak bases (e.g., ammonia).
• Is a major factor in fixing the pH and buffer capacity
of the water.
• Is usually determined by titration with standard acid
and then broken down into component parts by other
analytical and calculation methods.
Dissolved Gases
Oxygen, O2
• Can cause severe corrosion if present in even low
levels. Dissolved oxygen is a
• Recommended levels 20 parts per billion (ppb) to major contributor to the
minimize corrosion. corrosivity of oilfield
• Oxidizes soluble iron to precipitate iron oxides. waters.
• Can oxidize dissolved sulfides to form colloidal
sulfur.
• Promotes growth of aerobic, slime-forming bacteria.

Carbon Dioxide, CO2
• Acid gas that decreases pH of water.
• High concentrations increase corrosion rates.
• Influences formation and dissolution of carbonate
scales.
Hydrogen Sulfide, H2S

• Is highly toxic.
Hydrogen sulfide, a toxic • Acid gas that decreases pH at high concentrations.
gas with the smell of • Increases water corrosivity.
rotten eggs, is frequently
• Reacts with oxygen or other oxidizing agents to form
produced by bacteria in highly corrosive solution.
oilfield production
• Causes mechanical failure of steel components.
systems.
• May indicate active sulfide-producing bacterial (SPB)
population.
• Reacts with soluble iron to form plugging
deposits; corrosive precipitates; and oil-wet,
emulsion-stabilizing deposits.
Neutral Components
Silica
• Is usually present in low amounts (<100 ppm) except
when water is hot and/or has a high pH.
• Is a source of scale in boilers and steam generators.
• Is used as a geochemical thermometer.
Bacterial Content
• Bacteria biomass can plug and foul injection wells,
Bacteria must not only be surface treating facilities, and downhole equipment.
present, they must also be • An estimate of the type and number of bacteria is
necessary to assess the presence and severity of bacte-
active within the system
rial problem and to suggest remedial actions.
to cause problems.
• SRB and SPB generate toxic and corrosive hydrogen
sulfide.

• Acid-producing bacteria (APB) form corrosive organic
acids (e.g., acetic acid).
• Contributes to localized (pitting) corrosion and en-
hanced corrosion rates.
• Decarboxylates organic acids and decomposes other
organic material to form CO2.
• Usually exists in consortia or microniches where one
type of bacteria provides the carbon and energy
sources and the necessary environment for other
types of bacteria.
• May convert soluble material [e.g., soluble iron(II)] to
insoluble precipitates and scales.
• Biofilms and biogenic deposits can contribute to
underdeposit corrosion.
• Predominant factor in reservoir souring.
Oil-in-Water Content
• Must be low and meet environmental criteria for
discharge to surface waters.
• May decrease injectivity by forming “emulsion
blocks” in the pores of the formation or by increasing
the oil saturation and thereby reducing the relative
permeability to water.
• Acts as a cementing material for other suspended
solids.
• Can be used to estimate efficiency of separators and
oily water treatment equipment.
Total Residue
• Is the amount of solid material left after evaporating a
water sample and drying the residue at a specified
temperature.
• Composed of nonfilterable residue (suspended solids)
plus filterable residue (dissolved solids).
Suspended Solids
• Particulates that may plug injection wells, foul surface
equipment, or induce turbidity in receiving waters.

• Amount of suspended solids.
Suspended solids, along
Usually inversely related to water quality.
with dispersed oil, are the
Determined gravimetrically or by particle-size analy-
major cause of plugging sis.
of injection wells.
• Type of suspended solids.
May be corrosion products, scale deposits, insoluble
precipitates from incompatible waters or treatment
chemicals, bacteria and biomass, or formation fines
Identification of type of suspended solids may indi-
cate source.
Determines plugging properties: large, crystalline,
uniform-sized particles produce high-permeability
filter cakes; hydrated, small particles form low-
permeability filter cakes.
• Particle-size analysis.
Particle-size population — gives number (or volume)
of particles of a given size.
Particle-size distribution — gives fraction of total
number (or volume) of particles having a given size;
does not estimate the total number (or volume) of
particles present.
Population measurements are more useful than distri-
bution measurements.
Used to estimate plugging potential of suspended
solids, filtration requirements for injected waters, and
removal efficiencies of treatment chemicals and sepa-
ration equipment.
Total Dissolved Solids

• Either measured gravimetrically or calculated from
the sum of concentrations of dissolved components.
• Affects corrosion rates and apparent solubilities by
changing total ionic strength and activity coefficients.
• High dissolved solids content usually indicates high
corrosion rates and increased solubilities of precipi-
tates or scales.

Properties
pH
• Defined as the negative logarithm of the hydrogen ion
activity (concentration). Neutral waters have a pH
• Affects solubility of carbonate, hydroxide, and sulfide of 7. Acid waters have
precipitates or scales. pH’s less than 7. Alkaline
• Corrosion rate increases as pH decreases. or basic waters have pH’s
• Low pH may indicate presence of corrosive acid greater than 7.
gases, CO2 and H2S.
• Usually determined by the amount and type of weak
acids and bases present (or organic acid/organic acid
anion).
• May change rapidly in a poorly buffered system from
loss or gain of acid gases.
• Best measured in place in a pressurized system or in
the field immediately after sampling.
• Laboratory-measured pH may differ significantly
from field measurements because of changes in acid
gas concentration, hydrolysis reactions, precipitation
of basic and acidic components, or bacterial degrada-
tion of organic material.
Temperature
• Must be measured in the field.
• Strongly affects corrosion rates, precipitate solubili-
ties, and efficiencies of oil/water separations.
Turbidity
• Is a measure of water cloudiness or opacity.
• Is caused by scattering and absorption of light by
particulates (suspended solids and dispersed oil).
• Can be related to suspended solids and/or oil content
only if the system is well characterized and unchang-
ing.
• Is an indirect measure of water quality (high turbidity
indicates low water quality).

Color
• Is produced by dissolved, colloidal, or suspended
colored material in water.
• Is an indirect measure of water purity (low color may
mean high purity or at least the absence of colored
impurities).
• Perception of color strongly influenced by strength
and color of incident light.
Density
• Is defined as weight per unit volume.
Density and specific • Specific gravity is the ratio of the sample density to
gravity are numerically water density, each at some specified temperature.
equal only when the • Densities greater than pure solvent indicate the pres-
reference water has a ence of dissolved and suspended solids.
density of exactly • Correction factor used for some concentration conver-
1.0000 g/mL. sions.
• Can be used as a quality-control parameter because
density and total dissolved solids content are related.
Conductivity
• Measure of the dissolved ionic components.
• Resistivity (reciprocal of conductivity) used for well
logging.
• Can be a quality-control parameter because conduc-
tivity is related to ionic concentration.
Sampling
Sample location and identification, as well as sampling
Steps in chemical procedures and preservation techniques, are as important
analysis: as the choice of analysis procedure. The sample must
represent the operating system at some set of conditions.
1. sample preparation The sample should be uniquely identified, and the loca-
2. sample preservation tion and operating conditions at the time of sampling
3. chemical analysis should be recorded. Finally, multiple samples may be
4. reporting necessary: field analysis and specially preserved samples
for unstable components, unpreserved samples for stable
components, and separate samples for specialty analyses.

Sample and System Identification
Sample and system documentation are essential for
sample tracing. We need sufficient information to iden-
tify where, when, how, why, and by whom the sample
was taken. System operating conditions at the time of
sampling should be listed. This is especially important if
the system is not operating under normal conditions
when the sample is drawn. Table 2 shows the type and
extent of information needed.
Sampling Procedures
The sample must be representative of the operating
system. The system sampled should be operating as
close as possible to normal conditions of flow rate, pres-
sure, temperature, etc. Any departures should be noted
on the sample identification form. The sample should be
taken from a flowing, well-mixed stream, unless the
purpose of the sampling is to look at subnormal operat-
ing conditions.
Some system components or properties change rapidly
with time and cannot be adequately preserved or stabi-
lized for later laboratory determinations. These compo-
nents or properties must be measured or determined in
the field as close in time and location to the sample point
as possible. Other components may change with time
but can be preserved for later analysis. Still other com-
ponents are reasonably stable and do not need special
preservation techniques. A complete analysis involves
field analysis for some components and laboratory analy-
ses with an unpreserved sample and with several spe-
cially treated samples for the remainder.
All liquid samples for analysis or preservation should be
field-filtered as soon after sampling as possible. The Filtration in the field is an
purpose is to remove dispersed oil and suspended solids essential step in sampling
(scale deposits, corrosion products, formation fines, etc.)
present in the original sample. Chevron personnel devel- and sample preparation.
oped an automatic pressure filtration apparatus4 suitable
for field filtration. Carpenter and Campbell5 gave spe-
cific details for field sampling and filtration. Multiple
filtrations may be necessary if dispersed oil concentra-

Table 2 Information for Water Sample and System
Description
Sample Location
Field, lease, well, section, state, country,
gathering station, tank battery, pipeline,
pit, etc.
Date and Time of Sample
Sampled By
Sample Description
Source, zone, or formation
Color, presence of oil and/or solids, odor, any
unusual features
Sample Conditioning
Filtration, refrigeration, special preservatives
(type and amount)
System Operation
Normal, abnormal, shut in
Flow rate and pressure at sample point
Treatment chemicals (type and amount)
present
Any unusual or abnormal factors
Field Analyses Performed

Types of analyses, location of results
tions are high. Dispersed oil, even when present in

moderate quantities, quickly saturates and bleeds
through most membrane filters.
The only exceptions to field filtration are measurements
for turbidity and color. These measurements must be
made in the field with unfiltered samples. Turbidity and
frequently color result from suspended or colloidal
material that could be removed by filtration.
For laboratory analysis, we prefer using a glass bottle
that was washed with acid, rinsed with deionized water,
and dried. Place samples in individual glass bottles for

shipment to remote laboratories in a waterproof mailing
tube with enough packing material to prevent breakage.
Temperature-sensitive samples may need to be shipped
in insulated containers.
Note: Many oilfield samples contain materials considered
dangerous or hazardous. Contact the postal service or shipping Shipment of samples by
company for restrictions and necessary packaging and docu- commercial carriers
mentation before sending samples by commercial carriers. To
requires special
facilitate sample transport, use washed and rinsed plastic
bottles for all samples, except those for oil-in-water precautions.
content measurements. Place the plastic sample bottle in
a protective mailer, too. Trace amounts of some heavy
metal ions may irreversibly adsorb onto the plastic sur-
face and be unavailable for analysis. Again, acid-washed
glass bottles are best for these samples.
Field Measurements
The following components must be measured in the field
immediately after sampling and filtration:
• pH.
• Temperature.
• Turbidity (must be done with an unfiltered sample).
• Color (must be done with an unfiltered sample).
• Total alkalinity.
• Dissolved O2.
• CO2.
• Bisulfide, HS- (see Ref. 6 for a field analysis procedure
for low sulfide concentrations. As an alternative,
stabilize a separate sample with basic zinc solution).
• Soluble iron(II).
• Total suspended solids (primary filtration and wash-
ing with water performed in the field; subsequent
washings and weighings may be performed in the
laboratory).
• Bacteria filtered or cultured from the sample in the
field with subsequent incubation and enumeration in
the laboratory.

Preserved Samples
Before sampling begins, consult the laboratory perform-
ing the analysis to determine acceptable preservation
techniques compatible with the laboratory’s analytical
methods.
Cation Analysis — A field-filtered sample preserved
with either hydrochloric acid or citric acid 5 is taken for
laboratory analysis of the following cations:
Sodium, Na+.
Potassium, K+.
Calcium, Ca2+.
Magnesium, Mg2+ .
Barium, Ba2+ .
Strontium, Sr2+ .
Iron(II), Fe2+ .
Alkalinity Determination — Alkalinity is a measure of
Many produced waters the ability of a solution to react with hydrogen ions (H+)
from an added acid. Alkalinity is not a measure of any
contain components in
one particular system component; it is a measure of a
addition to bicarbonate system property. Components commonly contributing to
and carbonate that alkalinity in oilfield brines are carbonate and bicarbonate
contribute to the ions, water-soluble aliphatic and cyclic acid anions, and
bisulfide ions (HS-). Sulfide ions (S2-) usually do not
alkalinity of a water.
contribute because the pH of most oilfield waters is too
low for measurable amounts of sulfide ions to be present.
Ammonia (NH3), not ammonium ion ( NH +4 ), borate, and
phosphate ions can contribute to alkalinity if their con-
centrations are high and the solution pH is such that
these materials are in their base forms.
Current field analytical procedures are not sensitive
enough to distinguish the different forms of alkalinity
that might be present in a produced-water sample. A
separate sample is taken and preserved for laboratory
analysis by adding a known amount of standard hydro-
chloric acid (HCl) sufficient to decrease the pH of a
known volume of sample to at least 2.5. At pH 2.5, all
dissolved bases have been converted to acids, and HCl is
present in excess. In the laboratory, the volatile acids,

primarily carbonic (H2CO3) and hydrogen sulfide (H2S),
are removed by inert gas sparging or vacuum boiling.
The excess HCl added in the field for stabilization and
the nonvolatile acid content are determined by titration
with standard base. The first endpoint at pH 3.5 to 4 is
related to the excess acid; the second endpoint at pH 7 is
related to the nonvolatile acid. The total sample alkalinity
equals the total amount of HCl added to the sample
decreased by the excess HCl found in the titration to the
first endpoint. The carbonate/bicarbonate alkalinity equals
the total alkalinity decreased by the sum of the equiva-
lents of nonvolatile acids, bisulfide ions, and any other
alkalinity ions present in significant amounts.
Unpreserved Sample
A filtered sample with no preservatives or conditioners is
used for silica analysis. If the silica is expected to be Dilution is commonly
supersaturated at lower temperatures after sampling, the
used to preserve a
sample should be diluted with a known volume of silica-
free deionized water. The filtered sample also is used for supersaturated solution of
the common and stable anions (chloride and sulfate) and silica.
cations (sodium and potassium). An unpreserved sample
is used to measure specific resistivity (or conductivity)
and specific gravity (or density). Additional portions of
this sample are used to measure laboratory pH, labora-
tory alkalinity, carbonate and bicarbonate alkalinity, and
nonvolatile acid content. These measurements are made
to check field analyses and to indicate possible gas ex-
change reactions, bacterial activity, or precipitation and
hydrolysis reactions that might have occurred between
sampling and laboratory analysis.
Oil-in-Water Content
Separate samples, in individual glass bottles, are needed
for each oil-content determination (oil-in-water analysis). Currently, there is no
If total oil content (free or dispersed oil plus dissolved
analytical procedure that
oil) is desired, the sample is not filtered. Prefiltration will
remove dispersed oil and allow estimation of dissolved is specific for oil. Oil, by
oil. Water samples containing large amounts of dis- definition, is whatever is
persed oil may need to be filtered several times to re- detected by a specified
move all the free oil. The filter may become saturated
analytical method.
with oil and permit excess oil to bleed through. If the

interval between sampling and analysis exceeds about 2
to 4 hours, the sample should be preserved by adding
sufficient HCl or sulfuric acid to lower the pH to at least
2. See the Oil-in-Water Analysis section for specific
details on sampling and analysis.
Analytical Methods
Analytical methods for cations, anions, and dissolved
gases are summarized in Table 3; Table 4 lists the meth-
ods for neutral components and properties. The follow-
ing section gives brief descriptions of the methods.
Chemical and physical properties of the sample can be
used to determine the concentrations of components or
measurement of properties.
Chemical Properties
Various procedures involving the chemical properties of
the constituents are used in water analysis.
Gravimetric Analysis — In gravimetric analysis, the
Gravimetric analysis is desired chemical component is reacted completely with
an excess of another chemical to form an insoluble com-
usually very accurate. It is
pound of definite and known composition. The insoluble
used to prepare and compound is removed by filtration, washed to remove
determine analytical impurities, dried or ignited to a fixed composition, and
standards. It is a weighed on an accurate and sensitive analytical balance.
From the precipitate weight and composition, we can
laboratory method.
calculate the amount of the original component. For
example, we can determine barium ions by adding an
excess of sulfate ions to precipitate insoluble barium
sulfate and then digesting, filtering, washing, and drying
the precipitate.
+ −
Ba + SO 4 → BaSO 4
2 2
The amount of barium in the precipitate, and hence in the

original sample, is calculated by multiplying the precipi-
tate weight by the barium/barium sulfate molecular
weight ratio.
Wt. Ba 2 + =
(Wt. BaSO 4 )∗ (Mol. Wt. Ba)
(Mol. Wt. BaSO 4 )

Table 3 Analytical Methods for Cations, Anions,
and Dissolved Gases
ANALYTICAL
COMPONENT METHODS
Cations
Sodium AAS, FES, ICP, ISE,
calculation
Potassium AAS, FES, ICP, calculation
Calcium and Titration, AAS, ICP, ISE,
Magnesium gravimetric
Barium and Strontium AAS, ICP, turbidimetric,
gravimetric
Iron Titration, colorimetric,
ICP
Hardness Titration, AAS, ICP, ISE,
calulation
Anions
Chloride Titration, ISE, IC,
gravimetric
Salinity, Chlorinity Titration and calculation
and Chlorisity
Carbonate and Titration, calculation
Bicarbonate
Sulfate Gravimetric,
turbidimetric, IC
“Organic Acids” Titration, IC
Alkalinity Titration, calculation
Dissolved Gases
Oxygen Titration, colorimetric,
amperometric with
membrane electrode
Carbon Dioxide Titration, ISE, calculation
Hydrogen Sulfide Colorimetric, ISE, titration
Abbreviations:
AAS — Atomic absorption spectrophotometry
FES — Flame emission photometry
IC — Ion chromatography
ICP — Inductively coupled plasma spectroscopy
ISE — Ion selective electrode

Table 4 Analytical Methods for Neutral Components
and Properties
ANALYTICAL
COMPONENT METHODS
Neutral Components
Silica Gravimetric, colorimetric,
ICP
Bacterial Content Culturing techniques (see
separate Section on
bacterial effects)
Oil Content Colorimetric, gravimetric
(see separate Section on
Oil-in-Water analysis)
Total Residue
Suspended Solids
Amount Gravimetric
Type Colorimetric
Particle Size Particle size analyzer
Analysis
Total Dissolved Gravimetric, calculation
Solids
Properties
pH ISE, colorimetric
Temperature Thermometer
Turbidity Turbidimeter, colorimetric
Color Colorimetric
Density (or Specific Hydrometer, pycnometer
Gravity)
Conductivity (or Conductometric,
Resistivity) calculation
Abbreviations:
AAS — Atomic absorption spectrophotometry
FES — Flame emission photometry
IC — Ion chromatography
ICP — Inductively coupled plasma spectroscopy
ISE — Ion selective electrode

Gravimetric methods are usually the most accurate
and precise analytical methods. They have been used to Volumetric analysis is
determine atomic weights to seven significant figures. convenient, inexpensive,
However, the procedures are frequently long and compli-
and widely used for a
cated, and they are usually not suitable for field applica-
tions. A stoichiometric compound of sufficient insolubil- large number of chemical
ity is not always available for each desired component in components. It is
the sample. frequently done in the
Volumetric or Titrimetric Analysis — In titrimetric analy- laboratory but many kits
sis, a standard solution of accurately known concentra- are available for field
tion that reacts stoichiometrically with the sought
analysis.
constituent is added stepwise until all the sought com-
pound has reacted. This point of complete reaction is
called the endpoint. The endpoint is detected by an “indi-
cator” added to, or placed in, the solution. The indicator
may be a chemical compound that changes color at the
For accurate and precise
endpoint. Colored indicators are available for acid/base,
oxidation/reduction, and many precipitation or complex- volumetric analysis, the
ation titrations. The indicator may also be electrodes that end point must be readily
detect the electrochemical potential (activity) of a particu- and reproducibly detected
lar ion in solution (e.g., a pH electrode for acid/base
and correspond exactly to
titrations) or determine the electrical conductivity of the
ions in solution. From the concentration and volume of the equivalence point.
standard solution added to reach the endpoint, we can
calculate the amount of sought component in the sample.
Thus, for the precipitation titration of chloride ion with a
standard solution of silver ion,
+ −
Ag + Cl → AgCl
the endpoint occurs when an amount of silver ion

equivalent to the chloride ion has been added. The
endpoint can be detected with colored indicators, by
electrochemical methods, or by turbidity changes. The
amount of chloride ion in the original sample is given by
W = V∗ C∗ E
where
W = weight of chloride ion present, mg;
V = volume of silver standard added, mL;
C = concentration of silver standard, meq/mL; and

E = milliequivalent weight of chloride ions, mg/
meq.
Titrimetric procedures are available for a wide variety of
constituents. They are usually quite precise if specified
procedures are closely followed. In some cases, interfer-
ences in solution will reduce accuracy by giving an end-
point indication at a volume other than the equivalence
point. Instructions for the titrimetric procedures usually
indicate possible interferences and means to eliminate or
compensate for them. Small, portable test kits using
syringe-type burettes are available for many titrimetric
analyses. These are ideal for field analyses.
Colorimetric or Spectrophotometric Analysis — These
methods measure the amount of light of a particular
wavelength (color) either emitted or absorbed by the
sought component. Electromagnetic radiation in the
infrared, visible, or ultraviolet regions is most commonly
used for oilfield water analyses. Light may interact
directly with the sought component or with an added
material that will react specifically and stoichiometrically
with the sought component.
In the simplest analyses, the material absorbs or emits
The simpler colorimetric light of a characteristic wavelength under ambient condi-
tions (colorimetry or spectrophotometry). In more com-
and turbidimetric
plex methods, light of a specific wavelength is absorbed
methods can be used in or emitted when the sought material is excited in some
the field. The more manner. Atomic absorption spectrophotometry (AAS) is an
complex procedures example of light absorption by a thermally excited mate-
rial. Light of specific wavelengths characteristic of a
requiring extensive
component is emitted when the component is excited
equipment are laboratory electrically (emission spectroscopy), thermally (flame emis-
methods. sion spectroscopy, flame photometry, and inductively coupled
plasma spectroscopy, ICP), electronically (X-ray spectros-
copy), or photochemically (fluorescence spectroscopy).
In turbidimetric analysis, a related optical method, a finely
divided precipitate of the sought component is reproduc-
ibly formed by the addition of a precipitating agent,
usually in the presence of a dispersant. The turbidity of
the resulting solution, caused by the absorption and
scattering of incident light by the suspended particles, is
measured and related to concentration through

similar turbidity measurements on standards. This
method is frequently used to determine sulfate as
precipitated barium sulfate.
Colorimetric methods range from very simple (requiring
little or no additional equipment) to very complex (using
complicated and expensive equipment, frequently with
computer control and data acquisition and analysis).
Simple kits suitable for field sampling and analyses for
many components are available from:
Hach Chemical
P.O. Box 389
Loveland, CO 80539
In the Hach methods, the color developed by reaction of
the desired component with a color-forming reagent is
compared with liquid or solid color standards in the kit.
Sensitivity and selectivity in field applications can be
improved with a portable, battery-operated spectropho-
tometer with selective color-forming reagents.
The more complex emission and absorption methods
require increasingly complex equipment in a laboratory
environment. These methods, however, are usually
rapid, more versatile, and less subject to interferences.
Some are capable of multiple- element analyses on small
sample volumes. Most cations (metallic ions) can be
determined by published standard methods using AAS
or ICP.
All methods determine concentrations by comparing the
amount of light absorbed or emitted with that from
standard solutions of known concentrations. The pub-
lished standards usually give specific procedures, inter-
ferences, and indications of precision and accuracy.
Electrochemical Methods — In these methods, some
electrochemical property of the sought component is Many electrochemical
determined and related to concentration or activity. With analysis procedures have
potentiometric methods, an electrical potential or voltage
is measured with an electrode to give an ion activity that been adopted for field
is related to ion concentration in a known manner. Ex- usage.
amples are the pH electrode and ion selective electrodes
for Na+, Ca2+ , Ag+, S2-, Cl-, CO2, etc. These electrodes are
quite specific for each component, relatively free from
interferences, and usable over several orders of

concentrations. Rugged electrodes and portable, battery-
powered voltmeters are available for field measurements.
Concentration can be determined by single-point mea-
surements and comparison with standards, or by mul-
tiple additions or subtractions of standards. The poten-
tiometric electrodes can also be used as indicator
electrodes in volumetric titrations.
In amperometric or voltammetric analyses, the current
caused by the oxidation or reduction of an electroactive
species is measured and related to concentration. Selec-
tivity for individual components is achieved by measur-
ing the current at a specific applied voltage at which the
desired species is electroactive. Concentrations are
usually determined by comparison with currents ob-
tained with standards under similar conditions. Ex-
amples of these types of measurements are electrodes for
dissolved oxygen determination and various forms of
voltammetry and polarography. Amperometric methods
can also be used as indicator electrodes in titration or
electrochemical procedures. Instruments are available
for field measurement of dissolved oxygen and various
forms of chlorine. Most other determinations are done in
the laboratory. A variant method is electrogravimetric
(plating) analysis in which the amount of electro-
deposited material is determined by weighing.
Coulometric methods measure the number of coulombs
The dispersed and (ampere- seconds) required to completely oxidize or
dissolved water in crude reduce an electroactive species. Specificity is achieved by
controlling the potential at which the electrochemical
oil can be quickly and
reaction occurs. The amount of material reacted is deter-
accurately determined by mined from first principles — no chemical standardiza-
an automatic coulometric tion is required. Coulometric methods are very accurate
titrator (Karl Fisher and sensitive because of the availability of precise, accu-
rate methods for measuring small numbers of coulombs.
titration).
These methods are usually not suitable for field analyses.
Conductometric analyses measure the current carrying
capacity (conductance) of all ions present. The method is
not specific for any ion but measures all ions present. It
is frequently used to indicate the total dissolved ionic
concentration. As such, it can be used as a quality-con-

trol check. Battery-powered instruments are available for
field measurements. The method is calibrated by mea-
suring the conductance of standard solutions.
Chromatographic Methods — New chromatographic
techniques are being developed for the separation, Currently used
identification, and quantification of anions and cations. chromatographic methods
In ion chromatography, ions are separated on chromato-
have little or no
graphic columns with special absorbents and eluants.
Special in-line colorimetric or electrochemical detectors connection with color.
detect and quantify the separated ions. Identification of
the type of separated ion is based on the retention time of
the ion on the column. The amount of each separated
ionic species is determined from the detector response.
Each method is calibrated for retention time and detector
response by running standards. Many ion chroma-
tographic methods are still in the development stage.
They have not been published as “standards methods.”
Physical Properties
Measures of some physical properties of a water sample
are frequently needed. Most of these measurements are
relatively simple and self-explanatory. They include
density or specific gravity — measured with a hydrometer,
a pycnometer, or a Westphal balance — and temperature
— measured with a thermometer or thermistor. Many
portable pH meters can also provide temperature read-
outs.
Standard Analytical Methods

Specific analytical procedures for all components and
properties of interest in oilfield waters are readily avail- A number of
able in several published standards manuals. Recom- organizations publish
mended standards include those published by the Ameri-
standard analytical
can Society for Testing and Materials7 (ASTM) and by a
joint effort among the American Public Health Associa- methods. These methods
tion, the American Water Works Association, and the should be used whenever
Water Pollution Control Federation2 (APHA/AWWA/ possible to assure
WPCF). These two standards manuals are constantly
accuracy and precision.
being reviewed, revised, updated, and expanded. Many
of the analytical procedures were developed for low-
salinity, fresh waters. Note that high-salinity, brackish
waters and brines might possess interferences and re-

quire modifications in procedures. Interferences and
high salinities are particularly troublesome when pack-
aged test kits are used. A frequent problem is the pres-
ence of interfering colors and higher reagent demands
because of higher concentrations of reactants in oilfield
water samples.
The American Petroleum Institute8 (API) published a
As of June 1994, API is recommended practice (RP 45) for analysis of oilfield
considering issuing an waters that considers some of the problems presented by
high-salinity waters. Unfortunately, the listed procedures
updated version of RP45. are quite old (1968), and the manual has not kept up with
improvements in analytical procedures and techniques.
The U. S. Environmental Protection Agency9 published its
own standard procedures for components of importance
to the environment. These procedures must be used
when obtaining permits for water discharge. In many
cases, the procedures are the same as those published by
ASTM or APHA/AWWA/WPCF.
Most commercial and company laboratories have their
own standard procedures. Many are based on the pub-
lished methods, so the reliability of the procedure is
known. When procedures have been modified or devel-
oped by the individual laboratory, information about the
applicability and repeatability of the procedures is not
always available. Users of commercial laboratories
should request information on the analytical procedure
used for each component and an estimate of the precision
or reproducibility of each analytical measurement.
Analytical Report
Information from sampling and analysis is usually pre-
The analytical report is sented in a Water Analysis Report. The amount of infor-
the final step in the mation presented and the report format vary among
laboratories. In general, a report should contain suffi-
sampling and analysis
cient information to identify the sample point and system
procedure. The reliability conditions at the time of sampling. It should list the
of the data in the report components or properties determined and the units of
depends upon all of the concentration or measurement for each component or
property, respectively. Additional sections may present
preceding steps in the
solubility calculations, graphical display of water
procedure. composition, and water type or classification.

Sample Identification
The report should include sufficient information to iden-
tify where, when, how, and by whom the sample was
taken. This information should be available from a Water
Sample Description form completed for each sample
taken and submitted for analysis. This information,
discussed in the previous section, is summarized in
Table 2. Table 5 shows a Sample Data Sheet.5
Methods of Presentation of Components

Components are usually listed as elements, ions, radicals,
or neutral compounds. This manner of presentation is Components as presented
for the convenience of reporting. It does not necessarily in an analytical report are
indicate the form or composition of the materials as they
exist in the sample solution or the form in which they not necessarily in that
were determined. Thus, simple cations and anions (e.g., form in the sample.
sodium, potassium, chloride, and sulfate) are usually
listed as uncomplexed ions even though the ions are
hydrated in solution. Amounts of calcium, magnesium,
hardness, and alkalinity are sometimes expressed “as
calcium carbonate (CaCO3).” This does not mean that
calcium carbonate is actually there, but that the analyst
chose to convert the determined weight or number of
equivalent of the stated material to a chemically equiva-
lent weight of calcium carbonate. Weight conversions of
this type are through the gravimetric factor, which is the
ratio of the equivalent weight of the sought compound
(compound converted to) to the weighed compound
(compound converted from):
(eq. wt. CaCO 3 )

(Wt. as CaCO 3 ) = (compd. wt.)∗
(eq. wt. compd.)
To convert the number of equivalents of a substance to its

weight as CaCO3, merely multiply by the equivalent
weight of calcium carbonate, 50.04:
(Wt. as CaCO 3 ) = (# of equiv.)∗(eq. wt. CaCO 3 )

or
(Wt. as CaCO 3 ) = (# of equiv.)∗ 50.04

Table 5 Information for Sample and System Description
SAMPLE DATA SHEET
Date: Operator:
Sample designation:
Local contact:
Address: Phone:
API Number: Lease/Well:
Field: State:
Country: Location: Sec: Twp:
Rge:
Producing Producing
Intervals: Formation:
Method of Production: Rod Pump Centrifugal Pump Gas Lift

Hydraulic Lift Other:
Production Rates: Oil Gas Water (Day, Month)
Sample Point: Wellhead Flowline Separator Tank
Other:
Well Completion Date: Date of Last Workover:
Waterflood? Other EOR?
Target concentration of any downhole additives?
Target concentration of other additive in sample (corrosion inhibitor, scale inhibitor,

emulsion breaker, etc.)?
Type of Well Scale:

Remarks:
Sampled by:

These types of calculational conversions are discussed in
the Concentration Units section.
Anions of weak, multibasic acids (e.g., sulfide, phos-
phate, silicic, and boric) are usually represented in the
analytical report in their fully ionized form, even though
the pH rarely is high enough for complete ionization.
Thus, sulfide is represented as either hydrogen sulfide,
H2S, or sulfide, S2-, when at the pH of most oilfield wa-
ters, the predominant form is the bisulfide ion, HS-. The
carbonate/bicarbonate/carbon dioxide system is an
exception in that the amount of each reported form is
calculated from the pH and measured alkalinity. Such
calculations can be wrong, however, if the water sample
contains appreciable amounts of other species that con-
tribute to alkalinity (sulfide, phosphate, organic acids,
ammonia, etc.) and the contributions of these species to
the total alkalinity are not taken into account.
Silica can exist in aqueous solutions in a variety of poly-
meric forms that are dependent primarily on the solution
salinity and pH. Amounts present may be reported as
silica (SiO2) or sometimes as silicate without the chemical
formula for the silicate species specified. In the latter
case, converting the reported weights to weights in other
forms is impossible.
In all cases, calculational weight conversions from one
chemical form to another is possible through the gravi-
metric factor, as illustrated previously in conversion
involving weights as calcium carbonate. In the general
case, the conversion is
EW2
W2 = W1 ∗
EW1
where
W1 = weight in original form,
W2 = weight in converted form,
EW1 = equivalent weight of original form, and
EW2 = equivalent weight of converted form.

Units of Measurement
The units of measurement must be included for each
component or property listed in the analytical report.
Some form of concentration units will be listed for most
components. Properties typically have their own mea-
surement units.
Concentration Units — Concentration units express the
ratio of the amount of the specified substance or compo-
nent in a given amount of the total system. A large
number of concentration terms are possible, depending
on how the units of substance and system are selected.
Fortunately, only a few are used for oilfield water analy-
ses. Calculational conversion between units by math-
ematical factors is discussed later in Concentration Con-
version Factors.
Before discussing specific concentration units in detail,
we should define a few basic chemical terms.
Atomic weight — relative weight of an atom of the
Atomic weight — weight element compared with the weight of the carbon-12
of a single atom relative atom. Table 6 lists atomic weights (rounded to the
nearest half unit) for some elements usually included
to a carbon-12 atom.
in a water analysis. Atomic weights for all elements
are available in chemical handbooks and in Refs. 10
and 11.
Table 6 Atomic Weights of Some Common Elements
Element Symbol Atomic Weight

Hydrogen H 1
Sodium Na 23
Magnesium Mg 24
Calcium Ca 40
Carbon C 12
Oxygen O 16
Sulfur S 32
Chlorine Cl 35.5
Molecular weight —
weight of a molecule Molecular weight — relative weight of a single mol-
compared to the weight of ecule compared with the mass of the carbon-12 atom.
a carbon-12 atom. Molecular weight is equal to the sum of the atomic
weights of the atoms making up the molecule multi-

plied by the number of atoms present. Table 7 shows
the calculation of the molecular weight of sodium
sulfate, Na2SO4.
Table 7 Calculation of Molecular Weight of Na2SO4
Multiplier ∗ Multiplier ∗
Symbol Atomic Weight Product
2∗ Na = 2∗23 = 46
1∗ S = 1∗32 = 32
4∗ O = 4∗16 = 64
Sum = Molecular = 142
Weight of Na2SO4
Mole — has a mass in grams equal to its molecular

weight. The unit mass in most water analyses is the
gram (0.001 kg).
Equivalent and equivalent weight — chemical com-
bining power with respect to a standard material. For Equivalent weight is
most oilfield water analyses, the standard material is
relative to reacting
the hydrogen ion. For hydrogen ion equivalents and
acid/base reactions, the equivalent weight is the mass weight.
of material in grams that will react with or displace,
directly or indirectly, one equivalent (1 g) of hydrogen
ion. The equivalent weight is numerically equal to
the atomic or molecular weight divided by the abso-
lute value of the valence. Table 8 gives examples of
equivalent weight calculations.
Table 8 Calculation of Equivalent Weights
Atomic or Equivalent
Molecular Weight,
Substance Weight Valence mg/meq.
H+ 1 +1 1
Na+ 23 +1 23
Ca2+ 40 +2 20
Cl- 35.5 -1 35.5
−
HCO 3 61 -1 61
2−
CO 3 60 -2 30
CaCO3 100 2 50

There are four basic types of concentration terms, de-
pending on how the amounts of the substance and sys-
tem are specified. The amount of substance present can
be expressed in terms of its physical properties (mass or
weight and, in a few cases, volume) or its chemical prop-
erties (chemical reacting equivalents or stoichiometry).
The unit amount for the system can be expressed in terms
of its mass or its volume. (For water analyses, the sample
solution is the system.)
Concentration units based on the solution mass are
Weight-based and independent of temperature. However, sample mass is
more difficult to measure, particularly in the field. Con-
volume-based
centration units based on system volume are more com-
concentration units are mon because of the ease of accurate volume measure-
numerically equal only ments. However, sample density and hence
when the solution density volume-based concentrations vary with temperature.
This is not necessarily a significant disadvantage because
is exactly 1.0000 g/mL.
density changes are small over the temperature ranges
usually encountered. For example, water density varies
about 0.26% over the temperature range of 2°C to 30°C.
Frequently, weight- and volume-based units are used
interchangeably. This practice should be discouraged
because the two systems are numerically equivalent only
for low-salinity systems where the solution density is
insignificantly different from unity. In seawater, the two
concentration units differ by more than 2%. Conversion
between the two systems is through the solution density:
(Volume − based conc. ) = (Weight − based conc.)∗(Density).

Two other sets of concentration units are based on the
amount of the sought component present. Units may be
based on a physical property, such as mass, or a chemical
property, such as reaction stoichiometry. Reaction sto-
ichiometry, of course, depends on the type of reaction
being considered—acid/base, oxidation/reduction,
complexation, etc. The same component could have
different reaction stoichiometries in each of these reaction
types. For produced-water analyses, stoichiometry is
usually based on acid/base reactions and hydrogen ion
equivalents. Water analyses are more frequently reported
in terms of weight of components rather than equiva-
lents. These weights are usually derived from chemical

reactions, and understanding this concept is a necessity.
Reacting values are also used to check ionic balance and
for quality control.
Concentration Units Based Upon Physical

Properties
Milligrams per Liter (mg/L) — Weight, in milligrams
(mg), of the stated substance contained in one liter (L) of
solution. This is probably the most frequently used
concentration unit because the weight of the substance is
usually measured directly or calculated and the amount
of solution is invariably measured as a volume. The
mg/L concentration term is frequently confused with
and used synonymously for parts per million (ppm).
Mg/L and ppm are numerically equivalent only for
solutions with low total solids content where the solution
density is essentially 1.000 g/mL. Conversion between
the two units is by
mg / L = (density, g / mL)∗ (ppm)
Parts per Million (ppm) — Weight, in milligrams, of the
stated substance contained in one kilogram (kg) of solu- Concentration in parts per
tion. This unit is frequently used interchangeably with million and milligrams
mg/L. Such exchanges are correct only for dilute solu-
tions where the solution densities are 1.000 g/mL. They per liter are usually not
can be confusing and are not recommended. Because equivalent for water
sample amounts are usually not determined by weight in samples.
practice, water analysis forms listing concentrations in
ppm should be questioned to determine whether that is
truly the concentration term to be used. Was the sample
amount actually determined by a direct weight measure-
ment? Was it calculated from a measured sample volume
and a measured density? Conversion between ppm and
mg/L is by
(mg / L)
ppm = .
(density, kg / L)
Weight Percent (% or wt %) — Weight, in some unit, of

the stated substance in 100 weight parts of solution. Note
that the amount of solution is specified in terms of its
weight, not its volume. Frequently, this term is used
incorrectly where the volume of solution was measured

and where the density was assumed to be 1.000 kg/L.
When components are present in the percent range,
solution densities are greater than 1.000 kg/L. Signifi-
cant errors are introduced when solution weight in kilo-
grams and solution volume in liters are assumed to be
numerically equal. The wt % concentration unit is fre-
quently used for major components or components
present in large amounts to avoid the use of large num-
bers. For example, seawater contains roughly 35,000
ppm or 3.5% of dissolved solids. Factors for conversion
between wt % and ppm or mg/L are
wt.% = 0.0001∗ (ppm)
or
(mg / L)
wt.% = 0.0001∗ .
(density, kg / L)
Parts per Thousand (ppt or ‰) — The weight, in some

units, of the stated substance in 1,000 weight parts of
solution. This unit is frequently used for seawater analy-
ses. For example, seawater contains about 35,000 ppm or
35‰ of dissolved solids. The same precautions in terms
of sample weight versus sample volume apply here.
Conversion factor is
‰= 10∗ (wt.‰)= 0.001∗(ppm).

Grains per Gallon (gpg) — The weight in grains
(1 grain = 64.8 mg) of stated substance in one gallon
(1 gal = 3.785 L) of solution. This concentration unit is
sometimes encountered in water softening applications.
Conversion between mg/L and gpg is:
gpg = 17.12∗ (mg / L).
Concentration Units Based On Chemical

Properties
Milliequivalents per Liter (meq/L) — The number of
milliequivalents of the stated substance per liter of solu-
tion. This is the most frequently used concentration unit
involving the reacting capacity of a substance. Chemical
equivalence is always related to the reaction involved. In

analysis of oilfield waters, the chemical reaction used to
define equivalence is usually the combination or reaction Milliequivalents per liter
with hydrogen ions. This concentration unit is used are frequently used to
primarily as an analytical quality-control check. Because
estimate the reliability or
solutions are electrically neutral, the sum of the cation
concentrations, in milliequivalents/liter, should equal the correctness of a chemical
sum of the anion concentrations if the analysis for analysis.
charged species (ions) is complete and correct. The
concentration, in meq/L, is obtained by dividing the
concentration in mg/L by the milliequivalent weight of
the substance:
(mg / L)
meq / L = .
(milliequiv. wt.)
Equivalents per Million (epm) — The number of

milliequivalents of the stated substance contained in 1 kg
of solution. This unit bears the same relationship to ppm
as meq/L does to mg/L. Concentrations, in epm, are
calculated from the relation
(ppm)
epm =
(eq. wt.)
Milligrams per Liter (or Parts per Million) as Calcium

Carbonate [mg/L (or ppm) as CaCO3] — The weight of
the stated substance, in milligrams, converted to an
equivalent weight of calcium carbonate and expressed in
terms of 1 L (or 1 kg) of solution. The conversion is
performed by multiplying the weight of the substance by
the ratio of the equivalent weight of CaCO3 to the equiva-
lent weight of the substance, or by multiplying the num-
ber of milliequivalents of the substance by the
milliequivalent weight of CaCO3. The chemical reaction
usually involved in oilfield water analyses is hydrogen
ion replacement: therefore, a mole of calcium carbonate
contains two equivalents:
CaCO 3 + 2H + → Ca 2 + + CO 2 + H 2 O
and the equivalent weight is 50 — one-half the molecular

weight. This concentration unit is frequently encoun-
tered with cooling tower or boiler (steam generator)
water analyses. It is usually applied to hardness and
alkalinity. This concentration is related to equivalents

and can be used like meg/L to check a chemical analysis
for ionic balance. Calculation of concentrations is as
follows:
(ppm)∗ (eq. wt. CaCO 3 )

ppm as CaCO 3 =
(eq. wt. substance)
and
(mg / L)∗ (eq. wt. CaCO 3 )

mg / L as CaCO 3 =
(eq. wt. substance)
Normality (N) — The number of equivalents (weight of a

Normality is the substance divided by the weight per equivalent) con-
concentration term most tained in 1 L of solution. This unit is used most fre-
quently to specify concentrations of reagents used for
widely used by analytical chemical analysis. The number of equivalents in a mole
chemists. and the equivalent weight of a substance depend on the
chemical reaction involved — i.e., the number of hydro-
gen ions involved in an acid/base reaction or the number
of electrons involved in an oxidation/reduction reaction.
To minimize confusion, use of normality concentration
units should also include the defining chemical reaction.
There is an increasing tendency to avoid this confusion
by using molarity to specify reagent concentrations. The
calculation of normality is
(mg / L)
N = 0.001∗
(eq. wt.)
Molarity (M) — The number of moles (weight of sub-

Molarity is independent stance in grams divided by molecular weight in grams)
of chemical reactions. per liter of solution. This unit is used for analytical
reagents or systems containing a single compound. It is
related to normality as molecular weight is to equivalent
weight. It is not as confusing as normality, because a
reacting equivalence is not involved. Conversion to
molarity from weight concentration or normality is
(mg / L)
M = 0.001∗
(mol. wt.)
or

N
M=
(# of equiv./mole)
Molality (m) — The number of moles of substance in 1

kg of solvent. This unit is very seldom used for water Molarity is not
analyses. It is especially significant in physical chemical temperature dependent;
and thermodynamic calculations.
especially important in
Concentration Conversion Factors — Conversions be-
thermodynamic
tween the various concentration units were given earlier
for each unit. The factors for conversion between mg/L calculations.
and meq/L and between mg/L and mg/L as CaCO3 are
given in Tables 9 and 10, respectively, for a number of
cations and anions in oilfield waters. To convert from
one concentration unit to another, simply multiply the
given concentration by the appropriate factor. Table 11
gives formulas for conversions within and between the
physical and chemical concentration units. Substitute the
appropriate number in the formulas to convert between
various units.
Units Used for Properties

pH — The negative logarithm of the hydrogen ion activ-
ity (concentration). Pure water, where the activities of the
hydrogen ions and hydroxyl ions are equal, is neutral
and has a pH of 7. Acid waters have pH<7; alkaline
waters have pH>7.
Color — Determined by visual comparison of the sample
with standards made up of known concentrations of
colored materials. The standard color unit is that pro-
duced by 1 mg/L of platinum in solution in the form of
the chloroplatinate ion.
Turbidity — A measure of the ability of suspended par-
ticles to absorb and scatter incident light. Turbidity is Turbid waters are cloudy.
usually determined by comparison with specifically
prepared standards. Early turbidity measurements used
suspensions of silica in the form of Fuller’s earth, kaolin,
or stream bed sediments and so these turbidities where
measured in terms of ppm silica. Turbidities were mea-
sured by observation of the depth of a solution of sus-
pended solid just sufficient to obscure the transmitted
light from a standard candle. These turbidity units were

Table 9 Conversion Factors for Cations
To convert from To convert from

→meq/L
mg/l→ →mg/L
meq/l→ Cation →CaCO3
mg/L→ CaCO3→mg/L
multiply by multiply by multiply by multiply by
0.1112 8.994 A13+ 5.564 0.1797
0.2775 3.604 B3+ 13.89 0.07201
0.01456 68.67 Ba2+ 0.7286 1.373
0.04990 20.04 Ca2+ 2.497 0.4005
2+
0.03148 31.77 Cu 1.575 0.6348
2+
0.03581 27.92 Fe 1.792 0.5580
3+
0.05372 18.62 Fe 2.688 0.3720
+
0.9921 1.008 H 49.64 0.02014
+
0.1441 6.939 Li 7.211 0.1387
2+
0.08226 12.16 Mg 4.116 0.2430
2+
0.03640 27.47 Mn 1.822 0.5490
4+
0.07281 13.73 Mn 3.645 0.2744
+
0.04350 22.99 Na 2.177 0.4594
0.5544 18.04 NH +4 2.774 0.3605
+
0.009653 103.6 Pb 0.4830 2.070
2+
0.02283 43.81 Sr 1.142 0.8755
2+
0.03060 32.69 Zn 1.531 0.6533
meq/L → CaCO3, multiply by 50.04
CaCO3 → meq/L, multiply by 0.01998
related to the silica standards and were called Jackson

Turbidity Units (JTU). Because suspensions of the silica
standards were difficult to reproduce, they were replaced
by suspensions of formazin, a polymer that could be
readily and reproducibly prepared by mixing two simple
solutions. Use of this suspended solid as a standard gave
rise to the formazin turbidity unit (FTU). Instruments
that measure the light scattered rather than absorbed by
the particles were developed to measure low turbidity
levels. These instruments were called nephelometers to
distinguish them from generic turbidimeters that mea-
sured transmitted or absorbed light. Use of these instru-
ments gave rise to the nephelometric turbidity unit

Table 10 Conversion Factors for Anions
To convert from To convert from

→meQ/L
mg/l→ →mg/L
meq/l→ Anion →CaCO3
mg/L→ CaCO3→mg/L
multiply by multiply by multiply by multiply by
2-
0.02336 42.81 BO 1.169 0.8555
-
0.01251 79.97 Br 1.597 0.6262
-
0.02821 35.45 Cl 1.412 0.7084
0.03333 30.00 CO 3
2−
1.669 0.5995
0.01724 58.00 CrO 4
2−
0.8628 1.159
-
0.05264 19.00 F 2.634 0.3797
0.01639 61.02 HCO −3 0.8201 1.219
0.02084 47.99 HPO 4
2−
1.043 0.9590
0.01031 96.99 H 2 PO −4 0.5159 1.938
-
0.03024 33.07 HS 1.513 0.6609
0.01233 81.07 HSO 3− 0.6172 1.620
0.01030 97.07 HSO −4 0.5155 1.940
-
0.007880 126.9 I 0.3943 2.536
−
0.02174 46.01 NO 2 1.089 0.9195
−
0.01613 62.00 NO 3 0.8071 1.239
-
0.05880 17.01 OH 2.942 0.3399
0.03159 31.66 PO 4
3−
1.581 0.6327
2-
0.06238 16.03 S 3.122 0.3203
0.02629 38.04 SiO 3
2−
1.315 0.7602
0.02498 40.03 SO 3
2−
1.250 0.8000
0.02083 48.03 SO 4
2−
1.042 0.9589
meq/L → CaCO3, multiply by 50.04
CaCO3 → meq/L, multiply by 0.01998

2-44
Table 11 Con centration Con version Factors
CO NV ERSIO NS W ITH IN PH YSICA L CON CEN TR ATIO N U NITS
GIV EN C ONC ENTRA TION

SOU GHT m g/L wt % ppt ppm gp g
C ONCEN TRATI ON A B C D E
1E3*R*C
m g/L, A — 1E4*R*B 0.1*C R*D 5.84E-2*E
wt %, B 1E-4*A /R — — 1E-4*D 5.84E-6*E/R
ppt, C 1E-3*A /R 10*B 2E-3*C 1E-3*D 5.84E-5*E/R
ppm , D A/R 1E4*B 1.71E4*R*C — 5.84-2*E/R
gpg , E 17.1*A 1.71E5*R*B 17.1*R*d —
CO NV ERSIO NS W ITH IN CH EM IC AL C ON CEN TRA TION UN ITS

SOU GHT m eq/L epm m g/L as Nor m ality Mo larity Mo lality
C ONCEN TRATI ON F G C aC O 3 N M m
m eq /L, F — R*G H/50 1E3*N 1E3*#*M 1E3*#*S*m
epm , G F/ R — H/(50*R) 1E3*N/R 1E3*#*M/R 1E3*#S*m/ R
m g/L as C aCO 3 , H 50*F 50*R*G — 5E4*N 5E4*#*M 5E4*#*S*m
Nor mality, N 1E-3*F 1E-3*R*G 2E-5*H/# — #*M S*#*m
M olar ity, M 1E-3*F /# 1E-3*R*G/ # 2E- N/# — S*m
M olar ity, m 1E-3*F /(#*S) 1E-3R*G/(#*S) 5*H/(#* S) N/(#* S) M /S —
CO NV ERSIO NS B ETW EEN PHY SIC AL A ND CH EM IC AL C ON CEN TRA TION UN IT S

SOU GHT m g/L m eq/L Nor m ality Mo larity
C ONCEN TRATI ON A F N M
m g/L, A — J* F 1E3*J*N 1E3*#*J*M
m eq /L, F A/J — 1E3*N 1E3*#*M
Nor mality, N 1E-3*A /J 1E-3*F /# N/# —
A dditional definitions:
J = milliequivalent weight, mg
R = solution density, kg/L
S = (R − TDS∗1E − 6) , weight of solv ent in 1-liter of solution, kg
TDS = num ber of equiv alent/m ole
Revised: February 4, 1991
(NTU) as the preferred expression of turbidity. Formazin
standards are still used, but using NTU indicates the
manner in which the turbidity is measured.
Density, g/mL, or Specific Gravity — Density is the
weight in grams of 1 mL of solution (numerically equal
to the weight in kilograms of one liter of solution). Spe-
cific gravity is the ratio of the weight of a specific volume
of solution to the weight of the same volume of distilled
water. Because both water and solution volumes are
temperature-dependent, the temperatures at which the
density or specific gravity was measured should be
specified. The terms “density” and “specific gravity” are
frequently used interchangeably. This substitution is not
completely accurate. The density of distilled water, at all
reasonable pressures, is always less than one, so specific
gravities are always numerically greater than densities.
For many systems, though, the substitution is acceptable
because the density of water at ambient temperatures is
within 0.5% of 1 g/mL.
Specific Conductivity, mho/cm or µmho/cm — Conduc-
tivity is a measure of the ability of an ionic solution to The now-preferred term
conduct an electric current. The standard unit of conduc-
for specific conductivity
tance is specific conductance, k, defined as the reciprocal
of the resistance, at a specified temperature, of a solution is simply conductivity.
contained between two parallel electrodes, each 1 cm2 in
cross section and 1 cm apart. The unit of k is reciprocal
ohms (mhos) per cm. Conductance is sometimes stated
in siemens/cm, the SI unit, where 1 mho = 1 siemen.
Most solutions have a limited power to conduct a cur-
rent, so specific conductivities are frequently reported in
µmhos/cm.
Specific Resistivity, ohm-m — Resistivity, the opposition The now-preferred term
of an ionic solution to carry an electric current, is equal to for specific resistivity is
the reciprocal of the conductance. The unit of specific
resistivity used in water analysis usually is ohm-meter. simply resistivity.
Hypothetical Salt Combinations

The SI unit for
Some older water analysis forms gave concentration in
terms of neutral compounds (calcium carbonate, calcium conductivity is the
sulfate, magnesium sulfate, sodium chloride, etc.) rather siemen.
than individual ions. These combinations were arrived at 1 siemen = 1 mho
by matching certain cations with certain anions in as-

sumed and purely hypothetical combinations. The com-
binations used could vary from one analysis to another,
depending on the purpose or use of the analysis. Pre-
senting analytical results in this format is not recom-
mended because the combinations are arbitrary and
falsely portray the dissolved species as existing in solu-
tion as specific, nonionized compounds.
Solubility Calculations
Water analysis reports frequently include solubility
Solubility calculations calculations for calcium carbonate, calcium sulfate,
will tell if a precipitate barium sulfate, and sometimes strontium sulfate, the
most common precipitates in oilfield waters. Service
will form — they cannot
companies performing chemical analyses usually have
tell how fast a precipitate their own computer programs, some proprietary and
will form. some not, for these calculations. Patton10 (Pages 65-79)
describes some of the simple predictive calculations.
Solubility calculations are based on equilibrium, thermo-
dynamic data and ignore how fast a precipitate will form
(kinetics). Even when calculated solubilities are exceeded
for some components in solution, precipitates do not
appear in many systems because of tendencies to form
supersaturated solution or the presence of scale inhibi-
tors (added or naturally occurring). Solubility calcula-
Reliable solubility
tions are based on the chemical analysis of a specific
calculations at any point sample. A solubility calculation can be extrapolated to a
in a system requires system only if the sample and chemical analysis truly
accurate chemical analysis represent the system at its operating conditions. A com-
mon oversight is to use a laboratory-measured pH for a
at the same point.
carbonate scale calculation. The laboratory pH is usually
higher than the field pH because of loss of carbon diox-
ide. Thus, calculation based on the laboratory pH will
underestimate the solubility of carbonate scales at system
conditions. Another oversight concerns the interpreta-
tion of reported alkalinity. Many oilfield waters contain
components other than carbonate/bicarbonate that can
contribute to alkalinity. Assuming that all the alkalinity
of such waters results from carbonate/bicarbonate will
underestimate the solubility of carbonate scales. Some
earlier calculations for scaling tendencies were based on
relatively low-temperature, low-salinity systems. These
procedures lack a sufficiently extensive database to yield

reasonable estimates for extremes in salinity, tem-
perature, or pressure. They frequently neglect the effect Caution!!
of ion pairing upon ion activities in concentrated solu- Simple calculation
tions. Simple calculations based on analytically mea-
procedures may not be
sured ion concentrations rather than thermodynamically
calculated ion activities underestimate the solubility of adequate for complex and
CaSO4 in seawater because they neglect the reduced concentrated oilfield
activity owing to MgSO4° ion pair formation. Unless waters.
these program, database, and analysis limitations are
understood and accounted for, solubility calculations and
scaling tendencies reported on water analysis forms can
be misleading.
Composition Diagrams
A number of ways to express water analysis data graphi-
cally have been proposed. A graphical presentation
usually permits more rapid comparison of a number of
water analyses and highlights differences and similarities
that might be missed by someone scanning tabular data.
With the availability of PC’s and database programs for
data comparison, use of diagrams for comparison is
declining. Patton10 and Ostroff12 described a number of
these diagrams.
Quality Control
In the broadest sense, quality control or quality assurance
is the sum total of all methods, procedures, and practices
used to determine and maintain the quality of the ana-
lytical data produced by a laboratory. An excellent dis-
cussion of this aspect of quality assurance is given in Sec.
1020 of Ref. 2 (17th edition). In this chapter, quality
control is used in a more limited sense to indicate correct-
ness or reliability of analysis. A complete geochemical
analysis — including the major anions and cations, mea-
sured total dissolved solids, conductivity, density, and
pH — is required to check for correctness of analysis.
The anion/cation balance
Anion/Cation Balance is the primary method of
Determining the anion/cation balance is the primary checking the
method of checking an analysis. This procedure is based completeness of an
on the fact that aqueous solutions are electrically neutral
and therefore the sum of the concentrations of anions analysis.

must equal the sum of the concentrations of cations (all
concentration are expressed in milliequivalents per liter).
Earlier editions of Ref. 2 (15th edition published in 1980)
defined acceptable limits for the difference in anion and
cation concentrations (which would be zero in the perfect
analysis) according to
∑ (anions) − ∑ (cations) = ±[0.1065 + 0.0155∗ ∑ (anions)]

In the 17th edition of Ref. 2, the test is based on the per-
centage difference,
% difference = 100∗
[(cations) − ∑ (anions)]
[∑ (cations) + ∑ (anions)]
with a criteria of acceptance taken from Ref. 13:
Anion Sum Acceptable

(meq./L) Difference
0 - 3.0 ± 0.2 meq./L
3.0 - 10.0 ± 2%
20.0 - 800 ± (2 - 5)%
Calculation of the anion/cation balance has another use.

If the ion sums are exactly equal, there is adequate reason
to suspect that one or more components were determined
by difference rather than by actual analysis. Such an
analysis should be questioned, for the balancing proce-
dure has concealed any analytical or calculational errors.
Calculated vs. Measured TDS

The calculated TDS is obtained by adding the concentra-
tions, in mg/L, of all dissolved components:
Calc. TDS, mg / L = Na + + K + + Ca + + Mg + +K
2 2
The calculated TDS
2− − − 2−
+ CO 3 + HCO 3 + Cl + SO 4 + C 2 H 3 O 2 +K , mg / L
-
should be equal to the
measured TDS. Alkalinity and hardness, if expressed as mg/L as CaCO3,
must be broken down into the individual responsible
ions, with concentrations expressed in mg/L, before
being included in the above equation. Thus, total alkalin-
ity in mg/L as CaCO3 should be divided into mg/L of

− − −
CO 2−
3 , HCO 3 , C 2 H 3 O 2 , HS , and any other ion in the
base form that contributes significantly to the alkalinity.

Likewise, total hardness in mg/L as CaCO 3 is divided
into mg/L of Ca2+ and Mg2+. The standard method cal-
culation given in the 17th edition of Ref. 2 (Page 20) is
correct only in those rare cases where pH > ≅9.5 and all
alkalinity is due to CO 2− 2−
3 and only CO 3 . In all other
cases, use of this standard method will underestimate the

weight of dissolved solids contained in the alkalinity
term by up to one-half.
The criterion for acceptance based on calculated and
measured TDS is
measured TDS
1.0 < < 1.2
calculated TDS
Measured TDS is more likely to be greater than calcu-

lated TDS (1) because a significant component may have
been omitted in the analysis and hence in the calculated
TDS or (2) because of contamination or incomplete dehy-
dration. If the ratio of measured/calculated TDS ratio is
<1, the larger of the anion or cation sums and the mea-
sured TDS may be wrong and should be checked or
reanalyzed. If the ratio >1.2, components in the smaller
of the ion sums should be reanalyzed.
Calculated vs. Measured Specific Gravity

When materials are dissolved in water, the specific grav-
ity of the resulting solution is increased in proportion to Specific gravity is a
the amount of material dissolved. The expected specific reliable measure of TDS
gravity of a solution can be estimated from the measured
(or calculated) TDS content. Table 12 gives empirical only for high TDS
equations for estimating specific gravity. solutions.
Patton10 (Appendix 5, Page 320) presents a graphical
relationship between TDS and specific gravity. This
graph has a curvature and a set of outside lines to indi-
cate the expected spread in data. This method is not
sensitive for low-TDS solutions (<20,000 to 30,000 mg/L).
The curvature in the graph and the difference in the
proportionality constant in the two empirical equations

Table 12 Calculation of Specific Gravity from Measured TDS
Equation Reference
−6
Sp.Gr. = 1 + TDS(mg / L)∗0.695 × 10 Ostroff, Ref. 12, p. 34
−6
Sp.Gr. = 1 + TDS(mg / L)∗0.725 × 10 Jones, Ref. 14, p. 109
Abbreviations:
Sp. Gr. = Specific Gravity TDS = Total Dissolved Solids
in Table 12 indicate the uncertainties that should be

expected even for high-TDS solutions when this method
is used to compare TDS and expected specific gravity.
Methods Using Electrolytic Conductivity

The major components of oilfield waters exist in solution
Electrolytic conductivity principally as positively charged cations and negatively
charged anions. These ions can carry an electric current
is a reliable measure of
through the solution. This current-carrying ability is
the completeness of an called conductance; conductance is the inverse or recip-
analysis, particularly for rocal of resistance. The overall conductance of a solution
low TDS samples. is determined by the total number of ions present and the
current-carrying capacity of each type of ion. The latter
property is known for most ions from theoretical or
empirical studies, at least for dilute solutions. Therefore,
the expected conductivity resulting from dissolved ions
can be calculated from the reported analysis and used as
a quality-control parameter by comparison with the
measured conductivity.
Three methods that use conductivity as a quality-
control parameter are described in the following sections.
All methods using conductivity suffer from inaccuracies
for solutions containing many types of anions and cat-
ions at high concentrations. They also are inadequate for
solutions containing large amounts of complex-forming
or ion-pairing ions, such as Ca2+ or Mg2+ , that effectively
decrease the number or magnitude of charged ions. The
first method, comparing measured and calculated con-
ductivities, is more sophisticated and precise but in-

volves extensive calculations and dilutions for accurate
results. The other two methods, using ionic sums and
TDS, are simpler to use and give an approximate check
on accuracy.
Measured vs. Calculated Conductivity — Ref. 2 uses two
methods to calculate a “hypothetical conductivity” for an
analyzed sample. In the method described in earlier
editions (15th edition), a diluted conductivity is calcu-
lated by multiplying the concentration of each ion by a
conductivity factor, f, taken from Table 13 and summing
the products according to the following equation:
Calculated Conductivity = ∑ (c + f+ ) + ∑ (c − f− )
where c and f are concentrations and factors, respectively,

from Table 13.
Table 13 Conductivity Factors for Ions in Dilute Aqueous Solutions.

From Reference 2 (1980), p. 32.
Conductivity (25ºC)
µmhos/cm
Ion Per meq/L Per mg/L
Sodium 48.9 2.13
Potassium 72.0 1.84
Calcium 52.0 2.60
Magnesium 46.6 3.82
Carbonate 84.6 2.82
Bicarbonate 43.6 0.715
Chloride 75.9 2.14
Sulfate 73.9 1.54
The electrolytic conductivity of the analyzed sample that

has been quantitatively diluted to a TDS of 50 to 80 mg/L
(conductivity of 90 to 120 µmhos/cm) is measured. The
calculated “diluted conductivity” is obtained by multi-
plying the measured conductivity by the dilution factor,
([Vs + Vw]/Vs). The analysis is assumed to be correct if
the diluted conductivity is between 98% and 101.5% of
the conductivity computed by the above method. This
method is suitable for solutions with pH between 6 and
9. It is greatly affected by the accuracy of measurement

of the conductivity of the diluted sample and possible
errors from the large dilution factors that must be used
for high-TDS samples.
In the 17th edition of Ref. 2, conductivity is calculated
from the following theoretical equation:
G = λ C − (k 1λ + k 2 )C 2
3
where
G = conductivity of solution,
C = concentration of solution,
λ = equivalent conductivity at infinite dilution,
and
k1,k2 = constants for relaxation of ion cloud electro-
phoretic effects relative to ion mobility.
Calculation procedures13 for solutions of mixed anions
and cations are best performed on a PC. The theoretical
equations are valid up to a TDS concentration of about
5,000 mg/L. The complex calculations and dilutions
required for most samples make this method a second
choice. The first choice is the method using extensive
dilution and calculation with simple conductivity factors.
Measured Conductivity vs. Ion Sums — The anion and
cation sums, in meq/L, should be numerically equal to
approximately 1% of the conductivity, in µmhos/cm.
100∗∑ Anion( meq L)

= 0.9 − 1.1
Conductivity (µmhos cm)
and
100∗∑ Cation( meq L )

= 0.9 − 1.1
Conductivity(µmhos cm)
If either sum does not meet this criterion, that analysis is

suspect.
Measured Conductivity vs. Measured or Calculated TDS
— The ratio of the measured or calculated TDS, in mg/L,
to conductivity, in µmhos/cm, should fall within the
range of 0.55 to 0.7.

Measured TDS( mg L)
= 0.55 − 0.7
Conductivity (µmhos cm)
and
Calculated TDS( mg L )
= 0.55 − 0.7
Conductivity(µmhos cm)
For solutions with pH <5 or pH >9, the ratio will be <0.55

because of the high conductivity of the hydrogen and
hydroxyl ions, respectively. For high-TDS waters or
waters containing appreciable amounts of ions with
pronounced tendencies to form ion pairs (e.g., Ca 2+, Mg2+,
and ), the ratio will be >0.7 because of the presence of
fewer current-carrying ions.
Regions of pH and Carbonate Species

Sample pH can be used as an internal check for the pres-
ence or absence of hydroxide, carbonate, bicarbonate,
and carbonic acid species. For example,
If pH ≥ 8.5
OH − , CO 2− −
3 , or HCO 3 is possibly present, and
H2CO3(dissolved CO2) is definitely absent.
If 4.5 ≤ pH ≤ 8.5
HCO −3 or H2CO3 is possibly present, and

2− −
CO 3 or titratable OH is definitely absent.
The pH should be measured when the sample is anal- The pressure of hydroxyl,
yzed. This method depends heavily on the accuracy of carbonate, and
the pH calibration and analytical procedures used to bicarbonate ions and
determine the types of alkalinity present. It is not reliable
carbonic acids can be
for waters containing large amounts of organic acids that
act as buffering agents and thereby fix the pH. It applies inferred from the
only to the species present at the time of analysis and pH measured pH.
measurement.

Frequently, the concentration of ions that form slightly
Solubility or saturation soluble compounds (e.g., calcium carbonate, calcium
calculations are not sulfate, or barium sulfate) are compared with those
present in a saturated solution. If the analyzed ions are
reliable indicators of the present at concentrations greater than saturation, the
accuracy of an analysis. analysis is said to be suspect. Saturation or solubility
calculations for concentrations are not reliable quality-
control indicators. Oilfield waters are frequently super-
saturated with respect to precipitating solids. Or they
contain naturally occurring or added scale inhibitors or
other components that affect the activity (and hence the
apparent solubility) of dissolved ions without affecting
the analyzed concentrations. Also, the sample may not
have been adequately filtered, and some finely divided
precipitate may have been included in the analysis as
soluble ions.
Replicates, Standards, and Spiked Samples

Duplicate samples, standards, or spiked samples (regular
Duplicate samples, samples containing known additions of one or more of
standards, and spiked the analyzed components) are frequently submitted with
regular samples to check accuracy and precision of ana-
samples are frequently lytical procedures. The analytical results for components
used to check the in duplicate or standard samples should agree within the
reliability of an analysis. expected precision or standard deviation of the analytical
methods used. Recovery of added components in spiked
samples should also be comparable to the precision of the
analytical methods used. And as a final check, analytical
results may be compared with those obtained for samples
submitted previously from the same sample points and
under the same or similar operating conditions. Signifi-
cant deviations should raise a flag to determine whether
the variation results from a bad analysis or a change in
the process.
OIL-IN-WATER ANALYSIS
The objectives of this analysis are (1) to determine the
amount of oil in water (oil content) before discharge to
the ocean or other surface waters for regulatory pur-
poses, (2) to determine the amount of dispersed or free
oil in injection water for water-quality studies, or (3) to

determine the amount of dispersed oil for ascertaining
the operating efficiency of oily water treating chemicals
and separation equipment.
Free Oil vs. Dissolved Oil

Crude oil may exist as dispersed or free oil - a finely
divided, immiscible liquid phase separate from the water The distinction between
phase. Crude oil, or its individual components, may also free oil and dissolved oil
be truly dissolved as individual molecules in produced
is critical for
water (single liquid phase). The distinction between free
and dissolved oil becomes critical for oil-in-water analy- environmental concerns
ses. Thus, most equipment for oily water separations or when evaluating
will remove only free or dispersed oil. An analytical separation and treating
procedure that is simple, easily run in the field, and has
equipment.
little or no response to dissolved oil is most useful for
measuring the performance of such equipment and
associated chemicals. On the other hand, various regula-
tory agencies restrict the oil content for produced water
Free oil — separate,
discharged to surface waters. These agencies specify not
only the amount of oil to be tolerated but also the test immiscible liquid
method that must be used to measure the oil content. phases.
The specified test procedures do not always distinguish Dissolved oil — single
between free oil and dissolved oil. Indeed, “oil” is de-
liquid phase.
fined, in these test methods, as anything measured by the
method.
Dissolved Oil
The individual components of crude oil vary widely in
their solubilities in water. Table 14 lists water solubili- The solubilities of crude
ties15 of some typical hydrocarbons. General trends in oil components vary
solubility behavior are evident. For any given class of
hydrocarbon compounds (a homologous series), the widely.
logarithm of the solubility decreases linearly with the
molar volume of the hydrocarbon molecule; aqueous
solubility decreases as the number of carbon atoms in the
molecule increases. Ringed compounds (cycloalkanes)
are more soluble than paraffins (alkanes) with the same
number of carbon atoms. Double and triple bonds within
the carbon chain increase solubility with
alkyenes > alkadienes > alkenes > alkanes.

Table 14 Solubility of Hydrocarbons in Water at Room Temperature
Class Compound Formula Solubility, ppm

Alkane Propane C3H8 62.4 ± 2.1
n-Hexane C6H14 9.5 ± 1.3
n-Octane C8H18 0.66 ± 0.06
Alkene Propene C3H6 200 ± 27
1-Hexene C6H12 50 ± 1.2
1-Octene C8H16 2.7 ± 0.2
1, 5-Hexadiene C6H14 169
Alkyne Propyne C3H4 3640 ± 125
1-Hexyne C6H10 94 ± 3
1-Octyne C8H14 24 ± 0.8
Cyclic Cyclohexane C6H12 156 ± 9
Cyclohexene C6H10 213 ± 10
Cyclooctane C8H16 7.9 ± 1.8
Aromatic Benzene C6H6 1780 ± 45
Toluene C7H8 515 ± 17
Naphthalene C10H 8 34
Aromatic hydrocarbons are more soluble than any other

hydrocarbon of the same carbon content. Using the C6
hydrocarbons as an example, solubilities can be summa-
rized as follows:
Benzene Cyclo- Hexadiene Cyclo- Hexyne Hexene Hexane

hexene hexane
1780 ppm > 213 ppm > 169 ppm > 156 ppm > 94 ppm > 50 ppm > 9.5 ppm
Hetero-atoms (e.g., oxygen, nitrogen, and sulfur) that can

form hydrogen bonds with water will increase the aque-
ous solubility of organic molecules. This is true whether
Aromatics, unsaturates, the hetero-atom is within the carbon chain (ethers and
and oxygen-containing heterocyclics), at the end of a carbon chain (alcohols,
aldehydes, and acids), or a side element (ketones). The
organic molecules have carboxylic acid grouping deserves special mention. The
high water solubilities. free, un-ionized or undissociated acid, R-COOH, that
exists in solutions of low pH, has a much greater solubil-
ity that the paraffin hydrocarbon with the same number
of carbon atoms. In solutions of higher pH, where the

acid is dissociated into its base form (R-COO-), the solu-
bility increases by approximately three orders of magni-
tude over the undissociated acid form. Thus, for the C12
dodecane series, the variation in water solubilities is:
Dodecanoate Dodecanoic
(Laurate), (Lauric) Acid,
C11H 23COO - C11H 23COOH Dodecane C 12H26
42,000 ppm > 55 ppm > 0.01 ppm*

* Solubilities for dodecane were estimated from
Figure 4 of Reference 15.
Until now, this discussion has been concerned with the

solubility of the pure organic compound in water. In The water solubility of
oilfield waters, the organic compounds are in contact most organics is affected
with both a produced-water phase and a crude oil phase.
by their tendency to
The “soluble organics,” in this case, partition between the
aqueous phase and the organic phase. The partition partition between the
coefficient, which indicates the extent of distribution of a produced water and the
species between the two phases, is influenced by the crude oil phases.
solubilities of the species in each phase. The materials
under discussion, except for the lower-molecular-weight
acids in their anion (ionized or dissociated) form, R-COO-,
prefer the organic (crude oil) phase to the aqueous phase.
The net result is that soluble organics in the water phase,
except for the acid anions, are present in the tens of ppm
range, considerably less than their saturation amounts.
However, the acid anion, R-COO-, has a high affinity for
the aqueous phase and may be present in the thousands
of ppm range.
Free Oil Most of the dispersed oil

Crude oil may also exist as a discrete, immiscible phase is contained in larger,
in produced water. Oil droplet diameters range from readily separated oil
submicrometers to 100 micrometers or larger. The
droplets. Smaller droplets
larger droplets tend to be unstable and coalesce into still
larger droplets that rapidly separate and rise to the top of are more difficult to
the system. Although there are fewer large droplets than separate but contain
the small droplets, the large droplets contain the bulk of smaller fractions of total
the volume or weight of the dispersed oil. Because of
oil.

their size, they usually are easily removed by con-
ventional separation equipment — gravity separators,
flotation units, liquid/liquid hydrocyclones, filters, etc.
The small oil droplets tend to form stable dispersions.
According to Stoke’s law, the rise velocity of lighter oil
droplets in water is proportional to the square of the
droplet radius. The low rise velocity of small droplets is
easily surmounted by convective currents within the
system from temperature gradients and fluid flow and
mixing. The small droplets become stirred within the
system and do not rise to the top. Small drops can be
stabilized and kept from coalescing to more readily
separated larger drops by a variety of solid particles and
added or naturally occurring surfactants. Small droplets
frequently have large surface charge densities that fur-
ther impede coalescence. Although the number of these
droplets is high, the oil volume contained in them is
usually a small fraction of the total free oil. Small drop-
lets are difficult to remove with conventional separation
equipment. Despite their small size, they may cause
extensive reservoir plugging by altering the nature of the
surfaces in the pores of the reservoir rock and by acting
as a glue for other particulates present (e.g., corrosion
products, scale particles, formation fines, spent acids, and
precipitated asphaltenes).
Sampling
Sampling procedures for oil-in-water analyses are very
critical for obtaining results that are truly representative
of the bulk water stream. Free oil readily adsorbs onto
and contaminates most surfaces. All glassware used for
sampling and testing should be thoroughly cleaned and
then rinsed with the extracting solvent before use.
Samples should be taken and stored directly in glass
bottles with metal-foil-lined, screw-cap closures. Plastic
containers should never be used because free oil readily
adsorbs onto plastic surfaces and is difficult to remove
even with repeated solvent washes. See the previous
section on sampling for chemical analysis for precautions
about shipping samples in glass containers.

1. Sample from a well-mixed, flowing stream with a
thoroughly flushed sample cock and lines. Do not
sample from regions with low or no velocity. Samples
from the upper portions of pipes and vessels may
contain larger amounts of free oil than the bulk of the
system because of gravity separation.
2. Fill the sample bottle nearly to the top. Do not over-
flow the sample bottle. Leave an air space on the top
of the sample bottle.
3. Fill out the sample identification form (Table 2), label
the sample bottle, and mark the position of the water
meniscus on the bottle for subsequent measurement
of sample volume. If the sample cannot be analyzed
within a few hours, preserve it by adding 5 mL of 1:1
HCl per liter of sample and refrigerating at 4°C.
4. Collect a separate 1-L sample for the oil-in-water
determination. This sample should not be used for
any other analytical procedures. Do not transfer the
sample to another container before analysis.
Analytical Procedures
Several methods, differing in complexity, specificity to oil
and possible interferences, are available. The method of
choice is usually dictated by the ultimate use of the
acquired data; for example, to satisfy regulatory agencies
for NPDES permitting, U. S. Environmental Protection
Agency (EPA) Method 413.1 must be used. A measure of
free or dispersed oil (not including dissolved organics) as
given by the API colorimetric method or a modification is
more useful for evaluating oil water treating chemicals
and equipment.
Filtering the water sample before analysis is said to
distinguish between free oil and dissolved oil. The unfil- The distinction between
tered sample is said to contain “total oil” (free + dis- free oil and dissolved oil
solved); the filtrate is said to contain “dissolved oil.”
is not always possible in
This method of separation is not reliable or complete
because significant amounts of free oil may bleed an analytical procedure.
through the filter media and appear in the filtrate, espe-
cially when the samples contain large amounts of free oil.
Multiple filtrations may be necessary to remove all the

free oil. The additional filtration steps increase the possi-
All oil and grease bility that some dissolved oil will be lost because of
methods that use a adsorption on surfaces.
chlorofluorocarbon
EPA Method 413.1. Oil and Grease. Total,
solvent are being phased Recoverable (Gravimetric, Separator Funnel
out because of possible Extraction)
detrimental effects of the
The U.S. EPA Method 413.1 (Ref. 9, Page 413.1-1) is also
solvent. Replacement described in APHA/AWWA/WPCF Standard Method
solvents have not been 503A, “Oil and Grease, Partition — Gravimetric,” (Ref. 2,
approved as of June 1994. 15th edition, Page 461) or ASTM D 4281-83, “Standard
Test Method for Oil and Grease (Fluorocarbon Extract-
able Substances) by Gravimetric Determination,” (Ref.
16). This method is the only one approved by and ac-
ceptable to the EPA for NPDES permits. The method
EPA Method 413.1 is involves acidifying the water sample, extracting with a
usually the only fluorocarbon solvent, and gravimetrically determining
the residue in the evaporated extractant. In addition to
acceptable procedure for
dispersed oil, the method may pick up dissolved oil,
NPDES permits. other dissolved organics, and extractable sulfur, thereby
giving high results. For crude oils containing fractions
with limited solubility in the fluorocarbon solvent, ex-
traction is incomplete and low results are obtained. Light
hydrocarbons (gasoline through No. 2 fuel oil fractions)
and volatile extracted material may be lost during the
prescribed 70°C evaporation step, again giving low
results.
EPA Method 413.2. Oil and Grease. Total

Recoverable (Spectrophotometric, Infrared)
EPA Method 413.2 (Ref. 9, Page 413.2-1) is also described
EPA Method 413.2 usually in APHA/AWWA/WPCF Standard Method 503A, “Oil
and Grease, Partition-Infrared,” (Ref. 2, 15th edition,
recovers more “oil” than Page 462) or ASTM D 3921-85, “Standard Test Method for
does 413.1. However, it Oil and Grease and Petroleum Hydrocarbons in Water,”
may “over recover” some (Ref. 17). Extraction procedures are the same as in EPA
component such as Method 413.1, but the amount of material in the
extractant is determined by infrared spectrophotometry
organic acids. rather than by evaporation and gravimetric analysis. A
calibration curve of infrared absorption vs. oil concentra-
tion is prepared from known amounts of the crude oil in
question in the extracting solvent. If the crude oil is not

available, a reference oil is prepared by mixing n-
hexadecane, iso-octane, and chlorobenzene. Like Method
413.1, this method will detect dispersed and dissolved oil
and other organics that are extractable and have carbon-
hydrogen groups that absorb infrared radiation in the
region of measurement. Organic acids and other extract-
able materials may give high results if the calibration
curve is prepared from only oil or standard hydrocarbon
mixtures. (Organic acids form dimers in the extracting
solvent. These dimer acids have a broad absorption band
in the same region as the carbon-hydrogen bands and can
cause interference if the proper background level is not
selected.) This method usually gives higher results than
Method 413.1 because of smaller losses of volatile, light
hydrocarbons. The higher results could also be due to
spectral interferences of the type indicated for dimer
acids. Method 413.2 cannot be used for NPDES permit-
ting.
EPA Method 418.1 Petroleum Hydrocarbons.

Total Recoverable (Spectrophotometric,
Infrared)
EPA Method 418.1 (Ref. 9, Page 418.1-1) is also described
in APHA/AWWA/WPCF Standard Method 503E, EPA Method 418.1 is more
“Hydrocarbons,” (Ref. 2, 15th edition, Page 465) or specified for dissolved
ASTM D 3921-85, “Standard Test Method for Oil and
and dispersed
Grease and Petroleum Hydrocarbons in Water,” (Ref. 17).
This method is similar to Method 413.2, except polar hydrocarbons because
organic materials are removed from the fluorocarbon other polar organic
extract by adsorption onto silica gel before the infrared compounds are removed
determination. This method is more specific for dis-
by adsorption and silica
persed and dissolved oil because many other dissolved
organics in water are polar enough to be removed by the gel.
silica gel. Methods 413.2 and 418.1 are frequently com-
bined to give an oil and grease and a petroleum hydro-
carbon measurement on the same sample. This method
is widely used in Europe but is not acceptable in the U. S.
for NPDES permitting.

API Recommended Practice for Analysis of
Oilfield Waters, API RP 45
The API colorimetric method (Ref. 8) uses a chlorinated
API RP 45 colorimetric or a hydrocarbon solvent to extract dispersed and dis-
method is particularly solved oil from an unacidified water sample. This
method then determines the amount of extracted oil by
suitable for evaluating the
colorimetry or spectrophotometry in the visible region.
efficiency of separation Because the extracting solvent is not specified and can
equipment because it have carbon-hydrogen bonds (as is the case with the
responds primarily to infrared methods), a greater choice of extracting solvents
is available, and extraction efficiencies or recoveries of
dispersed oil.
hydrocarbon can be higher. The extracted oil must ab-
sorb radiation in the spectral region of interest. The
method is more sensitive for dark crude oils. Extracted
materials that are colorless (do not absorb significantly at
the analytical wavelength) are not detected. Extraction is
from an unacidified water sample, so many soluble, polar
organic acids in the water are in the ionized (base) form.
These anion forms are not extracted to a great extent.
Thus, they are not detected by this method. We can
control sensitivity and concentration ranges determined
somewhat by properly selecting the wavelength used for
the absorption measurements. This is commonly done by
determining the absorption spectra while preparing the
calibration curve. A calibration curve must be prepared
for each oil to be determined because of wide variations
in spectra and absorption coefficients of different crude
oils.
Quality Control
Five issues are involved in quality control for an oil-in-
water analysis:
1. Sampling procedure. How representative is the
analyzed sample of the system being studied?
2. Sample container material. How much of the oil in
the sample is irreversibly lost to the walls of the
sample container?
3. Extraction efficiency. The three EPA procedures dis-
cussed specify the extraction conditions and do not
permit variations. The designated fluorocarbon
solvent was chosen because of its relatively low

toxicity (compared with carbon tetrachloride) and its
lack of carbon-hydrogen bonds (a necessary condition
for infrared analyses). Using this solvent also means
that one specified solvent is used for all three meth-
ods. However, some crude oils are not completely
soluble in or extracted by this solvent. Under these
conditions, low analytical results would be expected.
On the other hand, some materials other than oil,
such as sulfur and certain organic acids, are soluble in
and extracted by the fluorocarbon, leading to high
results. Modification of the API colorimetric method
permits use of a more efficient extractant as long as
the extracting solvent is colorless in the region of the
analytical wavelength. With the option of a more effi-
cient and selective extractant, analytical results would
be expected to be more representative of actual oil
content, with less interference from colorless non-oil
components extracted from the sample.
4. Test accuracy and repeatability. Measurement repeat-
ability (precision) is best achieved by consistently Accuracy — closeness of
and completely following a prescribed set of steps in
determined value to
both sampling and analysis procedures. Even when
these precautions are followed, there can be consider- the correct or true
able variations between different operators. Personal value
variations can be minimized by using the same per- Precision — repeatability
sonnel for all tests in a given series. Precision can be
of measurements.
ascertained by separate analysis of replicate samples,
if there is reasonable assurance that there has been no
change in oil content between samples.
Accuracy is more difficult to assess. Accuracy de-
pends significantly on the type and properties of the Recovery factors, rather
oil in the sample, on the recovery efficiency of the
than accuracy, are usually
extracting solvent, on the volatility of the extracted
components, and on the specificity of the extracting specified for oil and
solvent and the measurement procedure for crude oil. grease methods.
Accuracy would be expected to improve by using
solvents with greater extraction selectivity and effi-
ciency for crude oil components, by using measure-
ment procedures that retain more of the volatile
components in the extract, and by calibrating the
method with the crude oil in question. The accuracy
of these determinations cannot be measured directly

for natural water samples. Recovery factors, rather
than accuracy figures, are usually specified. The EPA
methods list recovery factors of 93% to 99% for
samples spiked with fuel oil and a vegetable oil.
These factors are not representative of recovery fac-
tors or accuracy for produced-water systems where
there are potentially more extractable, non-oil materi-
als present than in the refined products used for the
recovery studies.
5. Significance of the measured quantity as truly being
None of the described oil. No property specific to oil alone is measured in
any of the described procedures. In each procedure,
analytical procedures
oil is defined as whatever is measured or detected by
measures a property that method. Thus, EPA Method 413.1 defines oil as
specific to oil. In each any weighable material, dissolved or dispersed,
procedure, oil is defined extracted from an acidified water sample by the
fluorocarbon solvent that is not lost by volatilization
as whatever is detected or
or decomposition during evaporation of the extract-
measured by that method. ing solvent at 70°C. The spectrophotometric method
in API RP 45 gives results that are more specific to or
representative of a colored crude oil itself. This is
perhaps the best and simplest method for measuring
dispersed oil for tests to determine separation effi-
ciency of equipment or chemicals. This test procedure
cannot be used for tests involved in NPDES permit-
ting.
The objective of a suspended solids analysis is to deter-
mine the types and amounts of suspended solids in the
water. This information can suggest sources of and
solutions to plugging, fouling, bacterial, corrosion, and
scaling problems. This discussion focuses on gravimetric
techniques to determine how much suspended solids are
present and qualitative techniques to identify the types of
solids. Particle-size analysis is not discussed.
SUSPENDED SOLIDS
Sampling and Analytical Procedures
A variety of analytical procedures can be used, depend-
ing on the type and sophistication of the information
desired. The sampling procedures for all analytical
methods for suspended material have one common goal:

the amount and composition of the suspended solids
sampled should be as representative as possible of those
in the system sampled. Therefore, fluid flow in the
system should be close to normal operating conditions.
The sampling valve and lines must be thoroughly flushed
with many volumes of fluid before the analytical sample
is taken. For suspended material in water samples that is
to be collected on a filter for subsequent analysis, filtra-
tion should be performed in the field with the filter
mounted in a suitable holder and directly attached to the
sampling line. If this is not practical, pressure filtration
should be performed in the field immediately after sam-
pling. Do not take the sample in a separate container and
perform the filtration later. The amount and composition
of suspended solids can change significantly in a rela-
tively short time.
National Association of Corrosion Engineers

Standard Test Method TM 0173-84
The National Association of Corrosion Engineers (NACE)
Standard Test Method TM 0173-84, “Methods for Deter- NACE TM 0173-84 can be
mining Water Quality for Subsurface Injection Using used to determine the
Membrane Filters”18 or a modification is frequently used
to determine qualitatively and quantitatively the sus- amount and the types of
pended solids (nonfilterable residue) in water. A known suspended solids in a
volume of water is filtered through a washed and water sample.
preweighed membrane filter of a specified pore size
(usually 0.45 µm). The solids retained on the filter are
washed, dried, and weighed to give the amount of total
suspended solids. The residue is then washed with a
suitable organic solvent (toluene, methyl chloroform,
etc.), dried, and reweighed. The weight loss upon wash-
ing with the organic solvent gives the hydrocarbon-soluble
suspended solids (primarily oil and organic material). The
weight loss upon subsequent washing with acid gives the
acid-soluble suspended solids (primarily carbonates, acid-
soluble sulfides, and iron-containing corrosion products).
The residue after acid washing is the acid-insoluble sus-
pended solids (primarily sulfate scales, acid-insoluble
sulfides such as CuS and FeS2, silicates, other formation
materials, and anything else that is not soluble in the
organic solvent and the acid). By varying the type and
concentration of acid used for washing, we can subdivide

the acid-soluble suspended solids into carbonates and
iron compounds. The hydrocarbon-soluble suspended
solids are frequently identified as dispersed oil. How-
ever, this method is not quantitative for dispersed oil
because oil can bleed through the membrane filter. Dis-
persed oil is not completely retained by the membrane
filter when the sample contains more than a few milli-
grams per liter of oil.
Frequently, these procedures listed in this NACE stan-
Hydrocarbon-soluble dard are also used to measure water quality for injection
by determining the filtration rate of a water sample
suspended solids are not
through a membrane filter under specified conditions.
equivalent to dispersed These tests are discussed in Chapter 4. Ref. 18, included
oil. as an Appendix in Chapter 4, gives specific details for
test performance and interpretation of results.
X-Ray Diffraction Analysis

X-ray diffraction (XRD) can be used for the qualitative
X-ray diffraction identification of the crystalline, chemical compounds
identifies crystalline present in significant amounts (>1 to 2 wt%) in a sample
of solid material recovered from the system. Amorphous
compounds present in a and very finely divided solids cannot be identified be-
solid sample. cause they do not give a recognizable diffraction pattern.
XRD requires extensive methods development (use of
internal standards, elimination or minimization of inter-
ferences and matrix effects) to quantify the amount of
each compound present. In some cases, XRD has been
combined with wet chemical analysis to yield better
quantitative information about the mineral composition
of a solid sample.
X-Ray Fluorescence Analysis

X-ray fluorescence (XRF) can determine the chemical
X-ray fluorescence elements in a solid sample. XRF cannot identify the
chemical compounds or how the elements are combined
analysis identifies
to form compounds. Sometimes, a map of the elements
chemical elements in a present can be used to suggest the presence of a chemical
solid sample. compound — e.g., calcium and sulfur in close proximity
may indicate a calcium sulfate compound. Low-atomic-
number elements — those with atomic numbers less than
sodium (atomic number 11) — are not detected.

Scanning Electron Microscopy
In some cases, experienced personnel can identify the
chemical compounds in a sample from the crystal size
and shape using a scanning electron microscope (SEM).
More frequently, the SEM is used to generate X-rays
characteristic of the chemical elements present. This
procedure, scanning electron microscopy/energy dis-
persive spectra (SEM/EDS), is similar to XRF but on
a microscopic scale. SEM procedures use high vacuum,
so samples must be dry and free of oil and other volatile
materials.
Other Procedures
Patton gives simple field tests suitable for qualitative
analysis of many scale deposits (Ref. 10, Pages 90-91; Ref.
11 Pages 75-76). For more detailed characterization,
specific laboratory procedures using wet chemical analy-
sis, either alone or in combination with XRD
(PETROCHEM analysis), are available for many solid
components. ASTM19-23 has published various procedures
for sampling and analyzing many water-formed deposits
that appear in oilfield systems.
Quality Control
Specific procedures to assess the accuracy and precision
of suspended solids analyses are not available. Duplicate
samples may show considerable variations and are not
reliable as quality-control checks. Strict and reproducible
adherence to established procedures will usually im-
prove precision.
Some suspended solids are unstable when dried or ex-
posed to air. For example, iron sulfide may be pyro-
phoric and rapidly revert to sulfur dioxide and iron
oxides when exposed to air. Samples for analysis should
be fresh and/or suitably preserved so that there is rea-
sonable assurance that we are analyzing what was origi-
nally present in the system. When identifying the com-
position of the solids is more important than knowing the
amount of solids present, field chemical tests may be
more suitable than laboratory analysis for samples that
might undergo changes.

REFERENCES
1. Ford, W. L. and Deevy, E. S. Jr.: “The Determination
of Chlorinity by the Knudsen Method,” Woods Hole
Oceanographic Inst., Woods Hole, MA (1946).
2. Standard Methods for the Examination of Water and Waste
Water, American Public Health Assn./American Water
Works Assn./Water Pollution Control Federation,
15th edition (1980) and 17th edition (1989).
3. Strumm, W. and Morgan, J. J.: Aquatic Chemistry,
second edition, John Wiley & Sons, New York City
(1981).
4. Thomas, N. L. and Campbell, W. L.: “Technical
Memorandum. Assembly and Operation of the Auto-
matic Pressure Filtration Apparatus,” COFRC
TM89000551 (June 1989).
5. Carpenter, A. B. and Campbell, W. L.: “Introduction
to Inorganic Geochemistry. Appendix C — Procedures
for Sampling and Chemical Analysis of Formation
Waters,” COFRC LN89000516 (1989).
6. Subcasky, W. J.: “Final Report — Evaluation of Sulfide
Ion Selective Electrode,” COFRC TS88000784 (July
1988).
7. Annual Book of ASTM Standards, Section 11 — Water
and Environmental Technology, American Soc. for Test-
ing and Materials, listed annually.
8. RP 45, Recommended Practice for Analysis of Oilfield
Waters,” American Petroleum Inst., Dallas (1968).
9. “Methods for Chemical Analysis of Water and Waste,”
U.S. Environmental Protection Agency, EPA-600/4-79-
020 (March 1983).
10. Patton, C. C.: Applied Water Technology, first edition,
Campbell Petroleum Services, Norman, OK (1986).
11. Patton, C. C.: Oilfield Water Systems, second edition,
Campbell Petroleum Services, Norman, OK (1981).
12. Ostroff, A. G.: Introduction to Oilfield Water Technology,
second edition, Natl. Assn. of Corrosion Engineers,
Houston (1979).

13. Oppenheimer, J. and Eaton, A. D.: “Quality Control
in Mineral Analysis,” Proc., American Water Works
Assn. Water Quality Technology Conference, Houston
(Dec. 8-11, 1985).
14. Jones, L. W.: Corrosion and Water Technology for Petro-
leum Producers, OGCI Publications, Tulsa, OK (1988).
15. McAuliffe, C.: “Solubility in Water of Paraffin, Cyclo-
paraffin, Olefin, Acetylene, Cycloolefin, and Aromatic
Hydrocarbons,” J. Physical Chemistry (April 1966), 70,
No. 4, 1267.
16. Standard Test Method for Oil and Grease (Fluorocarbon
Extractable Substances) by Gravimetric Determination,
ASTM D 4281-83, American Soc. for Testing and
Materials (1987) 11.02.
17. Standard Test Method for Oil and Grease and Petroleum
Hydrocarbons in Water, ASTM D 3921-85, American
Soc. for Testing and Materials (1987) 11.02.
18. Standard Test Method — Methods for Determining Water
Quality for Subsurface Injection Using Membrane Filters,
Standard TM 0173-84, Item No. 53016, Natl. Assn. of
Corrosion Engineers (1984).
19. Sampling Water-Formed Deposits, ASTM D 887-82,
American Soc. for Testing and Materials (1987) 11.02.
20. Identification of Crystalline Compounds in Water-Formed
Deposits by X-Ray Diffraction, ASTM D 934-80, Ameri-
can Soc. for Testing and Materials (1987) 11.02.
21. Preparation and Preliminary Testing of Water-Formed
Deposits, ASTM D 2331-80, American Soc. for Testing
and Materials (1987) 11.02.
22. Analysis of Water-Formed Deposits by Wavelength-Dis-
persive X-Ray Fluorescence, ASTM D 2332-84, American
Soc. for Testing and Materials (1987) 11.02.
23. Reporting Results of Examination and Analysis of Depos-
its Formed From Water for Subsurface Injection, ASTM D
4025-81, American Soc. for Testing and Materials
(1987) 11.02.

GLOSSARY
Accuracy — combination of bias and precision of an
analytical procedure, which reflects the closeness of a
measured value to a true value.
Acid-insoluble suspended solids — the amount of
suspended solids retained by a membrane filter after
an acid wash in NACE Standard Test Method TM
1073-84.
Acid-soluble suspended solids — the amount of sus-
pended solids removed by an acid wash in NACE
Standard Test Method TM 1073-84.
Acidity — a measure of the capacity of a water to react
with the hydroxide ions of an added base.
Alkalinity — a measure of the capacity of a water to
react with the hydrogen ions of an added acid.
Analyte — the component or material being determine in
a chemical analysis procedure.
Anion — negatively charged ions in solution that move
towards the anode (electrode at which oxidation
occurs) in an electrolysis cell.
Anion/cation balance — a primary method of checking
the reliability of an analysis. This procedure is based
on the fact that aqueous solutions are electrically
neutral and therefore the sum of the concentrations of
anions must equal the sum of the concentrations of
cations (all concentration are expressed in
milliequivalents per liter).
Anode — electrode at which oxidation (loss of electrons)
takes place.
Atomic weight — relative weight of an atom of the
element compared with the weight of the carbon-12
atom.
Black water — suspended iron sulfides, usually found in
reducing environments with measurable sulfide
levels.
Cathode — electrode at which reduction (gain of elec-
trons) takes place.

Cation — positively charged ions in solution that move
towards the cathode (electrode at which reduction
occurs) in an electrolysis cell.
Chlorinity — term used to describe the amount of dis-
solved solids, in terms of Cl- or Cl- equivalents, in
or concentration. Defined, in parts per thousand, as
the number of grams of silver necessary to precipitate
the Cl- and Br- in 328.5233 g of seawater.
Chlorisity — term used to describe the amount of dis-
or concentration. Calculated by multiplying the
chlorinity by the density of water at 20°C.
Colorimetric analysis — a method of chemical analysis
where the analyte is determined by measuring the
amount of light of a particular wavelength (color)
either emitted or absorbed by the analyte or a com-
pound chemically equivalent to it. Also called spec-
trophotometric analysis.
Conductivity, mho/cm or µmho/cm — a measure of the
ability of an ionic solution to conduct an electric
current. The standard unit of conductance is conduc-
tivity, k, defined as the reciprocal of the resistance, at a
specified temperature, of a solution contained be-
tween two parallel electrodes, each 1 cm2 in cross
section and 1 cm apart. The unit of k is reciprocal
ohms (mhos) per cm. Conductance is now stated in
siemens/cm, the SI unit, where 1 mho = 1 siemen.
Density, g/mL — the weight in grams of one milliliter of
solution (numerically equal to the weight in kilo-
grams of one liter of solution).
Dispersed oil — a discrete, immiscible liquid hydrocar-
bon phase separate from the water phase.
Dissolved solids — material in a liquid sample that
passes through a specified filter. Also called filterable
residue.

Duplicate samples — a quality control procedure used in
chemical analysis where two samples taken at the
same time from one location and submitted for analy-
sis.
Electrochemical analysis — a method of chemical analy-
sis in which some electrochemical property of the
analyte is measured and related to concentration
(activity).
Endpoint — the point in a volumetric analysis where the
“indicator” undergoes a significant and measurable
change. For accuracy in volumetric analyses, the end
point and the equivalence point must be nearly iden-
tical.
epm — see equivalents per million.
Equivalence point — point in a volumetric analysis
when the amount of added reagent is chemically
equivalent to the amount of the analyte. Not neces-
sarily equal to the end point as measured by an indi-
cator.
Equivalent weight — the weight of a compound that will
react with or is chemically equivalent with some
reaction standard. For acid-base reactions, the stan-
dard is the hydrogen ion; for oxidation-reduction
reactions, the standard is one electron.
Equivalents per million (epm) — the number of
milliequivalents of the stated substance contained in
one kilogram of solution.
Field measurements (analysis) — sample properties and
components that must be measured or determined in
the field immediately after sampling because they
change rapidly with time and cannot be adequately
stabilized (preserved) for latter laboratory analysis.
Free oil — see dispersed oil.
Gpg — see grain per gallon.
Grains per gallon (gpg) — the weight in grains (1 grain =
64.8 milligram) of stated substance in one gallon (1
gallon = 3.785 liter) of solution.

Gravimetric analysis — a method of chemical analysis
where the amount of the sought material is deter-
mined by weighing a separated, pure phase of known
composition that either contains the sought phase or
is chemically equivalent to it.
Gravimetric factor — numerical factor used to convert
the weight of one chemical compound to the weight
of another equivalent compound.
Hardness — divalent cations, primarily calcium and
magnesium, in solution. Originally named for the
divalent cations that form an insoluble precipitate
(scum) with soap.
Hydrocarbon-soluble suspended solids — the amount
of suspended solids removed by an organic solvent
wash in NACE Standard Test Method TM 1073-84.
m — see molality.
M — see molarity.
Meq/L — see milliequivalents per liter.
Mg/L — see milligrams per liter.
mg/L as CaCO3 — see milligrams per liter as Calcium
Carbonate.
Milliequivalents per liter (meq/L) — the number of
milliequivalents of the stated substance per liter of
solution.
Milligrams per Liter (mg/L) — weight, in milligrams, of
the stated substance contained in one liter of solution.
Milligrams per liter as Calcium Carbonate (mg/L as
CaCO3) — the weight of the stated substance, in
milligrams, converted to an equivalent weight of
calcium carbonate and expressed in terms of 1 liter of
solution.
Molality (m) — the number of moles (weight of sub-
stance in grams divided by molecular weight in
grams) in one kilogram of solvent.
Molarity (M) — the number of moles (weight of sub-
stance in grams divided by molecular weight in
grams) per liter of solution.

Mole — an amount of a compound equal to its molecu-
lar weight.
Molecular weight — relative weight of a single molecule
compared with the mass of the carbon-12 atom.
N — see normality.
Normality (N) — the number of equivalents (weight of a
substance divided by the weight per equivalent)
contained in one liter of solution.
Oil-in-water content — measured amount is defined by
the analysis method used.
Organic acids — low-molecular-weight (C2 to C4) ali-
phatic acids or naphthenic acids (saturated acids with
five- and six-membered rings of carbon atoms), a
major contributor to alkalinity in some produced
waters.
Oxidation — loss of electrons.
Particle-size distribution — gives fraction of total num-
ber (or volume) of particles having a given size; does
not estimate the total number (or volume) of particles
present.
Particle-size population — gives number (or volume) of
particles of a given size.
Particulate — suspended solids or dispersed oil in a
water sample.
Parts per million (ppm) — weight, in milligrams, of the
stated substance contained in one kilogram of solu-
tion.
Parts per thousand (ppt) — weight, in some units, of the
stated substance in 1,000 weight parts of solution.
pH — the negative logarithm of the hydrogen ion activ-
ity (concentration). Pure water, where the activities of
the hydrogen ions and hydroxyl ions are equal, is
neutral and has a pH of 7. Acid waters have pH<7;
alkaline waters have pH>7.
ppm — see parts per million.
ppt — see parts per thousand.

Precision — a measure of the degree of agreement
among replicate analyses of a sample, usually ex-
pressed as the standard deviation.
Preserved samples — samples subjected to specified
physical and chemical treatments that stabilize prop-
erties or components for latter analysis.
Quality control — in the broadest sense, the sum total of
all methods, procedures, and practices used to deter-
mine and maintain the quality of the analytical data
produced by a laboratory. Here, quality control is
used in a more limited sense to indicate correctness of
analysis.
Recovery factor — the amount of additional material
determined in an analytical procedure on a spiked
sample.
Red water — suspended iron oxides and hydroxides in
water, usually found in oxidizing environments.
Reduction — gain of electrons.
Resistivity, ohm-m — the opposition of an ionic solution
to carry an electric current. Resistivity is equal to the
reciprocal of the conductance.
Salinity — term used to describe the amount of dis-
or concentration. Total solids after all carbonate and
bicarbonate have been converted to oxides, all bro-
mide and iodide have been replaced by the equivalent
amount of chloride, and all organic matter has been
oxidized.
Soluble oil — crude oil, or its individual components,
truly dissolved as individual molecules in produced
water and existing in a single liquid phase.
Specific conductance — see conductivity.
Specific gravity — the ratio of the sample density to
water density, each density measured at some speci-
fied temperature.
Specific resistivity — see resistivity.
Spectrophotometric analysis — see colorimetric analysis.

Spiked samples — a quality control procedure used in
chemical analysis where known additions of one or
more of the analytes are added to regular samples.
Suspended solids — material in a liquid sample retained
by a specified filter. Also called nonfilterable solids.
Total residue — the amount of solid material left after
evaporating a water sample and drying the residue at
a specified temperature, also called total solids.
Total suspended solids — the total amount of suspended
solids retained by a membrane filter in NACE Stan-
dard Test Method TM 1073-84.
Turbidity — a measure of the cloudiness or opacity of a
water sample, caused by scattering or absorption of
light by particulates (suspended solids and dispersed
oil).
Volumetric analysis — a method of chemical analysis
that determines the amount of a sought component
by measuring the volume of a standard solution of
known concentration that is chemically equivalent to
the sought component. All volumetric analysis proce-
dures require an indicator to determine when the
equivalence point has been reached.
Water quality — the sum total of the physical, chemical
and microbiological properties needed for a water to
be suitable for a particular application.
Weight percent (wt %) — weight, in some unit, of the
stated substance in 100 weight parts of solution.
wt % — see weight percent.
X-ray diffraction analysis (XRD) — a chemical analysis
procedure be used for the qualitative identification of
the crystalline, chemical compounds present in sig-
nificant amounts (>1 to 2 wt %) in a sample of solid
material.
X-ray fluorescence analysis (XRF) — a chemical analysis
procedure be used for the qualitative identification of
the chemical elements in a solid sample.

C H A P T E R
Oil/Water Separation
Chapter 3: Oil-Water Separation 3-1

PREFACE
This chapter discusses the removal of dispersed oil from
water for reinjection, discharge, downhole disposal, or
reuse in EOR projects. Much of the chapter focuses on
the processes used to remove oil from water. However,
like the rest of this handbook, this chapter does not give
detailed design information on specific processes. The oil
removal processes and technologies are explained in
detail. The information presented is sufficient for select-
ing a specific process technology but not for designing a
process in detail.
An important part of this chapter is dedicated to inte-
grated treatment systems and equipment selection. If
you are designing, optimizing, or troubleshooting a
water treatment facility, this philosophy will help you
meet your goal of cost-effective water treatment.
This chapter also forms the basis for the Chevron Oil/
Water Separation Seminar. The seminar notes, available
from your colleagues who have attended, are another
source of information.
WATER QUALITY REQUIREMENTS

This section focuses on how clean produced water needs
to be for reinjection, discharge, and use in EOR. The
quality requirements for discharge are usually dictated
by regulations that set an acceptable parts-per-million
(ppm) level of oil in water. For injection, the water qual-
ity in terms of residual oil is not defined as well, but is
usually set by the reservoir’s tolerance to oil in the injec-
tion water. For EOR, the quality is usually set by the
processing facilities.
Injection Requirements
The effect of residual oil in injection water on the perme-
ability of subsurface formations is currently not well
understood. In certain reservoirs, the effects of emulsion
formation in the wellbore are known and injectivity loss
can be predicted. However, these emulsions are not
usually formed by the oil droplets in the injection fluid,
but by residual oil/injection water interactions. Our

ability to predict the effect of discrete, nonemulsified oil
droplets on well injectivity lacks a scientific basis, but
some general guidelines exist.
The water quality required for injection into a subsurface
formation varies from location to location. An acceptable
quality is usually defined by the amount of permeability
decline that is acceptable while the water is injected. In
other words, what is an acceptable loss in injectivity, and
how fast does that acceptable loss occur?
Identifying this parameter will determine the type and
degree of treatment required. Loss in injectivity is usu-
ally attributed to solids fouling, although the influence of
oil can be significant. The effect of oil-wet solids is also
not well defined, although it is usually characterized in
the same manner as “normal” solids fouling — i.e.,
through filtration and permeability theory.
Traditional methods of determining acceptable water
Corefloods set the criteria quality for injection have ignored the effects of oil. In
for solids removal but are most coreflood procedures, oil is removed from the water
before it enters the core. Therefore, results from
not used to determine oil corefloods do not set a criterion for oil removal, but they
removal requirements. do enable us to set a realistic filtration requirement and
help identify any water sensitivity problems.
There is no predefined limit for the amount of oil that
should be injected with our waters. In the past, we set
specifications based on equipment capabilities. For
example, in many onshore fields, oil concentrations in
injection water have been below 10 ppm, with no
injectivity impairment. Therefore, 10 ppm is adopted as
a specification because the flotation devices typically
used to remove oil can achieve this concentration if
operated correctly.
In our operations, we also remove oil as a precursor to
solids removal. This is done to minimize fouling of the
filtration systems. Hence, some of our specifications for
oil removal are not decided by the reservoir but by
equipment in the treating process.
It is well known that sand filters are susceptible to “mud
balling.” Oil, solids, and filter material form an agglom-
erate that is rounded during backwash. These mud balls
are often stabilized by chemical coagulants and, over

time, will cause poor filter performance. Because of mud
balling, many filter manufacturers impose oil concentra-
tion limits on filter influent. These limits are specific for
different types of filters but tend to range from 5 to
15 ppm. Hence, this operating restriction can set oil
concentration limits. (Chapter 4 gives more details.) In
most two-stage injection systems where filtration follows
oil removal, injection-water oil concentrations usually
range from 1 to 5 ppm and hence are acceptable for most
reservoirs.
Disposal Requirements
When defining disposal of oily waters, we generally talk
about subsurface disposal into a specific zone or reser-
voir. Surface disposal of oily waters is considered dis-
charge.
Subsurface-disposal water-quality requirements are
similar to those for injection. The water must meet the
quality constraints set by the disposal zone. Again,
injectivity loss must be minimized and filtration equip-
ment protected. Disposal wells can be drilled into zones
identified as suitable for disposal. Or existing wells
within an existing reservoir can be recompleted to dis- Many disposal wells are
posal standards. In both cases, the water will probably
be treated to a low level of oil, <10 ppm, before reinjec- completed in high
tion. However, many disposal zones are selected because permeability zones. This
of their high permeabilities and hence may be more minimizes the treatment
tolerant of oil than injection zones in the same field. We required for the injected
cannot yet define the ideal level of oil concentration for
subsurface disposal zones. The optimum level is usually water.
defined as the maximum oil concentration that the dis-
posal zone can tolerate with no injectivity loss or con-
tamination outside the disposal zone.
For disposal, the cost of oil removal is just an overhead
with no payback (except for the value of oil recovered);
the water will not generate incremental oil production.
Therefore, the goal is to remove just enough oil to main-
tain injectivity and wellbore integrity.

Discharge Requirements
For discharge to surface waters, regulatory authorities
usually set the limits on oil quantity. These authorities
set limits for the maximum allowable oil concentration
Most discharge oil-in- and, in some cases, the maximum volume of water dis-
water limits are based on charged. These limits are usually based on performance
criteria of separation equipment — i.e., the capabilities of
technology criteria — not
“the best available practical technology.”1 The definition
environment impact. of best available practical technology is different in differ-
ent parts of the world. In many places, traditional flota-
tion technology is the performance standard. This has
led to offshore discharges set in the 40- to 50-ppm range,
a typical outlet concentration from a flotation cell in
offshore use.
More recently in the U. S., the EPA considered ceramic
membrane filtration as a best available practical technol-
ogy with a proposed a limit of 7 ppm oil in discharge
water. This target discharge concentration is considered
achievable by ceramic filtration. In this particular case,
however, the operability of ceramic filter technology was
questionable; hence, implementation of this lower limit
was delayed.
Historically, limits imposed by the EPA have been
In 1993 the OCS oil-in- adopted or adapted by other countries wishing to control
produced-water discharge. Therefore, it is probably only
water limit was reduced
a matter of time before reduced oil-in-water discharge
from 42 ppm to 29 ppm limits are imposed in all areas of Chevron’s operations.
daily average.
When defining a limit for discharged oil, the authorities
also define a way to measure oil concentration. This
approved method defines “oil.” In many cases, the
definition of oil by the analytical method will account for
free and dissolved oil. Obviously, dissolved oil will not
be removed by traditional separation equipment, how-
ever well optimized. Further explanation of approved
analytical methods is given on Pages 2-75 through 2-88.
EOR Requirements
The steamflood is a common form of EOR in Chevron
operations. Produced water is treated and turned into
steam before reinjection into the oil reservoir. Several
treatment stages are required to meet the stringent inlet

specifications of the steam-generating boilers. Oil re-
moval is one. Most once-through oilfield boilers produc-
ing 65% to 80% steam quality require <1 ppm oil in the
feedwater to minimize boiler coking, etc. This appears to
be the industry standard, although Thermosludge steam
generators can handle oil concentrations of 250 ppm.2
As a pretreatment to steam generation, many produced
waters undergo some degree of softening. Softening
prevents scale deposits on the boiler tubes that cause
fouling, loss of efficiency, and in many cases, equipment
failure. Softening may take place in many ways: strong
cation exchange softening, cation/anion dual ion ex-
change, or reverse osmosis.
When ion exchange resins are used, the allowable oil
concentration depends on the type of resin used in the
bed. Some resins are more tolerant of oil fouling than
others, but all exhibit reduced ion exchange capability if
fouled by oil. Typical limits to maintain ion exchange
capacity and minimize fouling are oil concentrations of
1 ppm or less. The resin may tolerate higher concentra-
tions than this without permanent damage, but perfor-
mance will be reduced.
A similar situation exists for reverse osmosis membranes,
which can easily be fouled by oil. Less than 2 ppm oil
concentration is recommended to maintain membrane
integrity.
Note that, while EOR waters have special treatment
requirements, some EOR processes alter the characteris-
tics of produced fluids. For example, caustic/surfactant
flooding can produce very tight emulsions in the pro-
duced fluids, which can result in poor dehydration and
poor produced-water quality. If this produced water is a
source water for an EOR process, its treatment require-
ments may be more complex than a source water that is
not influenced by EOR. Of course, some EOR processes
enhance production operations. Steamflooding, for
example, often raises the temperature of the produced
fluids, simplifying crude dehydration and subsequent
water treatment.

OILY WATER TREATING EQUIPMENT
General
All oilfield oil/water separators are designed to exploit
the gravity (density) difference between the oil and water
phases. This density difference is the driving force for
separation. Many factors, such as fluid properties and
separation temperature, influence separation quality. But
the fundamental basis of separator design is to provide
an environment where the density difference can be
realized and separation can be effected. This is true for
crude dehydration (oil separation from water) and oily
water cleanup (water separation from oil).
Time is required for the density difference to effect sepa-
ration. Residence or settling time is the time allowed in a
separator for oil and water to separate. Residence time is
a key design parameter. Maximizing it for a minimum
vessel size is the designer’s goal. Many techniques —
fitting special inlet and outlet piping, fitting vessel
internals — are used to maximize residence time. Some
of these techniques and their effects are described below.
Some influencing factors, such as oil droplet size and
continuous-phase viscosity, can also be maximized and
minimized with process and design techniques. Again,
the use of vessel internals and heat can optimize the
influence of these factors on separation.
A simple mathematical relationship known as Stokes’
law exists among the separation driving force, influenc-
ing factors, and separation effectiveness. In its most
Oil droplet size is the key widely used form, Stokes’ law can be written as
parameter in oily water gd 2 ( ρ w - ρ o)
v = ,
cleanup. 18 µ
where v = separation velocity,

ρw = water specific gravity,
ρo = oil specific gravity,
d = oil droplet diameter,
g = 9.81 ms-2, and
µ = water viscosity.

As can be seen, the velocity of the separation of oil from
water is directly proportional to the density difference
between the phases and the square of the discrete-phase
droplet size, and inversely proportional to the continu-
ous-phase viscosity. To improve separation, droplet size
can be maximized chemically or mechanically, the viscos-
ity can be reduced by heating the fluid, and the force of
gravity can be increased by swirl or rotational move-
ment, as in liquid/liquid hydrocyclones.
Of all the factors influencing our ability to separate oil
from water effectively, oil droplet size is the most critical.
It is used as a design parameter in all oilfield separation
equipment. For example, three-phase primary dehydra-
tors are often designed to leave oil droplets smaller than
500 µm in the water phase. API separators, once consid-
ered the workhorse of refinery oily water treatment, are
designed to remove 150-µm or larger oil droplets.
By using oil droplet size as a design parameter, we gener-
ate a monitoring and optimization parameter. If we can
measure and maximize oil droplet size, we will maximize
the separation performance of the water treatment equip-
ment. Oil droplet size can be maximized mechanically
and chemically and by minimizing the shear of produced
water in our facilities. To achieve minimum shear in
water treatment facilities, we must begin at the process
design stage. Equations are available to describe the
maximum droplet size that can exist in a water treatment
system. These equations are derived from the principle
that dispersion (the reverse of coalescence) occurs when
the energy applied to a system exceeds the surface en- Oil droplet coalescence
ergy of coalesced oil droplets. This excess energy is
manifested in droplet breakup and often in poor separa- enhances separation; oil
tion efficiencies. Because the concept of surface energies droplet dispersion
is difficult to grasp in everyday operations, we can relate through shear degrades
droplet breakup to changes in shear of the water phase as separation.
it passes through piping, valves, etc. Hinze3 developed
an equation to predict the maximum droplet size in a
given system that relates shear and residence time to
pressure drop.
2/5 3/5
 t   σ 
d max = 432 r    ,
 ∆p  ρw 

where dmax = diameter of droplet above which only 5%
of the oil volume is contained (mm),
σ = surface tension (dynes/cm),
ρw = density (g/cm3),
∆p = pressure drop (psi), and
tr = retention time (minutes).
Knowing that droplet size is critical and that minimizing
shear is an important design consideration should im-
prove our treatment processes. If we have no choice but
to design a high-shear system, we should install equip-
ment to coalesce sheared oil droplets or select separation
equipment that efficiently separates small droplets. For
example, selecting plate-pack separators as oil/water
treating equipment downstream of a control valve with a
high differential pressure across it will result in poor
water quality. In most cases, high-differential pressure-
control valves cause excessive shear and reduce oil drop-
lets to smaller than 30 µm.4 Because plate-pack separa-
tors are designed to remove 60-µm and larger droplets,
poor oil removal efficiencies will be observed.
Hence, treatment facilities design plays a critical role in
Shear can be caused by oil droplet size. To optimize our facilities and maximize
valves, elbows, orifice oil droplet size, we need a way to measure oil-droplet-
size distributions. The Appendix contains a technical
plates, etc.
memorandum, TM90000301, that reviews on- and off-
line techniques for measuring oil droplet size.
DEHYDRATION SEPARATORS
In many designs of three-phase separation vessels, the
primary purpose is to separate water from oil. These
vessels are usually designed as crude dehydration vessels
and optimized for crude quality, but their influence on
water quality cannot be underestimated.
In the dehydration of crude oil, both chemical and me-
chanical processes occur. The mechanical process pro-
vides enough residence time for emulsion to be resolved
and the water to drop out of the crude. Traditionally,
vessel designs have been based on oil-phase residence
time.5

For clean water, water-phase residence time is also im-
portant. During water settling, some oil will be drawn
into the bulk water phase. To obtain clean water at the
vessel outlet, this oil must be allowed to return to the oil
phase. Longer effective water-phase residence times
allow more oil to return to the bulk oil phase.
To maximize the water-phase residence time and oil
droplet size, vessel internals (plates, packing, vortex
breakers, etc.) are usually used. The role of the vessel
internals is two- or three-fold. Increasing residence time
by ensuring minimal vessel short-circuiting is usually our
primary reason for installing internals. However, reduc-
ing water-phase turbulence and acting as oil droplet
coalescing media are additional benefits.6
SETTLING SKIM TANKS

Settling or residence-time tanks are the simplest of all
separation devices. They consist of a large tank whose
sole purpose is to provide a quiescent domain with
enough residence time to effect oil/water separation by
gravity. Typical residence times range from 10 minutes to
several days, depending on the system. Most settling
tanks are cylindrical vessels operating at atmospheric
pressure. Many tanks are blanketed by gas to minimize
oxygen ingress and hence mitigate any potential corro-
sion problems. One major challenge in any settling tank
design is to maximize residence time. This is achieved by
using inlet and outlet nozzle configurations, baffles, Maximizing residence
spreaders, and other vessel internals. No vessel design
time is the key to effective
has proved to be more effective than the others, although
many designs exhibit less-than-acceptable performance.7,8 skim tank performance.
The main reason for lower-than-expected performance is

short circuiting. The water entering the vessel takes a
preferential route to the outlet and bypasses the majority
of tank volume available for separation. The result is a
reduction in oil/water separation efficiency.
To combat this lack of use of available residence time,
several tank designs attempt to remove the short-circuit-
ing option (Fig. 1). As Fig. 1 shows, most involve differ-
ent inlet configurations and internal baffle designs. Al-
though these invariably help, evidence exists that
optimum separation does still not occur.9 We recommend

working with vessel and internals manufacturers, such as
NATCO, to evaluate and optimize designs. Their insight
into hydraulic and separation efficiency maximization
often leads to optimized separation criteria for new and
retrofit designs.
Despite the difficulties of maximizing the available resi-
dence time for separation, settling tanks are usually the
cheapest and most cost-effective way to separate oil from
water. Hence, they are considered the first choice for
onshore systems where flow variations are minimal and
land is available for large facilities. This type of facility is
not considered suitable for offshore use because of its
excessive space and weight requirements.
COALESCERS
Coalescers provide a solid surface that can come in con-
tact with and be wet by small oil droplets. These small
oil droplets accumulate and saturate the solid media,
forming a cohesive oil film. When the cohesive forces of
the film are overcome, oil elutes from the media in large
droplets. These larger drops separate significantly faster
than the small droplets in the feed stream in accordance
with Stokes’ law (Fig. 2). Some coalescers can separate
the enlarged oil droplets and thus can be considered true
separators. Some coalescers perform only droplet ag-
glomeration and must be used with separation equip-
ment downstream. Each type of coalescer plays an
important role in effective separation of oil from water.
Three types of coalescers are currently available: plate-
pack, loose-media, and fixed-media coalescers.10,11 In this
section, we will consider only media coalescers. Plate-
pack coalescers are covered in the next section.
Loose-Media Coalescers
Loose-media coalescers are vessels containing a medium,
Coalescers provide a such as sand, that acts as a coalescing surface for oil
droplets. These coalescers may be upflow or downflow.
surface for oil droplets to
They essentially provide a surface area and contact time
contact, agglomerate and for the oil droplets to coalesce. Upflow coalescers are
grow. typically used in oilfield applications; downflow
coalescers are used in refinery applications. These de-
vices operate quite simply. Oil droplets enter the vessel

and pass into the media bed, where they are held on the
surface of the sand grains and coalesce. Oil gradually
saturates the medium and eventually breaks through into
the outlet water stream. The coalesced oil is then sepa-
rated, usually by a weir or baffle system, and piped
continuously from the vessel.
These coalescers invariably act as filters to some of the oil
and to any suspended solids present. Therefore, they
must be backwashed to minimize fouling. However,
these devices are not designed to remove solids effec-
tively. In most loose-media coalescers, sand grain size
and flux rates are chosen to maximize oil/sand contact
time, not for solids entrapment.
Effective backwashing is critical to optimizing coalescer
performance. Inefficient backwashing leads to residual
oil and solids in the bed, which act as a glue to fresh oil
and solids in the influent stream. This leads not only to
rapid increases in pressure drop but also to the formation
of mud balls, which rapidly deteriorate coalescer perfor-
mance.
Fixed-Media Coalescers
Fixed-media coalescers provide an oleophillic medium
for oil droplet contact and coalescence. Oil droplet size
changes when the droplets coat the medium and elute or
coalesce within the medium. The coalesced droplets are
then separated by gravity in the coalescer separation
chamber.
Typically, the media come in two distinct configurations:
a sponge type and a fibrous cartridge similar in design to
a filter cartridge. Sponge-type coalescers offer a porous
oleophillic environment for coalescence and are usually
housed in horizontal or vertical separator vessels. Oily
produced water enters the separator and flows through
the sponge, where oil droplets coalesce in the pores and
saturate the surface. These droplets then elute from the
medium and pass into the quiescent separation zone of
the vessel. There, oil is drawn off at the top and “clean”
water is drawn from the bottom.

During the coalescing process, the medium can become
saturated with oil and solids, thus increasing the pressure
drop across it. At some preset level, usually 8 to 10 psig,
the medium must be cleaned to maintain performance.
This cleaning process, sometimes called regeneration, is a
combination of squeezing and releasing the foam me-
dium to force out the incumbent oil and solids. This
cycle is usually done several times, and the final step is
usually a rinse with clean water. Because rinsing occurs
only once during regeneration, the waste stream volume
generated is very small. The oil squeezed out of the
coalescer during the preliminary squeeze process is, of
course, fed to the separated oil outlet. Fig. 3 is a sche-
matic of the sponge-type fixed-media coalescer.
Fibrous coalescers usually consist of concentric layers of
fibrous material spun around a central support/distribu-
tor tube. The coalescer elements are set vertically in a
separation vessel similar in design to a cartridge filter
vessel. The influent oily water enters the cartridge
through the central tube and flows radially through the
fibrous medium into the separation chamber. Again, the
oil droplets coat the fibrous medium and coalesce in the
voidage between the fibers before eluting into the separa-
tion section of the vessel. Several methods — including
the use of a netted, crimped, outer layer for the cartridge
— are used to ensure an even flow of coalesced oil drop-
lets from the cartridges. These methods encourage the
coalesced oil to hug the surface of the cartridge and rise
rapidly through the separation section of the vessel. This
prevents droplet re-entrainment in the clean water outlet
stream and allows the cartridges to be placed closer
together in the separation vessel without impairing
performance.
Typically, these cartridges are not backwashed but are
replaced when they become fouled with suspended
solids and the pressure drop across them becomes exces-
sive. Fig. 4 is a schematic of the fibrous coalescer.

PLATE PACKS (INCLUDING SP-PACK AND
VERTICAL TUBE COALESCER)
Plate-pack separators (PPS) were first used in the oil
industry in the 1950’s. Introduced by Shell, they were the
first separation device designed to give API separator
capacity and performance in a compact vessel. Plate-
pack separators come in many different configurations,
but all are derivations of the same basic design.
This basic design used a series of parallel flat plates
installed at a 45° angle to the flow direction. The plates
themselves sit in a rectangular tank that has inlet distri-
bution weirs to ensure adequate flow distribution to the
total plate system. All designs have a weir arrangement
for oil removal and a sump to collect separated solids.
The plates act as a coalescing medium for oil droplets
that attain a critical mass and then progress along the
underside of the plates to the top of the vessel, where oil
is skimmed off. Any solids in the system settle in the
laminar quiescent region between the plates and fall to
the base of the vessel.
As Fig. 5 shows, the flow of the oil droplets along the
plate surface is countercurrent to the water flow. Hence,
to maintain the coalescing action of the plates, laminar
flow must be maintained to avoid stripping of the oil
film. Solids that fall to the bottom of the channel can
build up and block the laminar flow region. This reduces
the surface area available for coalescence and hence oil
removal efficiencies. The balance between having a large
number of plates in a vessel to maximize coalescence and
having a wide enough plate spacing to avoid solids
blocking is a key consideration in the design of a PPS for
solids-laden waters.
The plates themselves have been the focus of many
design derivatives. Corrugated plates are popular be- Corrugated Plate
cause they provide more surface for coalescence than flat Interceptors (CPI) are the
plates; they also provide a concave channel for the oil to most common and
flow upward. This design has become very popular effective plate pack
recently as improvements in the oil collection weirs and
solids-handling sump accompanied the development of separators.
the corrugated plate concept.

Significant derivatives of the traditional plate-pack sepa-
rators are the SP-Pack Coalescer and the Vertical Tube
Coalescer. The SP-Pack, a serpentine-path coalescer, uses
free-flow turbulent coalescence to increase oil droplet
size and thereby enhance separation efficiency. The
device itself is essentially a collection of pipes joined by a
series of helical swirl bends that cause the water to flow
in a pattern conducive to coalescence without generating
enough turbulence to shear oil droplets. The primary
role of the bends is to generate this flow pattern, but
evidence shows that they also provide a surface to assist
coalescence.12 This device does not operate as a separator
but merely as a coalescer. Thus, it must be used with
other equipment. This device can be used as a pretreat-
ment device for flotation cells and hydrocyclones. But it
probably is best used in settling tanks where it can act as
a coalescer and inlet flow spreader (Fig. 6).
The Vertical Tube Coalescer operates like a plate pack,
but the plates are replaced with vertical tubes. The
vertical tubes offer a five-fold increase in coalescing area
over traditional plate packs. In addition, because the flow
is across the tubes, oil rises more easily to the separation
weir (as opposed to the PPI, where the oil flow is coun-
tercurrent to water flow).13 The tubes are made from
polypropylene and look like a loosely knit cartridge filter
(Fig. 7). Because the material is oleophillic, it easily
attracts small and large oil droplets. The inlet flow
passes through the tubes, where oil coalesces and rises to
the surface to be skimmed off. Solids and sludge fall
through the tubes and are collected in a sump at the
bottom of the vessel. As in the PPI, the vessel itself
consists of an inlet tank arrangement, flow distribution
baffles, the tube tank, and an oil collection system.
FLOTATION
Flotation has become the industry standard for de-oiling
Flotation has been the produced water because of its excellent separation capa-
bilities. Conceptually, it is a simple process. Gas bubbles
industry standard for oil
unite with oil droplets to reduce their apparent specific
removal for many years. gravity, thus accelerating their rise velocity and separa-
tion. Practically, flotation occurs in a vessel that provides

bubble generation, a contact zone for the gas and oil,
retention time for the separation process, and an “oily
froth” removal device.
The three basic types of flotation systems are designated
by their mode of bubble generation: dissolved flotation, The three basic flotation
rotor- induced flotation, and eductor-induced flotation.
mechanisms have been
In the dissolved gas system, oily water and gas are com- recently supplemented by
bined under pressure, usually less than 50 psig. This
sparger flotation. This is
mixture then flows across a pressure control valve into
the atmospheric flotation tank. The pressure relief causes direct gas injection
tiny bubbles to be generated. These bubbles then can through a porous tube
unite with the oil droplets to initiate flotation (Fig. 8). which reduces mechanical
In a rotor-induced gas system, a fine dispersion of gas complexity of traditional
bubbles is generated in the water stream by drawing gas designs.
from the surface of the flotation cell and mixing it with
the water with a rotating impeller (Fig. 9). In these sys-
tems, the flotation device usually operates at 6 to 12 in. of
water gauge pressure, which is usually enough to pre-
vent air ingress. (Air ingress is undesirable in terms of
explosive mixture/safety and corrosion mitigation.)
The eductor flotation cell is similar to the rotor-induced
system, except that gas and water are contacted in the
eductor and then fed to the flotation cell (Fig. 10).
In all three variants, the separation theory is the same. It
consists of five basic steps.
1. Small gas bubbles are generated in oily water.
2. A gas bubble and an oil droplet suspended in the
water come in contact.
3. The gas bubble attaches to the oil droplet.
4. The gas bubble/oil droplet rise to the liquid surface
for removal.
5. The oil-rich froth is removed.
Dissolved Gas Flotation

A dissolved gas flotation system has three basic modes of
operation: full flow pressurization, partial flow pres-
surization, and recycle pressurization. Fig. 11 shows
these schemes diagrammatically .

In full flow pressurization, the entire flow stream is
injected with gas and pressurized. This configuration
maximizes the gas/water ratio, which improves bubble
population density and thus the probability of oil capture
and subsequent separation. However, it also requires the
largest pump and the largest retention vessel.
In partial flow pressurization, only part of the stream is
processed, usually at higher pressure. This technique
effectively seeds the major influent stream with a gas-rich
sidestream, which reduces pump size and operating
costs. However, this scheme results in a lower gas/water
ratio, and oil droplets may degrade through the pump
and control valve.
In recycle pressurization, the full flow stream is fed into
the flotation cell. Twenty to fifty percent of the cell efflu-
ent is injected with gas, pressurized, and recycled to the
flotation cell, where it is blended with the full flow
stream. The advantages of this system are that a small
pump is used and that recycling treated water negates
the oil droplet degradation seen if untreated water is
used. This is the primary reason for its widespread use.
Induced or Dispersed Gas Flotation

Induced gas flotation (IGF) systems are induced by rotor
or by eductor. The separation mechanism is the same in
both; only the way that the gas is introduced into the
separation cell is different. In each type of IGF system,
the ability of the device to separate oil from water de-
pends on correct design and operation to maximize oil
droplet capture by the gas bubbles. The design must take
into account the five specific fluid kinetic regions that
make up the operating separator (Fig. 12). To optimize
performance, the following criteria must be met.
1. Sufficient gas must be provided to the unit to effect
flotation. Gas is usually routed from a low-pressure
gas header if the produced water does not contain
sufficient dissolved gas at the inlet to the device to
effect flotation. (A pressure drop across the inlet flow
control valve usually is sufficient to ensure gas
breakout in the flotation cells.)

2. The water recirculation rate must be sufficient to
ensure adequate contact between oil droplet and gas
bubbles, yet it should be not cause short circuiting.
3. The two-phase mixing region must have enough
shear to supply a satisfactory bubble size range while
ensuring good oil drop/gas bubble contact.
4. The quiescent region must be large enough to allow
unhindered flotation of the bubble/droplet agglomer-
ate and must not promote re-entrainment.
5. The skimming region must provide a surface flow
pattern that enables skimming of the collapsed foam
without disturbing the flotation region.
In practice, if one or more regions of the separator fluid
kinetics are disturbed, oil removal efficiency will be
reduced.
Mechanical IGF Units

This type of device is the most common flotation design
used today (see Fig. 9). This device operates quite sim-
ply. An impeller with several straight blades rotates in
the influent water to produce a vortex. The resulting
negative pressure draws gas from the gas blanket down
through a standpipe, where it becomes entrained in the IGF’s are often know by
water. The impeller rotation also causes water to circu- their most common
late from the bottom of the cell into the impeller blade variant name: WEMCO.
system, where it comes in contact with the entrained gas.
Dispersed gas bubbles form, and the liquid/gas mixture
passes from the impeller via a diffuser into the flotation
region. The diffuser acts to contact the gas and oil drop-
lets further and to change the tangential flow regime at
the impeller into a radial flow regime entering the quies-
cent zone. In the quiescent zone, flotation takes place
and the gas/droplet agglomerates rise to the surface to
be skimmed by paddles on either side of the cell. Many
designs incorporate a hood over the diffuser to keep the
skimmings region in a quiescent state.
The rate of skimming from the device depends on the
inlet water rate. It is usually 5% to 10% of the inlet water
volume. The number of cells in a flotation device varies
among manufacturers and ranges from one to four. The
most usual configuration is four cells in series, each with

a retention time of 1 minute. The devices also incorpo-
rate an inlet box and a discharge box with level control
equipment to ensure operation control. Note that, al-
though mechanical IGF units exhibit excellent perfor-
mance in steady-state conditions, they are affected by
flow-rate changes. In most successful installations, surge
capacity is available upstream of the IGF unit to mini-
mize flow surges and maximize oil removal efficiency.
IGF Selection
On-site tests should be carried out to determine whether
an IGF unit will successfully treat an existing produced
water. These tests use a bench-scale IGF unit, which
gives an excellent indication of the performance of a full-
scale unit. This procedure is recommended if flotation is
being considered for an existing field’s water production.
Eductor IGF Units

Eductor IGF units are similar in design to the mechanical
IGF units, except the complex mechanical impeller/
diffuser assembly is replaced with a simple eductor. Fig.
10 shows the assembly of the eductor and associated
equipment. In this device, the gas is induced into the cell
by recycling part of the cleaned discharge water through
an eductor. This creates a venturi effect, which draws gas
into the eductor, where intimate mixing with the recycled
water occurs. The water/gas mixture then passes
through a standpipe into the body of the cell. The fluid
kinetic regions are like those in Fig. 8, albeit less clearly
defined.
Gas bubbles typically are smaller than in impeller-type
IGF’s. Bubble size is controlled by the gas rate. The gas
rate, in turn, is controlled by the water recycle rate, gas
inlet orifice size, and eductor design.
The traditional hydraulic eductor-type units typically do
not perform as well as the mechanical units,14 primarily
because bubble/oil droplet agglomerates are re-entrained
into the bulk fluid. Also, the gas transfer per unit volume
is typically less than in impeller units. This also tends to
decrease oil removal efficiency. Note, however, that
several second-generation designs are becoming avail-
able. These devices tend to be of two types: the four-cell

improved eductor type and the single-cell external educ-
tor type. Both devices offer more efficient mixing of gas
and water, which results in more efficient separation. In
the four-cell type, the eductor design and agglomerate
dispersion in the flotation cell are improved. Other
advantages of the four-cell eductor design are its capabil-
ity to be operated at pressure and the use of a weir/level
control system to optimize skimmings collection and
flow surge capacity. This is typically more efficient than
mechanical skimming because a smaller volume of water
is removed with the floated oil. In addition, no moving
parts lie within the separator vessel, which reduces the
need for vessel entry.
The single-unit design uses a high gas/water ratio at
high velocity to generate very small bubbles, which
improves capture efficiency. The gas/water contact
occurs in an eductor external to the separation vessel.
The gasified influent passes from the eductor into the
separation vessel through a coalescer pack that enhances
gas bubble/oil droplet contact. This, coupled with a
circular cross-sectional cell design, leads to minimal
disturbance in the quiescent flotation zone. The result is
an efficient separator that produces a tight foam that
reduces skimming volume. Again, a weir arrangement is
used to remove the skimmings, eliminating moving
parts.
Dissolved Gas Flotation Units vs. IGF’s

Dissolved gas flotation (DGF) units do not compare
favorably with IGF units for oilfield use. Typically, they
are larger and more expensive than IGF units owing to
the need for long gas/liquid contact time. However, they
are less susceptible to upsets from flow-rate variations
and typically produce a smaller float or skimmings
volume.
Factors Influencing Flotation Cell

Performance
Many factors affect the selection and optimization of a
flotation process. Strickland 15 first determined the major
influences on flotation cell performance in 1980. They are
included below.15 Strickland looked at both DGF and IGF

systems. While these investigative tests were carried out
in a laboratory, the results have been shown to transfer
directly to field installations.16
Gas Concentration
A high gas concentration is desirable because it will
increase oil removal. High concentrations will increase
the population of gas bubbles available to capture oil
droplets. A high gas concentration can be achieved by
generating small bubbles in a DGF unit or by using an
IGF gas unit with a high gas/water ratio. For a dissolved
unit, the mean gas bubble size typically ranges from 80 to
100 µm. For a dispersed unit, the gas bubble size is
typically >100 µm. Hence, a DGF unit develops a more
favorable bubble size than an IGF unit. However, this
advantage is offset by the actual gas volume available for
bubble generation. In a DGF unit, this volume is about
0.5 ft3/bbl. It is limited by the solubility of the gas in the
produced water. For an IGF system, however, the
amount of gas available for bubble generation can be as
high as 35 ft3/bbl. This more than offsets the unfavorable
bubble size generated in an IGF unit.
Note that oil droplet size can influence the size of bubbles
generated in a flotation device. Small oil droplets
(<10 µm) cause gas bubbles to coalesce and hence reduce
gas concentration and efficiency. This is more critical in
DGF systems where high gas concentrations are achieved
through generation of very small bubbles.
Salinity of Produced Water

Oil recovery from flotation processes increases with
increasing salinity up to 3% to 4% NaCl. Above this
level, oil removal efficiency remains constant. This
increase in efficiency is correlated to decreasing bubbles
size with increasing salinity, although electrolyte effects
may play a role in oil removal performance. Most oil-
field waters contain enough dissolved solids to be good
candidates for flotation; however, some steamflood
operations with 4,000 to 7,000 total dissolved solids will
generate larger bubbles and show lower removal efficien-
cies.

Inlet Oil Concentration
Oil recovery is influenced by the inlet oil concentration.
Strickland’s tests showed that, in the DGF and IGF units,
an increase in oil concentration from 100 to 200 ppm
increased oil removal efficiency. Again, this effect is
probably the result of the influence of population density
on the capture efficiency of the gas bubbles. However,
when discussing oil removal efficiencies, we must be
aware that unit performance is not being fully addressed.
Thus, using this removal efficiency as a sole measure of
performance may be misleading. The final oil content in
the outlet stream is the most important parameter, and
relating efficiency to this value gives a more meaningful
interpretation of performance.
For example, a flotation cell removing oil to 100 ppm
from 10,000 ppm has a separation efficiency of 99%. The
same cell removing oil to 40 ppm from 200 ppm has a
separation efficiency of only 80%. If the flotation cell
outlet requirement is 40 ppm, then the cell is operating
successfully only in the 80% efficiency case. The fact that
higher oil removal efficiencies are achievable at higher
inlet loading is irrelevant if the discharge specification is
not met.
Temperature
Strickland showed that increasing the produced-water
temperature will improve separation capabilities as a
result of a lower continuous-phase viscosity. However,
experiences with flotation systems in the North Sea
indicate that an upper temperature limit of 180 to 200°F
exists. At these elevated temperatures, steam condensing
in the gas blanket of a flotation cell reduces the gas vol-
ume that can be induced by the impeller of an IGF unit.
This decreased gas volume reduces gas concentration
and thus oil droplet capture efficiency.

Flotation Aids and Surface Chemistry
Strickland’s results showed that adding a surfactant
chemical to improve froth formation improved oil re-
moval efficiencies dramatically. In many operating
flotation systems, oil droplet coagulant aids or froth
promoters are used with various degrees of success.17
The total produced-water chemistry will affect the perfor-
Effective chemical mance of both DGF and IGF processes, but the surface
chemistry of the dispersed oil droplets is of primary
selection is often the key
importance. Oil droplets typically have a negative sur-
to successful flotation. face charge, which facilitates bubble/droplet attachment
because a positive static charge is imparted to the
bubbles during generation.13
Water-soluble flotation aids are often used to improve oil
removal efficiency. Many types of chemicals can, by
altering the surface chemistry of the dispersed phase,
improve separation performance. Cationic polyelectro-
lytes are used as coalescing agents to increase droplet
size; amine-based surfactants are used to enhance the
foaming capability of the water; and metal salts are used
to generate flocs to enhance solids separation.
The type of chemistry appropriate for enhancing separa-
tion should always be determined by screening potential
candidates in the field. This can be done using a bench-
scale flotation unit on the water to be treated. This
bench-scale test, if carried out in the field, is an extremely
accurate way to select chemicals. If the chemical is effec-
tive in the bench unit, it will be effective in the full-scale
flotation device.
Selecting the correct chemical is critical in many instances
because some surfactants and polyelectrolytes can cause
stable emulsions to form in the oil-rich froth, making
resolution of the oil and water phases very difficult.
Chapter 8 discusses this in more detail.
HYDROCYCLONES
Hydrocyclones have been used for many years to sepa-
rate solids from liquids and from air. These devices are
used as clarifiers, classifiers, and thickeners in a variety
of industries, including mining.

The devices typically are small and have a length/diam-
eter ratio of around 5:1. Depending on the design, the
diameter ranges from 0.01 to 0.102 m. These devices are
not suitable for removing dispersed oil from water.
The hydrocyclone used to separate oil from water is Hydrocyclones are the
known as a liquid/liquid hydrocyclone (LLHC). This current state of the art in
device has a vastly different geometry from the solid/ oil removal equipment.
liquid hydrocyclone.
The LLHC used today was developed by Southampton
University in England in the late 1970’s. Its length/
diameter ratio is about 45:1. The LLHC operates quite
differently from the traditional mining variety. Fig. 13
illustrates the differences between the two designs. This
“Southampton design” is the basis for most commercially
available cyclones used in oil fields today. This device
has become the separator of choice for offshore systems,
where the space and weight benefits of the small cyclones
can reduce topsides facilities costs significantly.
Design and Principle of Operation
Static Hydrocyclones
All static hydrocyclones currently available (Conoco’s
Vortoil and Hydropack, Amoco’s Hydroswirl, and Krebs’
De-Oiler) are similar in design, and all three have the
same principle of operation: generation of centrifugal
forces by fluid acceleration through a device of complex
geometry. The static hydrocyclone usually consists of
three distinct parts:
1. A cylindrical swirl section with a tangential inlet and
reject stream orifice.
2. A tapering conical body.
3. A cylindrical tail section with clean water outlet.
In all three devices, the feed stream enters the cylindrical
swirl section tangentially. This causes a high-velocity
vortex, which generates forces exceeding 1,000 g. The
fluid accelerates through the conical section, where,
because of its lower gravity, oil moves to a central core.
The majority of separation occurs in this section. The
fluid then passes into the cylindrical tail section, where

smaller oil droplets are separated. Clean water emerges
from the outlet port, while an axial flow reversal carries
the oil core out of the hydrocyclone through the reject
orifice. The total residence time in the hydrocyclone is
less than 2 seconds.
Dynamic Hydrocyclones
Only one dynamic hydrocyclone is currently available for
oil field use: the Dynaclean from Alstholm. This device
operates quite differently from the static units, generating
the separating forces by rotation. The dynamic
hydrocyclone is essentially a rotating cylinder with an
inlet port at one end and an outlet port at the other. The
reject stream outlet is via a conical reject orifice at the
outlet end. An external electrical motor with a variable-
speed drive rotates this device (Fig. 15).
The Dynaclean separates oil from the feed stream by
generating a free vortex in which oil migrates to a central
core because of its lower gravity. The feed stream enters
the device axially and then passes through a vane that
rotates at the same speed as the hydrocyclone wall. This
rotating vane imparts the rotational motion to the inlet
fluid. Separation takes place in the hydrocyclone body.
The clean water and the oil-rich reject stream exit the
device concurrently. The residence time for both streams
is a few seconds.
The pressure drop across the device is much lower than
for the static unit because it is caused only by the inlet
and outlet losses and a loss resulting from vortex genera-
tion.
Factors Influencing Performance

As in all oil/water separation equipment, oil/water
separation in static and dynamic designs obeys Stokes’
law. Stokes’ law states that the velocity of separation of
oil droplets in water depends on the oil/water differen-
tial gravity, oil droplet diameter, and water viscosity. In a
finite-residence-time vessel like a hydrocyclone, separa-
tion velocity is directly proportional to separation effi-
ciency. Stokes’ law can be expressed as

gd 2 (ρ w − ρ o )
V=
18 µ
where v = separation velocity,

ρw = water specific gravity,
ρo = oil specific gravity,
d = oil droplet diameter, and
µ = water viscosity.
We can see from Stokes’ law that the driving force for
separation is the specific gravity difference between the
oil and water phases. The fact that oil droplet diameter is
a squared term also plays an important part in separa-
tion. This has been proved in practice. Several tests have
shown that droplet size is a critical parameter.
Temperature also influences separation performance by
altering the water-phase viscosity. A temperature in-
crease usually will improve hydrocyclone performance
by reducing the water-phase viscosity.
Stokes’ law indicates the factors influencing the perfor-
mance of both static and dynamic hydrocyclones; how-
ever, some influencing factors are specific to the type of
hydrocyclone in question. Static hydrocyclone perfor-
mance is influenced greatly by two factors: operating
pressure and reject ratio.
Operating pressure is critical for successful hydrocyclone
operation. For a given flow rate, a minimum inlet pres-
sure is required to generate the vortex inside the device.
When the minimum inlet driving pressure is reached,
inlet-to-outlet and inlet-to-reject differential pressures
control separation performance. For most current cy-
clone designs, the minimum inlet pressure for controlled
operation is 50 to 90 psig. Typically, this yields a reject
stream pressure of 2 to 5 psig, which is required in most
applications for control.
The new 1” diameter
Conoco, Amoco/MPE, and Krebs engineers recently cyclones offer better oil
introduced 1-in.- diameter cyclones that can operate at
pressures as low as 25 psig. This low-pressure driving removal performance
force is obtained at the expense of capacity, which is than the large designs —
reduced to around 15 gal/min per cyclone. Field operat- but at a cost penalty.

ing data for these units have shown a performance im-
provement exceeding the traditional 35-mm-diameter
designs.
Reject ratio is the ratio of reject flow to inlet flow ex-
pressed as a percentage. It influences performance in
operating below and above the optimum ratio.
Operating below the optimum reject ratio results in low
oil removal efficiencies because the separated oil is not
being removed from the hydrocyclone. Operating above
the optimum reject ratio does not impair oil removal
efficiencies but adds to the volume of the reject stream.
This may be important if the stream is to be processed
further. Typical operating reject ratios range from 0.5% to
3%.
Dynamic hydrocyclones are operated slightly differently
from the static variety, and the effects of pressure and
reject ratio on performance are not as pronounced. The
inlet pressure required to drive a rotating hydrocyclone is
less than the 90 psig required to drive a static unit. The
reason is that no pressure drops cause by complex geom-
etry must be overcome. Typically, 50 psig is required to
operate a rotating unit at minimum flow rate. The effect
of reject ratio is not important in rotating hydrocyclones;
the critical parameter is reject flow. The reject flow is
constant across the whole inlet flow range of the device.
Hence, reject flow, not reject ratio, is the optimum param-
eter.
A parameter that greatly influences oil removal efficiency
is rotational speed. Higher rotational speeds give better
oil removal efficiencies at a given flow rate. However,
this improvement in efficiency is at the expense of higher
inlet pressures. The rotational speed for a dynamic
hydrocyclone usually is between 1,600 and 3,000 rpm.
Typical Performance
Static Hydrocyclones
The Vortoil, a 35-mm unit, has an operating range of 28 to
50 gal/min at 60 to 350 psig. With a standard 4-mm
reject orifice, the optimum reject ratio is 2% in most test
cases.

The Hydropack does not have a characteristic diameter
but is only slightly smaller than the Vortoil unit. The
operating range of this device is 25 to 40 gal/min at 60-
to 300-psig inlet pressure. With a 3-mm orifice, the opti-
mum reject ratio is around 1% in most test cases. The
Amoco Hydroswirl has an operating range of 22 to
37 gal/min at 60- to 100-psig inlet pressure. It operates
best with a reject ratio of around 2%.
In a number of Chevron tests, the Vortoil, Hydropack and
Hydroswirl devices showed oil removal efficiencies of
50% to 90% across the entire operating region. The major
contributor to the variation in operating efficiency is oil
droplet size. In Chevron tests, this was more pronounced
than the effects of oil/water specific gravity difference.
Similar results were obtained for the Vortoil cyclones in
20 API, 0.08 differential gravity as in 30 API, 0.2-differen-
tial-gravity systems. Increasing the median oil droplet
size from 5 to 15 µm gave a 25% increase in oil removal
efficiencies for both devices. At a median diameter of 15-
µm, operating efficiencies of 90+% can typically be
achieved.
Dynamic Hydrocyclones
The Alstholm Dynaclean unit used in Chevron tests was
a Model 2 unit. Its operating range is 30 to 90 gal/min at
50- to 250-psig inlet pressure. The nominal flow rating
for this device is 73 gal/min at 2,500 rpm. The rotational
speed varies from 1,600 to 3,000 rpm. The device consis-
tently achieved oil removal efficiencies of 90% at maxi-
mum rotational speed and nominal flow rate. Reduc-
tions in separation efficiency were seen at higher flow
rates and lower rotational speeds. The Dynaclean unit
separates small oil droplets more efficiently than the
static units and will give higher removal efficiencies for
droplets smaller than 15 µm in diameter. Fig. 16 com-
pares typical static and dynamic cyclone performance.
Applications to Date
Most hydrocyclones in use today are permanent installa-
tions on offshore platforms. The space and weight ad-
vantages of LLHC’s over plate-pack separators and
flotation units are most useful, and savings in platform

structural cost make them the separator of choice. The
offshore installations typically provide the high natural
driving pressures required to run LLHC’s.
Hydrocyclone Selection
With the evolution of less expensive cyclone designs and
low-pressure second-generation cyclones, this technology
is also becoming applicable in onshore operations. Sev-
eral pieces of information are required to select a cyclone,
including available driving pressure, water temperature,
maximum and minimum flow rates, steady-state and
upset inlet oil concentration, desired outlet oil concentra-
tion, existing chemical treatments, and, if possible, an
inlet oil droplet size distribution. The last item is ex-
tremely valuable information for predicting cyclone
performance that is not available in most situations.
Armed with the above information, the cyclone manufac-
turers should be able to predict cyclone performance and
to provide a cost estimate for your application.
With a new facility in the process design stage, the manu-
facturers’ predicted performance criteria should be used
Run field evaluations of if backed up by field performance data from similar
hydrocyclones to operating conditions. If not, then the origin of the data
for performance prediction should be established. Our
establish their operating
experiences indicate that manufacturers’ predictions of
capabilities. performance are not always accurate. In many cases, the
actual cyclone performance exceeded manufacturers’
predictions.
With an existing facility, on-site evaluation of cyclone
performance should be standard procedure. Small test
skids are available from each manufacturer. These skids
are easy to use and will yield useful performance and
control data. If possible during this field test, droplet size
and oil removal information should be used to character-
ize cyclone performance. This information is valuable in
designing and operating upstream facilities to minimize
droplet breakup and to determine whether a downstream
residence tank will act as a useful polishing treatment
stage.

FILTERS
In general, most filters are not used as oil/water separa-
tors, nor are they designed to be used in this manner.
Filters are usually designed to remove solids from water.
However, some filters can remove oil from water and are
more tolerant to oily water service.
Many types of filter are in use today. Most are covered in
the filtration section of this handbook. Some useful
guidelines about operating and selecting filters for oil-
field use are given below.
Downflow Sand/Multimedia Filters

Sand/multimedia filters usually can operate in waters
where the oil concentration does not exceed 15 ppm.
Mudballing and oil bleed-through should be expected if Filters are not designed to
this limit is exceeded. This filter is not designed as an oil remove oil and they
removal device, but it will separate free oil from water if
the inlet concentration is low (<10 to 15 ppm). Extended should not be used for
use of filters with >10 ppm oil concentration is not rec- this purpose.
ommended. Extended backwashing with surfactants is
usually the result of an oiled filter bed. This gives rise to
a backwash waste stream, which is very difficult to treat
because solids and oil released from the bed can form
emulsions stabilized by the surfactant washing chemical.
Recycling this type of stream will result in process upsets.
Hence, it is not recommended.
Nutshell Filters
These types of filters are designed with produced-water
use in mind. They are more tolerant to oil than any other
type of filter in oilfield use and are reasonable oil separa- Nutshell filters are more
tors. Typically, these filters do not act as true separators tolerant to oil than sand
but as oil accumulators. The oil in the feed stream enter- filters.
ing the filter is retained within the filter bed and is re-
moved during backwashing. One of the three commer-
cial variants, however, has the option of using an oil
take-off valve for any free oil that floats to the top of the
filter.

These filters can typically tolerate up to 50 ppm of oil in
their influent and can reduce this influent concentration
to <5 ppm. Therefore, they are best used as a polishing
stage after flotation for treatment of produced water for
reinjection.
THE INTEGRATED TREATMENT SYSTEMS

APPROACH TO COST-EFFECTIVE WATER
TREATMENT
The concept of an integrated treatment systems (ITS)
approach to water treatment is simple yet powerful. If
we consider water treatment an integrated part of our
oilfield fluid processing facilities and not just an add-on
piece of equipment, we will achieve more efficient sepa-
ration.
Considering water treatment as a process and not a piece
of equipment will help us select the most efficient unit
operations to reach our goals. These unit operations
include mechanical processes (e.g., flotation) and chemi-
cal processes (e.g., coalescence and flocculation). An
ITS approach looks at the implications of both chemical
and mechanical aspects of water treatment and results in
harmonious selection and operation of processing stages.
Just as chemical and mechanical aspects of treatment
must be harmonized, so must the separation processes
themselves. In many cases, separation of oil and solids
from water is done by separate processes — e.g., gravity
separation and media filtration. Process selection will
affect the final quality of the treated water. Poor oil
removal may lead to poor filtration, which in turn leads
to poor-quality water. The interaction of both processes
must be understood and then optimized as a total sys-
tem.
The ITS philosophy encompasses more than the unit
operations of water treatment; the impact of upstream
and recycle processes will obviously influence the perfor-
mance of the water treating facilities and thus the final
Integrated Treatment water quality.
Systems = Cost effective The effect of crude oil dehydration on water quality
cannot be overemphasized. Poor dehydration will lead
operation.
to an excessive concentration of oil in the water phase to

be treated and/or will result in a stabilized oil-in-water
emulsion that is difficult to treat. All water treating
equipment is designed to remove oil from produced
water within defined ranges of concentration and oil
droplet size. If these ranges are exceeded by high oil
concentrations or small droplets (in a stable emulsion), Integrated Treatment
then the performance of the separation device will be System = Optimized
reduced.
Design + Optimized
Because dehydration performance is often influenced Operation.
directly by the demulsifier chemistry, correct chemical
selection is critical to the downstream water treatment
processes. Overdosing the demulsifier chemical is often
the cause of tight oil/water emulsions, which are very
difficult to treat in traditional water treating facilities.
Another important aspect of the ITS approach is under-
standing the effect of recycle streams on final water
quality. The recycle stream that is most important to the
water treatment process is the oil recovered in the water
treating facilities. This recovered oil is often in the form
of IGF skimmings, PPI skimmings, settling-tank skim-
mings, or hydrocyclone reject streams. In most systems,
the recycle stream consists of an oil/water mixture and is
usually recycled back into the dehydration stream. While
intuitively this seems to be an ideal place to recycle,
problems occur if the recycle stream contains such chemi-
cals as flotation aids or coagulants. These chemicals tend
to stabilize emulsions in the dehydration system, which
result in interface pad buildup in the dehydration ves-
sels. This may lead to poor oil quality, but almost cer-
tainly to poor water quality because the interface pad
sloughs into the water phase, leading to dirty water.
This interface pad, a very good emulsifying agent, will
cause a very stable emulsion to form, thereby further
decreasing the performance of the water treating equip-
ment. To improve performance, we may be tempted to
increase the dose of any water treating chemical in the
system, which in turn will lead to excess chemical in the
recycle stream, which degrades dehydration, etc.
In essence, we create a spiral of degradation, which
results in poor facilities control and poor water quality.
The solution is to select water treatment chemicals that
minimize the effect of emulsion stabilization and are

compatible with the demulsifier chemistry selected.
Also, we should consider pretreating the recycle stream
to recycle dry crude oil, which is chemical-free.
Hence, using an ITS approach to design and optimize the
total treatment system as a whole can eliminate prob-
lems. Pretreating recovered oil before recycling is an
example of the point source treatment concept. An
integral part of the ITS philosophy,, this concept is out-
lined further in Chapter 10.
We can illustrate the ITS concept best with a simple
example. Fig. 17 Illustrates a simple water treatment
facility and its associated upstream facilities. The system
itself consists of a three-phase separator for crude oil
dehydration, and a flotation cell for oil removal from
produced water. Upstream of the flotation device is a
surge drum to minimize flow variations to the IGF unit.
Using an ITS approach to design and operate this facility,
we should note the following points:
1. Demulsifier injection occurs far upstream of the
dehydration vessel. This allows the demulsifier to act
effectively and minimizes the chance of overdosing.
The chemical was selected to give optimum dehydra-
tion performance and good water quality. It was also
subjected to extensive tests to ensure compatibility
with other chemicals used in this system.
2. The dehydration vessel is designed and operated to
give sufficient water-phase residence time to allow a
significant number of oil droplets to be dragged into
the water phase during dehydration to return to the
oil phase. As a result, the outlet water stream typi-
cally has an oil concentration of <200 ppm.
3. The coagulant/flotation aid is selected to give an
adequate foam in the IGF that is easily destabilized.
The chemical itself is very water-soluble, which limits
its concentration in the oil skimmings stream. Again,
it has been selected to be compatible with all other
chemicals used in the system. The chemical injection
point is as far upstream of the IGF as possible. An in-
line mixer is used to enhance contact of the chemical
and the oil droplets. The chemical injection pump is
selected to deliver the correct dose rate effectively. It

is a positive displacement pump with a small stroke
length but a high stroke rate. This ensures even
injection of the chemical continuously. Large-stroke/
low-rate pumps effectively batch treat pockets of fluid
entering the IGF. This leads to intermittent overdos-
ing, stabilized emulsified skimming, and poor water
quality.
4. The IGF skimmings are treated before recycling in a
residence-time vessel, designed to give “dry” oil and
clean water. The tank also has a cone bottom, allow-
ing the effective removal of solids that fall out.
5. “Dry” oil from the skimmings separator, not the entire
skimmings stream, is recycled. (If dry oil cannot be
obtained, the operation of the flotation cell and
chemical coagulant/flotation aid need to be investi-
gated and optimized.)
6. Separated water from the skimmings tank is recycled
downstream of the surge tank and upstream of the
IGF. This point is chosen to eliminate the possibility
of contaminating the surge tank if plant upsets occur.
Integrating the water treating facilities, waste-stream
handling facilities, and chemical treating strategy into an
overall process results in optimized produced-fluids
processing.
As the above example shows, ITS is effectively a total
system approach to water treatment. It recognizes the
impact of upstream processes, chemical treatments,
recycle streams, and poor monitoring and optimization
procedures. Consulting with equipment and chemical
suppliers before finalizing a design will pay dividends in
the final operating facility.
PROCESS/EQUIPMENT SELECTION
Using an ITS approach is the preferred way to handle
produced- water treatment. In the ITS philosophy, each
unit operation is considered an integral part of the whole
treatment process. Consequently, the impact of chemical
pretreatment and waste-stream handling will be consid-
ered during selection of oil/water separating equipment.
Several facilities templates are available in the ITS phi-
losophy for selecting oil/water separation equipment.

Fig. 18, a selection flow chart, outlines these templates.
These template systems are not intended as complete
designs or as exclusive processes. Each operations re-
quirement differs slightly from the others. Using an
ITS approach should result in an optimized system: the
templates can be used as a guide or first stage in the
facilities and process selection procedure.
As Fig. 18 shows, the systems are broken down into
offshore and onshore, injection and discharge scenarios.
As discussed earlier in the Water-Quality Requirements
section, different standards of oil removal are required
for injection and discharge. This is evident in the process
templates, where primary oil removal is followed by
water polishing in filters for water injection systems.
Using an ITS approach and considering chemical and
recycle stream effects, the template systems are
Chevron’s favored processes for each application if we
start with a clean sheet of paper. Each process has sev-
eral unit operations integrated into the treatment system,
and correct selection of the unit operations is critical to
achieving good water quality.
The final selection of a piece of equipment should obvi-
ously be made on a cost-performance basis. This should
include installed and projected maintenance costs, not
just capital cost. Selection will also depend on whether
the existing facilities contain some water treatment
equipment or whether this is a new facility, and on
whether separation can be considered a coarse or polish-
ing stage of the overall treatment process.
For adding equipment into old facilities, we should
consider whether modifying existing processes will give
better cost performance than adding new facilities. Of-
ten, retrofitting vessel internals to improve performance
is more cost-effective than adding new facilities.
Again, water treatment equipment should not be selected
in isolation. Ancillary chemical and separated waste
stream facilities and the main process facility should be
considered. We can minimize incompatibilities and
reduce operation and maintenance costs only by consid-
ering all aspects of the treatment system.

MONITORING AND MEASUREMENT
General
Oil-in-water concentrations are determined for two
primary reasons: monitoring plant operation and report-
ing discharge to the regulatory authorities. While report-
ing standards are important, monitoring plant perfor-
mance from an optimization standpoint is also
important. Most facilities today rely on manual sampling
and analysis for optimization and reporting purposes.
However, emerging technology may be used to monitor
plant operation and to determine discharge standards.
On-Line Methods
Currently, no on-line methods exist to measure oil-in-
water concentrations in an operating oilfield repeatedly,
accurately, and cost-effectively. Some on-line monitors
are commercially available, but they have less-than-ideal
operating accuracies and are prone to high maintenance.
These monitors use a variety of techniques to measure oil
concentrations, and all are prone to problems. However,
new monitors using the techniques described below are
being developed, and initial laboratory results are en-
couraging. Technical Memorandum TM91001083 in the
Appendix includes a description of this testing.
Four basic on-line techniques are used to measure oil-in-
water concentrations: infrared light scattering,
infrared absorption, ultraviolet absorption, and ultra-
sonic.
Infrared Light Scattering

This technique uses an infrared light source and one or
more detectors to measure oil concentration. Usually, the
light source, a photodiode emitting infrared light at
8,800 Angstroms, is placed perpendicular to the flow-
through sample cell. If no discontinuities are present, the
light passes through the cell. When oil or solids are
present in the cell, the light is scattered and picked up by
the detectors. The detector offset angle is chosen to
maximize the sensitivity of oil-scattered light and to
minimize the sensitivity of solids-scattered light. The
intensity of the scattered light depends on the detection

angle, the oil droplet density, and the droplet particle size
relative to the wavelength of the light. Hence, wave-
length is critical to accurate measurement of oil concen-
tration. Most manufacturers choose 8,800 Angstoms
because that value maximizes oil droplet detection and
minimizes the effects of water color and solubles. This
type of instrument typically operates at 0 to 200 ppm.
This technique has proved to be one of the most accurate
on-line methods. However, it still suffers from inaccura-
cies, notably loss of accuracy at small droplet sizes
(<10 µm) and loss of repeatability when samples contain
free gas.
Infrared Light Absorption

Two types of infrared absorption techniques are used:
direct absorption and solvent extraction/absorption.
Direct Absorption
This technique uses the principle of absorption of
infrared light by discontinuities in the fluid stream.
Usually, a sample is drawn from the process stream into
the unit’s sample cell, where the amount of infrared light
absorbed by the oil is measured. The wavelength of the
light is specifically chosen to maximize sensitivity to oil.
The wavelength for all commercial units is 34,000 Ang-
stroms. A second wavelength of 36,000 Angstoms, which
is insensitive to oils, is also used to detect solid materials.
This enables a “net oil concentration” to be measured.
Unlike systems that extract oil from water with a haloge-
nated hydrocarbon solvent to avoid the high absorbance
of the water itself, this system compares the absorbance
of the oily water with that of a de-oiled reference stream.
This reference stream, ultrafiltered process water, pro-
vides a background base absorbance. The difference in
absorbance between the reference and sample streams is
linearly proportional to oil content. This type of analyzer
has an operating range of 0 to 2,000 ppm.
This technique is fairly accurate over a wide range of
droplet sizes, but it is very sensitive to temperature
changes. Controlling the flow rate of the sample is also
critical for repeatable, accurate results. Two negative

aspects of this type of device are its size and complexity.
The device has feed pumps, oil drop dispersers, and an
ultrafilter system for the reference sample.
Solvent Extraction/Infrared Absorption

This technique also uses infrared absorption, but on oil
extracted from a sample of the process stream by a halo-
genated hydrocarbon (usually freon). Absorption is
measured at a wavelength of 34,000 Angstroms.
In this device, the sample is fed via a constant-head
device into the unit. Oil is extracted continuously from
the sample and the extractant is analyzed by infrared
light. The solvent is then reclaimed with activated car-
bon adsorption. Before the solvent is recycled, it is
passed through the infrared measuring cell to detect any
residual oil, which is then included in the background
light absorption. This type of device operates at 0 to
100 ppm.
Although relatively accurate, this type of device is very
maintenance-intensive. Thus, it is not suited to continu-
ous unattended operation. It also consumes about 1 kg
of solvent a month. The device cannot rapidly determine
oil concentration because it usually requires several
minutes to reach a steady reading. The biggest draw-
back, however, is that not all crudes are soluble in freon.
This leads to erroneous readings and, in some cases, cell
fouling.
Ultraviolet Absorption
This instrument measures oil concentration much like the
infrared absorption units, but it uses ultraviolet light at
2,540-Angstom wavelength. Most devices of this type are
dual wavelength: one to measure oil concentration and
one, a reference, to compensate for solids and optical
anomalies. At this reference wavelength, oil does not
absorb significant ultraviolet energy; hence, the oil com-
ponent in the total absorption spectrum can be isolated.
The operating range of ultraviolet absorption oil in water
monitors is 0 to 100 ppm.

These devices are accurate, but also complex and mainte-
nance-intensive. The use of a reference wavelength is
also prone to error because very small oil droplets inter-
fere with ultraviolet absorption by solids. This leads to
an increase in “background” absorption, which in turn
leads to underestimated oil content.
Laboratory Methods
Laboratory methods of oil-in-water determination are the
most common form of monitoring separator perfor-
mance. The methods are outlined in the Analytical and
Test Methods section (pp. 2-75 to 2-88).
As outlined in this section, the methods themselves
define “oil.” Some methods include soluble hydrocarbon
species in the oil concentration measured. It is important
to note that all the equipment and separation processes
discussed in this chapter are designed to remove only
free oil.

REFERENCES
1. “Determination of Best Practicable Control Technol-
ogy Currently Available to Remove Oil from Water
Produced with Oil and Gas,” Brown and Root Inc.,
report prepared for Offshore Operator’s Committee
(USA), March 1984.
2. Somani, A. H. et al.: “Produced Water Treatment
Technologies for Reuse or Disposal,” Zhou’Zhou
(Oct. 26-30, 1987).
3. Hinze, J. O.: “Fundamentals of the Hydrodynamic
Mechanism of Splitting in Dispersion Processes,”
AIChE J. (Sept. 1955).
4. Arnold, K. and Stewart, M: Surface Production Opera-
tions, Gulf Publishing Co., Houston (1986) I, 215.
5. Three-Phase Separator Design, IHRDC Bookware Series,
Paragon Engineering Services, Houston.
6. “Designs for Water Quality Improvement,” Oilfield
Water Quality Improvement Training Manual, C. E.
Natco (1985).
7. Stires, J.: “Design of a High Rate, High Volume Oil/
Water Separator,” JPT (Nov. 1982).
8. Bradley, B. W.: “Qualitative Separation = Theory +
Judgement,” OGJ (Oct. 14, 1985).
9. Dodge, F. T.: “Scale Model Study of Oil/Water Sepa-
ration in Wash Tank for Duri Steam Flood Gathering
Station,” Southwest Research Inst., San Antonio, TX
(April 1983).
10. Bradley, B. W.: Two Oil Field Water Systems, R. E.
Krieger Publishing, Malabar, FL (1987).
11. Patton, C. C.: Applied Water Technology, Campbell
Petroleum Series, Norman, OK (1986) Chap. 6.
12. Jones, P. S. et al.: “Evaluation of Static and Dynamic
Hydrocyclones for Removal of Oil from Produced
Water, Murphy Coyote Lease,” TM89000928 (June-
July 1989).
13. Murti, D. G. K., Al-Maskati, A. H., and Sood, L. K.:
“Improved Disposal-Water Treatment at Bahrain Oil
Fields,” SPE Production Engineering (Nov. 1988).

14. Leech, C. A.: “Oil Flotation Processes for Cleaning
Oil Field Produced Water,” paper presented at the
AIChE Annual Meeting, Houston, April 1987.
15. Strickland, W. T.: “Laboratory Results of Cleaning
Produced Water by Gas Flotation,” SPEJ (June 1980).
16. “Field Test Results with Petreco Flotation System for
Oil Removal from Produced Water,” Petrolite Corp.,
St. Louis, MO.
17. Jackson, G. E.: “Oil Wastewater Treatment in the
Production of Crude Oil,” Chemicals in the Oil Industry
1983, Royal Soc. of Chemistry, London.

GLOSSARY
Coagulation — The neutralization of surface charge on
an oil droplet or small solid particle.
Coalescence — The rupturing of the interfacial film
between agglomerated oil droplets which results in
the formation of one large droplet from several
smaller droplets.
Dehydration — The resolution of crude oil into its oil
and water components.
Demulsifier — Chemical used to enhance/effect crude
oil dehydration. This is usually a blend of organic
components in a solvent.
E. O. R. — Enhanced Oil Recovery
Emulsification — Generation of emulsion. Requirements
are oil + water + emulsifier + agitation. All must be
present to form an emulsion.
Emulsion — A stable mixture of oil and water.
Filter Backwashing — The washing of a filter to remove
solids accumulated during the filtration cycle. This is
usually carried out when the filter reaches a given
pressure drop indicating that it is totally “full” of
solids.
Flocculation — The agglomeration of neutrally charged
oil droplets or solids.
Flotation Aid/Reverse Demulsifier — Chemical used to
enhance the performance of a flotation device. This is
usually a cationic polyelectrolyte.
Ion Exchange — Substitution of Sodium and Hydroxide
ions for Calcium, Magnesium and Carbonate ions in
water. This softens the water reducing the ability of
the water to scale at elevated temperatures.
Mudballing — The agglomeration of sand and oil in a
media filter. Mudballing is an indication that filter
backwashing is inefficient or that the feed oil concen-
tration is to high for the filter to deal with.
Permeability — The ability of a reservoir rock to allow
flow through it. Higher permeability = easier injec-
tion. Units of permeability are Darcys or Millidarcys.
Steamflood — Injection of steam into a reservoir as a
secondary recovery process.

APPENDIX

C H A P T E R
Filtration
We are currently revising this chapter to include new

cartridge filter technologies and chemical
optimization protocols for media filters.
Chapter 4: Filtration 4-1

C H A P T E R
Scaling and
Water Formed Solids
Chapter 5: Scaling and Water Formed Solids 5-1

INTRODUCTION
This chapter focuses on common oilfield scales, empha-
sizing their prediction, prevention, and removal. In
addition to the material in this chapter, several useful
papers are included in the Appendix. Interested readers
may contact CPTC for copies of references not included
in the Appendix.
SCALES AND THEIR PREDICTION

The key concept in scaling (precipitates depositing from a
brine) is solubility. Solubility is the limiting amount of a The key concept in Scale
solute that can dissolve in a solvent (water or brine)
Formation is solubility,
under a given set of physical conditions. Chemical
species of interest in oil- and gasfield brines are present the limiting amount of
as ions. Certain combinations of these ions have a rela- solute in the brine.
tively low solubility in water. Solids (scales) may deposit
from the brine once this capacity, or solubility, is ex-
ceeded.
The mechanisms for exceeding the solubility limits are
associated with changes in:
1. Water composition (e.g., mixing two incompatible
waters).
2. Physical conditions (e.g., pressure or temperature
changes can reduce the solubility enough to result in
precipitation.
Solid precipitates may either stay in suspension in the
water or form an adherent scale on a surface such as a
pipe wall. Both are undesirable. Suspended solids may
cause problems like formation plugging. Adherent scale
deposits can restrict flow in pipes and damage equip-
ment such as pumps. Corrosion and microbiological
activity are often accelerated under scale deposits. Be-
cause water-formed scales are responsible for many
production problems, effective scale control is a primary
objective of any efficient water handling operation.
The references provide further details for the interested
reader. Patton1 provided one of the best overviews of
this subject. Other excellent sources of information are
Cowan and Weintritt’s2 and Ostroff’s3 work.

Common Scales
Table 1 lists the most common water-formed scales in
oilfield waters. This table includes the primary variables
that affect their solubility. Table 2 lists the common
causes for the formation of these deposits and possible
chemical solvents to remove them.
A few general remarks about the most common scales are
given below. Scales formed in oilfield operations are
usually a mixture of two or more of these scales and
organic solids (asphaltenes, paraffins, etc.). Refs. 1
through 3 provide further details.
Calcium Carbonate
Calcium carbonate, the most common scale in oil- and
gasfield operations, occurs in every geographic area.
Calcium carbonate precipitation occurs when calcium ion
is combined with either carbonate or bicarbonate ions as
follows:
++ =
Ca + CO 3 → CaCO 3 (s) (1)
Ca
++
( )
+ 2 HCO −3 → CaCO 3 (s) + CO 2 + H 2 O (2)
Eq. 2 shows that the presence of CO 2 increases the solu-

bility of CaCO3 in brine. Increasing the concentration of
CO2 in solution shifts this reaction to the left, resulting in
pH is an important factor less calcium carbonate scale. Increasing CO2 also makes
in calcium carbonate the water more acidic (decreases the pH). Often, calcium
solubility. carbonate scaling occurs with a pressure drop (e.g., at the
wellbore of a producer). This reduces the partial pressure
of CO2, thereby increasing the pH and decreasing the
CaCO3 solubility.
An unusual and very important property of calcium
carbonate is that its solubility decreases with increasing
temperature.
Calcium Sulfate
The precipitation of calcium sulfate is given by the reac-
tion
Ca ++ + SO =4 → CaSO 4 (s) (3)

Chapter 5: Scaling and Water Formed Solids
Table 1 Common Oil Well Scale Deposits — Solubility Factors

Most Important Factors Affecting Solubility
Chemical Mineral Partial Total Total
Deposit Formula Name Pressure CO2 pH Pressure Temperature Salinity Corrosion H2S Oxygen
Calcium CaCO3 Calcite X X X X

Carbonate
Calcium CaSO4 • 2H 2O Gypsum X X X
Sulfate CaSO4 Anhydrite
Barium BaSO4 Barite X X X
Sulfate
Strontium SrSO4 Celestite X X X
Sulfate
Iron FeCO3 Siderite X X X X X
Carbonate
Iron Sulfide FeS Trolite X X X
Iron Oxide Fe2 O3 Hematite X X X
Fe3 O4 Magnetite X X X
Sodium NaCl Halite X X
Chloride
Magnesium Mg(OH)2 Brucite X X
Hydroxide
Silicates Variable X X X
5-5
5-6
Table 2 Common Oil Well Scale Deposits — Causes and Removal Chemicals
Chemical Most Frequent Causes Removal
Deposit Formula Mineral Name of Scale Deposit Chemical
Calcium CaCO3 Calcite Mixing Brines, Changes in 15% HCL
Carbonate Temperature and Pressure
Calcium Sulfate CaSO 4 • 2H 2 O Gypsum Same as Above Converting
CaSO 4 Anhydrite Solutions, EDTA
Type Dissolvers
Barium Sulfate BaSO4 Barite Mixing of Brines ?
Strontium Sulfate SrSO4 Celestite Mixing Brines, Changes in ?
Temperature and Pressure
Iron Carbonate FeCO3 Siderite Same as Above Sequestered
Acid
Iron Sulfide FeS Trolite Corrosion by Sour Crude or H 2S Gas Same as Above
Iron Oxide Fe2O3 Hamatite Reaction of Oxygen with Dissolved Same as Above
Fe3O4 Magnetite Ferrous Ion
Sodium Chloride NaCl Halite Evaporation of Water Water or 1–3%
HCL
Magnesium Mg(OH)2 Brucite Excessive Amounts of Oxygen Enter 15% HCL

Hydroxide the Well or Alkaline Fluids in Well.
High Temperature
Silicates Variable Cooling of Hot Brine High in HCL:HF Acid
Dissolved Silica Mixtures
This scale may occur in different forms. Gypsum
(CaSO4.2H2O), the most common in oilfield brines, is Gypsum is the most
associated with lower temperatures. Anhydrite (CaSO4) common calcium sulfate
may occur at high temperatures. Theoretically, anhydrite
scale.
would be expected to precipitate above 100°F in prefer-
ence to gypsum because of its lower solubility. However,
gypsum may be found at temperatures as high as 212°F.
With the passage of time, gypsum may dehydrate to
anhydrite.
Gypsum solubility increases with salinity up to about
150,000 mg/L total dissolved solids. Further increases in
salt content increase its scaling tendency. In contrast to
calcium carbonate, gypsum solubility is almost indepen-
dent of pH.
A common mechanism for gypsum precipitation in the
oil field is a reduction in pressure (e.g., at the production
wellbore). The solubility increases with higher pressure
because, when the scale is dissolved in water, the total
volume of the system decreases. 4,5
Gypsum scale is perhaps the most common in west Texas
oil fields because these brines often have high concentra-
tions of calcium and sulfate.
Barium Sulfate
This scale is especially troublesome. It is extremely
insoluble and almost impossible to remove chemically. Barium sulfate is the most
Fig. 1 compares the solubilities for common oilfield scales difficult oil field scale to
in distilled water. Barium sulfate scaling is likely when
deal with.
both barium and sulfate are present, even in low concen-
trations.
++ =
Ba + SO4 → BaSO 4 (s) (4)
Most barium sulfate scales also contain some strontium

and radium sulfate because these cations are chemically NORM (radioactive scale)
similar to barium. The presence of radium is a special
is associated usually with
problem because it makes the scale radioactive. Extra
precautions must be taken in the disposal of barium barium sulfate.
sulfate scales if the radioactivity is high.6,7
Barium sulfate scale is common in North Sea reservoirs,
such as Chevron’s Ninian field. These fields often have
barium in the original formation brine. Seawater injec-

tion (high sulfate concentration) for secondary oil recov-
ery causes the scale problem. As the waterflood matures
and the seawater breaks through, these incompatible
waters mix and the barium scale forms.
Generally, barium sulfate solubility increases with
temperature and salinity. Similar to gypsum, BaSO4
solubility increases with an increase in total pressure and
is largely unaffected by pH.8,9
Strontium Sulfate
Strontium sulfate is similar to barium sulfate, except
fortunately its solubility is much greater.
Sr++ + SO 4 → SrSO 4 (s) (5)
Strontium sulfate solubility increases with salinity (up to

175,000 mg/L), temperature, and pressure. Again, pH
has little effect.10-13
Pure strontium sulfate scale is rare except for some fields
in the Middle East. SrSO4 deposits in producing wells
where the strontium-rich formation water mixes with the
sulfate-rich injected seawater.14,15
Iron Compounds
The iron deposits are much more complicated than
The oxidation state of scales. One reason is that the iron may come from the
formation water, corrosion, or both. Another complica-
iron is important in the tion is that the dissolved iron may be present in two
form these scales take. oxidation states: Fe++ (ferrous) and Fe+++ (ferric). The two
cations form compounds with the same anions but with
very different solubilities.
CO2 will react with the ferrous ion to form iron carbonate
scale. This scale has similar solubility behavior as cal-
cium carbonate vs. pH, temperature, etc., except the
solubility of FeCO3 is approximately 100 times lower.16,17
Hydrogen sulfide readily causes iron sulfide to form as a
corrosion product. This sulfide typically is very insoluble
and forms a thin, adherent scale. Suspended iron sulfide
is the cause of “black water.” This also may occur by
mixing one stream containing dissolved H 2S with an-
other containing dissolved iron.

Oxygen can form a number of different compounds
when it comes into contact with water containing dis-
solved iron. Examples include ferrous hydroxide
[Fe(OH)2], ferric hydroxide [Fe(OH)3], and ferric oxide
[Fe2O3]. “Red water” is caused by suspended particles of
Fe2O3. Oxygen also initiates the formation of “black
water” when it comes into contact with a water contain-
ing dissolved H2S and iron.
Predicting Scale Formation

This section discusses the usefulness of solubility calcula-
tions in predicting the formation of certain types of scale.
The various methods are discussed briefly here; Refs. 1
through 3 give details and examples. Newer computer-
aided solubility calculations are described later in this
section.
Solubility calculations may be performed to determine
the theoretical amount of scale-forming ions that can be
kept in solution. Comparison with the actual concentra- Scaling tendency is a
tion of the scaling ions in solution indicates the scaling
tendency or the likelihood of scale formation. measure of the driving
force or likelihood of
Note that these calculations only provide a guideline and
are not necessarily exact. Simplifying assumptions have scale deposition.
been made in the derivation of all predictive equations;
the solubility of inorganic compounds in naturally occur-
ring waters is a complex phenomenon.
Saturation Index
Consider for example a water containing barium and
sulfate. The theoretical solubility product, Ksp , is given
by
(
K sp = C Ba
++
)( )
=
C SO 4 (at saturation) (6)
where (CBa++) is the barium concentration and () is the

sulfate concentration. As explained previously, Ksp can be
estimated for a given brine salinity, temperature, and
pressure based on laboratory data.

The supersaturation ratio (SR) is defined as the ratio of
the ion product (IP) actually present in the brine to the
solubility product:
IP = C Ba ++ × C SO 4 = (7)
IP
SR = (8)
K sp
In terms of SR, the possibilities for precipitation are:

1. SR < 1: The solution is undersaturated; no precipita-
tion can occur.
2. SR = 1: The solution is saturated.
3. SR > 1: The solution is supersaturated; precipitation
can occur.
Calcium Carbonate Scaling Calculation

The scaling tendency for a brine with respect to calcium
carbonate is commonly expressed as a saturation index.
The saturation index, SI,
This is the logarithm (base 10) of the SR (actual ion prod-
is the logarithm (base 10) uct to the theoretical solubility product). This index is
of the supersaturation commonly denoted by SI or Is.
ratio. The larger the value of SI, the greater the likelihood that
scale will deposit. A rough guide to interpret SI values is:
1. SI < 0: Undersaturated; no scaling.
2. SI = 0-1: Small scaling tendency; inhibitors may
not be needed in clean system.
3. SI = 1.1 - 2.3: Scale likely; probably controllable by
scale inhibitors.
4. SI > 2.3: Severe scale; inhibitors may not control.
Several investigators18-22 developed methods to calculate
SI. The Oddo-Tomson20 method is the newest and the best
(see the Appendix). Refs. 1 through 3 present equations
and examples. Another useful calculation is to estimate
the maximum amount of CaCO3 scale that may deposit.
Valone and Skillern23 stated that, based on Texaco’s expe-
rience, this technique can also indicate the severity of the
scaling problem.

Calculations of Sulfate Scaling Tendencies
Sulfate scaling tendencies (gypsum, barite, and celestite)
are generally determined by comparing the actual ion
product concentrations to the theoretical solubility.
The most commonly used method of predicting gypsum
solubility in oilfield brines is Skillman et al.’s.24 They
measured the solubility of gypsum in simulated oilfield
brines in brines with salinities as high as 6 molar at
temperatures from 50 to 176°F. Templeton’s 9 solubility
data can be used to estimate the solubility of barium
sulfate for waters containing predominantly sodium and
chloride ions. This method underpredicts the actual
barite solubility if the brine is high in magnesium or
calcium because these cations can tie up some of the
sulfate, leaving less available for reaction with the
barium.
The data of Jacques and Bourland’s11 data cover the
widest range of conditions for the solubility of SrSO4.
Data for pressure effects up to 3,000 psig are also in-
cluded.
Computer Programs for Scaling Tendency

Calculations
Two convenient computer programs for performing
scaling tendency calculations are commercially available: Computer programs are
(1) Patton1 sells an IBM PC-compatible program (2) OLI
Systems Inc. markets a mainframe program. available that will
calculate scaling
The Patton program is simply a computerized version of
the equations presented in his book for determining the tendencies.
solubility of CaCO3, CaSO4, BaSO4, and SrSO4. This
floppy disk costs about $100 and is available from:
Campbell Petroleum Series
1215 Crossroads Blvd.
Norman, OK 73072
(405) 321-1383
The purchaser receives the program (Scale-1) and a
backup copy. This program is copy-protected. It is
recommended that the user have access to Patton’s book
(and errata) when using Scale-1 because the program
documentation refers to it extensively.

CPTC purchased the license for the OLI System ProChem
water chemistry software. One component of that pack-
age is the ScaleChem program. This program is available
to anyone in Chevron through the MVS/TSO system on
the IBM mainframe computer in La Habra or through the
VM system on the Houston IBM computer.
For both the Patton and ScaleChem programs, the user
inputs a brine analysis and the computer calculates the
scaling tendency of the common oilfield precipitates.
Both programs are user-friendly and simple to run. The
advantage of the Patton program is that it runs on a PC.
The advantage of ScaleChem is that it is valid over a
wider range of temperatures and pressures than Patton’s
program. ScaleChem can also calculate the solubility of
iron carbonate, a feature that is not included in Patton’s
program. 17
SCALE PREVENTION
Avoid Mixing Incompatible Waters
One primary cause of scale formation is the mixing of
two or more incompatible waters. The individual waters
may be quite stable at all system conditions and present
no scale problem. However, once they are mixed, reac-
tions between the ions dissolved in the individual waters
may form scales. When this occurs, the waters are said to
be incompatible.
The scaling tendency calculations discussed above may
be applied to the projected mixture of waters. We highly
recommend that such a calculation be performed before
two or more water sources are mixed in the field. The
best policy is simply to avoid mixing waters if at all
possible.
If, for example, two surface waters are to be injected, two
methods are available to handle the waters without
We recommend not to mix mixing them:
incompatible waters, if
1. Split system — inject each water into its own system.
possible.
2. Sequential injection — inject the waters alternately.

Adjusting Brine Chemistry
Water Dilution
Sometimes precipitation can be halted in a scaling water
by deliberately mixing it with another usually fresher
water so that the mixture is stable (recognizing the in-
compatibility restrictions noted above).
pH Control
A decrease in pH will increase the solubility of iron
deposits and carbonate scales. This method must be used
with caution because it tends to make the water more
corrosive. Adjusting the pH has little impact on sulfate
scales.
This approach is generally practical only if a minor shift
in pH will be sufficient to solve a scale problem. Precise
pH control is required and is often difficult to attain in
the oil field.
Removal of Scale-Forming Gases

Dissolved gases (e.g., H2S, CO2, and O 2) can be removed
chemically and mechanically. This technique is most
suitable to the prevention of iron compounds.
Note that simply removing the CO2 from the water can
accelerate carbonate scaling. However, the pH can be
lowered enough to convert all carbonates and bicarbon-
ates to CO2. Then removing the CO2 will prevent carbon-
ate scale deposits.
Removal of Scale-Forming Ions

Such processes as water softening by ion exchange can Removing scale-forming
remove scale-forming ions like Ca++ and Mg++. This is
ions like Ca++ is normally
generally too expensive to use routinely. Exceptions are
ion-exchange units to soften water for use as boiler practical for water fed to
feedwater in gas processing plants and for steam genera- steam generators.
tors in thermal recovery operations.

Addition of Chelators
Certain chemicals like EDTA (ethylenediaminetetraacetic
acid) will prevent scale deposition by reacting
(complexing or chelating) with scaling ions to form a
water-soluble complex. This effectively removes the ion
from solution.
The basic disadvantage of using these chemicals as scale-
control agents is their inefficiency. Generally, the dosage
of chelant must be equimolar to the scaling ion. For
example, an equimolar ratio of Na4 EDTA to Ca++ is
equivalent to a mass ratio of about 10 to 1. Another
possible disadvantage is that chelator solutions can be
corrosive (see Chapter 6). Generally, chelators are used
for the chemical removal of some scales (see the Scale
Dissolvers section) rather than as scale preventers. An
important exception is the inclusion of chelators in acid
treatments. Chemicals such as sodium citrate, sodium
gluconate, and EDTA are often included to prevent the
precipitation of iron compounds released by the acid
treatment.
Environmental Controls
Another approach is to control the temperature and
pressure to avoid creating scaling conditions. The pro-
cess usually dictates these parameters; the operator has
limited ability to make the required adjustments.
These chemicals are perhaps the most common method
of preventing undesired water-formed precipitates.
Scale inhibitors are the Therefore, this topic is treated in greater detail.
most common method to
prevent precipitates. SCALE INHIBITORS
Principle of Use
Scale inhibitors are chemicals that delay or prevent scale
formation when added in small concentrations in nor-
mally scaling water. Use of these chemicals is attractive
(compared with chelation agents) because a very low
dosage (several ppm) can be sufficient to prevent scale
for extended periods of time for either surface or down-

hole treatments. The precise mechanism for scale inhibi-
tors is not completely understood but is thought to in-
clude two possibilities25:
1. Scale inhibitors may adsorb onto the surface of the
scale crystals just as they start to form. The inhibitors
are large molecules that can envelop these micro-
crystals and hinder further growth. This is consid-
ered to be the primary mechanism.
2. In some cases, the chemical may simply prevent the
precipitate from adhering to the solid surfaces.
Scale inhibitors that actually prevent precipitation are
clearly preferable for water injection operations. Sus-
pended solids (nonadherent scales) are not acceptable.
Because these chemicals function by stopping the growth
of scale crystals, the inhibitor must be present before the
onset of precipitation. This suggests two basic rules in
applying scale inhibitors:
To be effective, inhibitors
1. The inhibitor must be added upstream of the problem
should be added at a
area.
sufficient dosage
2. The inhibitor must be present in the scaling water on
a continuous basis to halt the growth of each scale upstream of the problem
crystal as it precipitates. area.
Types of Scale Inhibitors

The common classes of scale inhibitors include:
• Inorganic polyphosphates.
• Organic inhibitors.
– Phosphonates.
– Phosphate esters.
– Polymers.
Fig. 2 describes the chemical structure of these different
classes of inhibitors.26
The inorganic polyphosphates are noncrystalline inor-
ganic solids. They are available as plain polyphosphates
or as controlled-solubility polyphosphates. They are
seldom used in oilfield operations today and are not
discussed further here. Their disadvantages are that they
are solids (inconvenient to handle) and are susceptible to

degradation. They can decompose (hydrolysis or rever-
sion) rapidly, particularly at low pH or high temperature.
On the other hand, organic-based inhibitors usually are
conveniently packaged as a concentrated liquid and are
inherently more stable chemically. Ref. 2 provides fur-
ther details on inorganic polyphosphates.
Table 3 summarizes the attributes of each type of scale-
inhibitor chemistry. One key variable is system tempera-
ture. The phosphate esters can be very cost-effective but
are not recommended for temperatures above 175°F
where they may hydrolyze in a few hours. The
phosphonates are good to perhaps 300°F. Polymers like
acrylates can be used up to 400°F. An important factor
for high-temperature applications is how long the inhibi-
tor must function. Cheaper, less stable inhibitors may be
acceptable for short durations, but not for squeeze treat-
ments where the chemical must survive in the formation
for months.
Table 3 Scale Inhibitors

Hydrolytic Temperature
Type Stability Stability Detectability
Inorganic Poor Poor Good
Polyphosphonates
Organic Phosphate Good Fair Good
Esters
Organic Excellent Good Very Good
Phosphonates
Organic Polymers Excellent Excellent Difficult
Another important consideration is whether a simple,

accurate method is available to determine the scale-
The ability to measure the inhibitor concentration in oilfield brine. In surface treat-
ments, we must be able to verify that the appropriate
inhibitor concentration is
amount of chemical is added. Determining the scale-
important, especially in inhibitor concentration is vital in squeeze treatments
squeeze treatments. because this is the only means of determining if enough
chemical is being swept from the formation where it has
been squeezed and into the produced water.

The phosphonates and phosphate ester inhibitor
concentrations may be determined easily and reasonably
accurately by a wet chemical colorimetric method.27
Standard kits may be purchased for this purpose. A
newer technique under development relies on ion chro-
matography.28 There are no widespread, accepted ana-
lytical methods for the polymer-based inhibitors. This
limits their use in squeeze treatments. Nalco claims to
have a suitable method for polymeric inhibitors, but they
have not yet published details.
Selection of Scale Inhibitors for Further

Evaluation
Some factors in the selection of scale-inhibitor candidates
for consideration in performance tests include:
• Type of scale. Knowing the scale composition, one
can select the best scale-inhibitor chemistry.
• Severity of scaling. Fewer products are effective at
high scaling rates.
• Cost. Considering inhibitors that encompass a range
of costs and meet the other requirements is a good
idea. Sometimes the cheaper products prove to be the
most cost-effective; sometimes the more expensive
products do.
• Temperature. The relative thermal stability of the
different types of scale inhibitors was discussed
above. Higher temperatures and required longer life
(e.g., squeeze treatments) limit the types of chemistry
that are suitable.
• pH. Most conventional (phosphonate) scale inhibitors
perform less effectively in a low-pH environment.
This can be a problem for inhibiting sulfate scales in
conjunction with acid treatments or CO2 flooding for
EOR.29 A good case history is Chevron’s experience
with inhibiting barium sulfate scale in CO2 break-
through wells at the Rangely field.30
• Weather. The pour point should be considered if it is
a cold-climate operation.

• Chemical compatibility. The scale inhibitor must be
compatible with other treatment chemicals, such as
oxygen scavengers, corrosion inhibitors, and biocides.
Also, the scale inhibitor must be compatible with the
water itself. Some scale inhibitors may react with
high concentrations of calcium, magnesium, or
barium to form a scale (a pseudoscale, see Chapter 8).
• Application technique. This is most important if the
inhibitor is to be squeezed into the formation. This
means that the scale inhibitor must survive for several
months under reservoir conditions. This also means
that an accurate detection method is available. As
mentioned, there is a standard method for phosphate
esters and phosphonates, but the analytical methods
for the polymeric scale inhibitors are uncertain.
Scale Inhibitor Evaluation — Laboratory

Performance Tests
For larger projects, we should consider doing a series of
laboratory tests to reduce the number of candidate prod-
Lab tests can rank the ucts for final field evaluation. A good laboratory testing
program discriminates between the good and the medio-
performance among
cre or poor products for a particular application. Because
candidate inhibitors. laboratory tests can only approximate field conditions,
test results only estimate the inhibitor dosage required to
prevent the undesired scale.
The different types of laboratory tests commonly used
are:
• Static (bottle) tests.31,32 A series of solutions is pre-
pared that contains a scaling brine with different
concentrations of candidate scale inhibitors. The
concentration of the scaling ion (e.g., barium, calcium)
is determined before and after the test period. The
concentration of the scaling ion remaining in solution
for the samples containing inhibitor are compared
with blank samples that have no inhibitor to deter-
mine inhibitor effectiveness. A 100% effective inhibi-
tor will keep the scaling ion concentration the same
(no precipitation) during the test period.

• High-pressure/high-temperature cell. This follows the
same basic procedure as the bottle tests, except that
testing is performed at elevated pressure in an auto-
clave. Chevron has this apparatus.
• Flow-loop test.32-34 In this test, incompatible waters
are mixed and sent through a capillary tube, and the
pressure drop is monitored (Fig. 3). As scale forms,
the pressure increases. The pressure drop remains the
same if no scale forms (an effective inhibitor is
present) that plugs the narrow tubing. This proce-
dure is more complicated than the bottle tests, but it
permits testing at process pressure and temperature
in a flowing system.
Ref. 32 is included in the Appendix because it provides a
good review of the different inhibitor evaluation meth-
ods.
Scale Inhibitor Testing — Field Performance

Monitoring
We can use several techniques to determine whether the
candidate scale inhibitor is performing in the field as
planned. These include:
• Pipe spools or nipples. These are simply short sec-
tions of installed pipe that may be removed easily and
inspected to determine whether solids have built up.
They frequently are installed in a short bypass loop so
that normal operations may continue while the spool
is being removed.
• Coupons. These are similar to corrosion coupons
except that they are perforated with at least 6 to
8 holes. The coupon is placed with the flat side facing
the direction of flow to accelerate scale deposition.
The coupon is weighed before and after to determine
scale deposition.
• Visual inspection. The operator regularly looks
inside the tanks and lines where scale is most likely to
form.

• Increased pressure drop/loss of production. Increased
flow resistance in a piping network or a sudden
decrease in the overall fluid production in a well are
symptoms of scale formation.
• Decreased injectivity. This indicates formation plug-
ging that may be caused by scale particles.
• Change in water analysis. A sudden drop in the
concentration of scaling ions in the brine may result
from precipitation farther upstream.
Application of Scale Inhibitors

As mentioned earlier, the two rules for the effective
application of scale inhibitors are that they be added
upstream of the problem area and that they be present
continuously in sufficient concentration.
Inhibitor application for surface treatment is straight-
forward once the problem area is found. Typically, the
product is metered in continuously upstream of the
scaling area (e.g., sudden pressure drop, turbulent zone,
or the place where two incompatible brines mix).
Designing a treatment program for downhole scale
Designing a treatment prevention is more difficult. We are less certain where
program for downhole scale deposition begins (where the inhibitor must be
scale prevention is more placed to be effective), and applying the chemical at the
difficult. desired concentration on a continuous basis is more
difficult.
In production wells, scale deposition may start in the
formation itself, in the perforations, in the pump or other
downhole equipment, on the tubing, or on the piping on
the surface. The “best” treatment is the most cost-effec-
tive one that gets the proper concentration of scale inhibi-
tor into the brine before deposition begins.
Table 4 lists the most common techniques used to place
scale inhibitors downhole.
Batch Treatments
Batch treating a producer by periodically pouring scale
inhibitor down the annulus is the simplest downhole
application technique. This method has two major draw-
backs.

Table 4 Methods to Apply Scale Inhibitors Downhole
Comments
Batch Treatment Simple Poor Control
Continuous Recirculation More Complex Good Control
• Bypass Down Annulus
• Downhole Coiled Tubing (SPE 11853)34
• Downhole Chemical Injection Pump (SPE 14403)35
Squeeze Treatments Complex Protection Starts Inside the

Formation
1. It provides little control over the concentration of

scale inhibitor entering the produced brine. The
chemical concentration usually is high initially and
then drops off rapidly. This means overtreatment
followed by undertreatment.
2. The scale inhibitor reaches only partway down the
tubing. If the scale begins to form at the bottom of the
tubing, in the perforations, or in the formation, the
chemical enters too late.
Continuous Recirculation
An improved, but more complex, method is to pump the
scale inhibitor downhole continuously. Fig. 4 illustrates
three continuous placement methods35,36: annulus flush,
coiled tubing, and downhole chemical injection pump
(DHCIP). Table 5 compares their characteristics.
The main advantage of these methods is the increased
control in injecting the treatment chemical. The scale
inhibitor can be injected into the produced water as far
down as the bottom of the tubing and at the optimum
concentration on a continuous basis. However, these
methods do not prevent scale deposition in the perfora-
tions or in the formation itself.
All techniques have the disadvantage of requiring extra
equipment (capital and operating costs) compared with
batch treating. The increased complexity means that
such systems require attention (maintenance) to operate

Table 5 Continuous Inhibitor Treatments
Characteristic Annulus Flush Coiled Tubing DHCIP
Production Loss Yes Yes Yes
(Recycle)
Protect All Tubular No Yes Yes
Goods
Capital Cost Low High High
Risk of Mechanical Low High Medium
Failure When
Installed
Special Problems Should Monitor, Plug Tubing, Need Unproven
Poor Mixing, Regular Technology,
Chemical Build-up Maintenance Plugging DHCIP
Intake
properly. Common problems include pump failures and

plugging of critical components. The annulus flush
method and coiled tubing are used frequently. The
DHCIP, tested at Rangely field, is still under evaluation.
Scale Inhibitor Squeeze — Product Selection

Squeeze treatments are another common way to apply
The major advantage of scale inhibitor downhole. The major advantage of the
squeeze technique is that the inhibitor is placed into the
the squeeze technique is
reservoir, thereby providing protection starting inside the
that the inhibitor protects formation. Fig. 5 gives details.
the reservoir.
Often the well is treated first to remove existing scale
(most often acidized). After the treatment fluid (spent
acid) is allowed to return, any preflush chemicals
(demulsifiers, surfactants) are injected. This is followed
by the scale-inhibitor solution (often several percent
concentration in field brine) and then an overflush (usu-
ally field brine) to push the inhibitor several feet away
from the wellbore. The well is shut in for several hours
to allow the scale inhibitor to be retained in the formation
by adsorbing onto the rock surfaces or by precipitating in
the formation (usually from excess calcium). Finally,
normal production is resumed.

The produced water entering the treated zone near the
wellbore picks up the chemical, either by desorption or
by dissolving a portion of the inhibitor precipitate. As
long as enough inhibitor enters the produced water, no
scale should form in the formation, perforations, down-
hole equipment, or tubing. The entire well is protected.
Unfortunately, the chemical feedback concentration
cannot be controlled easily. Fig. 5 illustrates the typical
scale-inhibitor return curve from a squeeze treatment.
Initially, little chemical is seen as the overflush returns.
Next is a high concentration of inhibitor representing the
material that did not readily adsorb or precipitate. Fi-
nally, there is a long, gradual depletion of the chemical,
perhaps stretching out over thousands of barrels and
several months of production. When the inhibitor con-
centration finally falls below its minimum effective
concentration for that brine, the squeeze treatment must
be repeated to maintain protection. The number of
barrels of produced water treated or the duration of the
treatment is called the squeeze life.
Obviously, this method wastes chemicals. The water is
overtreated initially, and some inhibitor is left in the
formation when the fluid concentration falls to the mini-
mum acceptable level. The rule of thumb is that one-
third of the inhibitor comes out at too high a concentra-
tion, one-third provides an effective treatment, and
one-third is left in the formation at the end of the
squeeze.29
Fig. 6 presents an ideal inhibitor return curve where the
chemical is not wasted. In this case, the inhibitor goes
into the produced water at just above the minimum
requirement for the duration of the squeeze. Inter-
national Drilling Fluids (IDF) developed a new polymer
product that exhibits this behavior. This product (ESL)
had some success at Ninian field in the North Sea and is
being tested at Rangely.37-39 Recently, IDF sold this tech-
nology to TR Oil Services and Unichem.
Besides a favorable retention/release behavior, there are
two key requirements for selecting a scale inhibitor for
squeeze treatments. Although noted earlier, they are
repeated here for emphasis:

• Chemical (thermal) stability. The inhibitor is re-
Thermal stability and tained inside the reservoir for weeks or months before
detectability are key it is released into the produced water. The chemical
must not degrade during that time.
requirements for selecting
a scale inhibitor for • Detectability. The treatment is monitored by the
measured concentration of scale inhibitor in the
squeeze treatments.
produced water; the end of the squeeze is determined
when the concentration falls below the acceptable
level. Thus, there must be an accurate and convenient
analytical method to determine these residual concen-
trations.
Phosphonate scale inhibitors are the most common
choice for squeeze treatments because they have good
thermal stability and because we can use a standard test
to measure their concentration in brine.40 As mentioned,
the phosphate esters suffer from relatively poor thermal
stability, and most polymers are not used in squeeze
treatments because their concentration in oilfield brines is
very difficult to determine accurately. Some polymer
products (such as ESL) circumvent the detection problem
by incorporating a phosphorous group into the molecule.
This permits analysis by the conventional method for
phosphonates. Some recent laboratory work reported in
the literature41 suggests that the phosphonates also are
preferred because of their better retention/release charac-
teristics compared with esters.
Squeeze Treatment Design

Besides the choice of an effective chemical, we must
consider a number of factors when designing a scale-
inhibitor squeeze treatment. These factors are discussed
briefly in this section; Refs. 29 and 37 through 51 provide
greater detail. Meyers and Skillman’s40 paper and
Meyers et al.’s48 work provide good reviews of the scale-
inhibitor squeeze process. Ref. 40 is appended to this
chapter.
• Production rate. The higher the water production
rate, the larger the squeeze job required to treat the
greater volume of brine.47 As a first approximation,
each drum of scale inhibitor should treat 10,000 to
100,000 bbl of produced water. One related factor is
the fluid velocity in the treated zone. Our data and

the literature suggest that the placement and desorp-
tion of the scale inhibitor can be kinetically controlled
and hence is sensitive to flow rate.42,45
• Amount of scale inhibitor. The more chemical used,
the longer the squeeze life. However, increasing the
inhibitor by itself usually gives a diminishing return
on squeeze life. For example, doubling the scale-
inhibitor concentration alone typically increases the
squeeze life, but by less than a factor of two.
• Overflush volume. The overflush volume needs to be
large enough to drive the scale inhibitor several feet
into the reservoir. This smears out the chemical,
giving it an adequate chance to adsorb or precipitate,
and decreases the high concentrations that return
initially. A rule of thumb is to make the overflush
volume about twice the inhibitor slug volume.
• Minimum effective concentration. The squeeze life
can be improved considerably if the inhibitor concen-
tration can safely be allowed to fall to lower values.
This option may be available at production wells
where the scaling tendency is low.
• Repeated treatments. The squeeze life tends to im-
prove with subsequent squeeze treatments because
they take advantage of the chemical left behind in the
formation by earlier squeezes.49
• Retention/release characteristics. The way that the
inhibitor is retained and subsequently leached into
the produced water can greatly affect squeeze life. As
a general rule, squeeze life is longer for treatments
that rely on precipitation than those that rely on
strictly adsorption.44 In these precipitation squeezes,
calcium is introduced either into the inhibitor slug
itself or in a preflush or overflush. One danger of the
precipitation squeeze method is that the calcium/
inhibitor salt may form too quickly and cause forma-
tion damage. A Chevron mathematical
Ref. 42 describes a Chevron mathematical model for the model for the adsorption
adsorption squeeze method and explains some trends squeeze method explains
seen in the adsorption squeezes performed at Ninian trends seen in data from
field.38,39 This model and some literature data suggest Ninian field.

that the following procedure is useful in interpreting
inhibitor squeeze data and predicting squeeze life
(Fig. 7).
1. Plot the inhibitor concentration in the produced fluid
vs. the cumulative produced water volume on log-log
scale. Often, the data for the latter part of the squeeze
form a straight-line decline.46 If so, this suggests a
method for extrapolating the return data for that
squeeze.
2. Measure the slope of this line. A consistent slope may
result for all the wells using the same scale inhibitor.
If so, this gives a more general approach to predicting
squeeze performance. Finally, if the slope is steep
enough (an absolute value greater than one), then the
data may be compared vs. the published Chevron
mathematical model. This particular model requires a
steep decline because of the theory used (Freundlich
isotherm) to account for inhibitor adsorption/desorp-
tion.
Experience has shown that often the field data exhibit too
small a slope (show longer squeeze lifetimes) to be
consistent with this model. This is particularly true for
precipitation squeezes where the inhibitor can return at
almost a constant composition for some time, presum-
ably from the slow dissolution of the inhibitor salt. Thus,
the model tends to give conservative estimates of
squeeze life, especially if it is (mis)used to explain data
from precipitation squeezes.
Other methods proposed to improve squeeze treatments
include:
• Preflush with surfactants or mutual solvents. This
preflush is designed to strip the residual oil and make
the rock surfaces water-wet. This is supposed to
improve the adsorption of the injected inhibitor on
the formation.29
• Add calcium or other cations. As mentioned, this
technique is designed to precipitate the inhibitor in a
controlled manner in the reservoir. The inhibitor salt
has a very low solubility in the produced water,
causing it to put a low, but effective, concentration of
chemical into the water.43,44

• Diverting agents. Use of diverting agents is intended
to force relatively more inhibitor into the low-perme-
ability zones. This strategy makes sense if the scaling
problem is worst in these zones. 47
• pH adjustments. Phosphonate solutions can range
from nearly neutral to low pH. Low-pH squeezes can
be used to cause an in-situ precipitation squeeze. If
the reservoir contains appreciable carbonate minerals,
an acidic scale-inhibitor solution will react with these
minerals and release calcium. As the acid spends,
calcium phosphonate salts will begin to precipi-
tate.40,44
• Acid retarders. It can be advantageous to include an
acid retarder in an acidic inhibitor solution squeezed
into a highly reactive (limestone) reservoir. This
delays inhibitor precipitation, thereby placing the
chemical away from the immediate wellbore area.40
• New inhibitor chemistry. As mentioned, TROS and
Unichem have a product (ESL) designed to give an
ideal inhibitor feedback (Fig. 6). This polymer has a
proprietary additive that makes the polymer aggre-
gate at reservoir conditions. This is similar to, but not
quite the same as, a precipitation squeeze. The inhibi-
tor has a phosphonate group grafted onto the poly-
mer chain so that the standard analytical method for
phosphonate products may be used to monitor the
ESL concentration. Disadvantages of this product are
the high cost and the customized chemistry needed
for each new field.37 Nalco has developed a similar
product but has not yet tested it in the field.
• Mixed chelant method. Conoco reported a method
for performing a precipitation squeeze in clean sand-
stone formations (no available carbonate minerals). A
single solution containing chelated calcium and scale
inhibitor is squeezed into the well and displaced with
overflush. After a controlled delay, the inhibitor’s
calcium salt begins to precipitate. Conoco is field
testing this method.50
• Polymer/phosphonate blends. Arco reports that
including a high-molecular-weight maleic copolymer
with the phosphonate scale inhibitor decreases the

inhibitor desorption rate, thereby increasing squeeze
life. Pfizer (the polymer supplier) reports that Arco is
evaluating this process at Prudhoe Bay. This benefi-
cial effect was not seen with other polymer products
tested.51
SCALE REMOVAL
If preventive steps fail to halt undesirable scale deposi-
tion, chemical and mechanical methods are available to
Scale removal is the last
remove this material.
resort for fixing a
Note that scale removal is the last resort for curing a
deposition problem.
precipitation problem. Preventing scale deposition is
much preferable.
Scale Identification
One key in scale removal is first to identify the composi-
tion of the deposit. A suggested procedure for qualita-
tively identifying scales in the field include (Table 6):
Table 6 Qualitative Analysis of Scales

Soluble in HCI
Soluble in
Component Magnetic Reaction Acid Color Smell Water
CaCO3 Very Strong
CaSO4
BaSO4 and
SrSO4
FeS Weak Strong Yellow H2S
Fe2O3 Weak Yellow
Fe3O4 Strong Weak Yellow
FeCO3 Very Strong Yellow
NaCl Yes
Sand,
Silt Clay

1. Soak the sample in a solvent to remove hydrocarbons.
2. Check whether the sample is magnetic. If it is
strongly magnetic, magnetite (Fe3O4) may be present.
A weakly magnetic sample indicates a lesser amount
of magnetite or iron sulfide.
3. Immerse the sample in 15% HCl. A violent reaction
indicates calcium carbonate. If there is an H2S odor,
an iron sulfide compound is probably present. Note
the color of the acid. Yellow indicates the presence of
iron.
Note that, over time, iron sulfide will convert to iron
oxide when exposed to air. Analyses performed
several days or weeks after sample collection will
frequently find predominantly iron oxide and little or
no iron sulfide.
4. Check the solubility in fresh water. Sodium chloride
is water-soluble.
These simple tests do not distinguish sand, silt, clays, or
the various sulfate scales. Sometimes close examination
with a magnifying glass will reveal obvious sand grains
or sulfate crystals.
It is a good idea to submit a sample for laboratory analy-
sis to confirm the field analysis and to obtain a quantita-
tive result. A fresh, well-wrapped sample works best. At
least 30 g of material is necessary for accurate laboratory
chemical analysis.
Chemical Removal
General Comments
When using chemical solutions to remove scale deposits,
you should:
• Incorporate scale prevention into the program so that
the problem does not recur. In particular, we usually
follow a scale-dissolver treatment with a scale-inhibi-
tor squeeze to prevent future scaling.
• Bring the solvents back to the surface immediately
following treatment. The injected chemicals may
become supersaturated and reprecipitate if left in the
formation.

Calcium Carbonate
The most common method to dissolve calcium carbonate
scale is with HCl. Acid concentrations normally range
from 5% to 15% HCl. A 15% HCl solution can dissolve a
maximum of 1.84 lbm of CaCO3 per 1 gal of acid.
CaCO3 + 2HCl → H2 O + CO 2 (g) + CaCl 2 (9)

A corrosion inhibitor is added to the acid to minimize
acid attacks on tubular goods. Often a surfactant is
included to remove any oil film covering the scale, which
can significantly retard the acid reaction.
Chelating agents are another approach to dissolving
unwanted calcium carbonate deposits. As mentioned,
chelant solutions can be corrosive (see Chapter 6). The
most common example is EDTA (ethylenediaminetetraacetic
acid).
CaCO 3 → ++ =
← Ca + CO 3 (10)
EDTA −4 + Ca ++ →
← Ca EDTA
=
(11)
Left alone, reaction (Eq. 10) tends to be on the left side of

the equation--i.e., only a small amount of Ca++ will be in
solution. However, the second reaction (Eq. 11) will
complex the calcium and remove it from solution. This
drives reaction (Eq. 10) to the right, thus dissolving the
calcium carbonate scale. How much scale dissolves
depends on the solubility of the salt and how strongly the
chelant reacts with the cation.
The disadvantages of the chelants are that they are rela-
tively inefficient (e.g., it takes 7.4 ppm EDTA to chelate
1 ppm Ca++) and costly. Thus, HCl is much more cost-
effective for removing calcium carbonate for normal
oilfield operations.
A possible advantage of chelants is less formation dam-
age following scale removal. Arco uses EDTA instead of
HCl at Prudhoe Bay because of significant production
declines seen after acid treatments and little or no pro-
duction decline after EDTA treatments.52

Calcium Sulfate
Calcium sulfate is largely insoluble in acid. The maxi-
mum solubility of CaSO4 is less than 2% in HCl at ambi-
ent conditions.
Chelating agents are often used for gypsum removal.
The comments made about calcium carbonate removal
apply to gypsum removal. EDTA has successfully
treated gypsum-scaled production wells at Chevron’s
Virden field in Manitoba, and Amoco reports successful
field tests in Levelland field in Texas.53,54
Our laboratory results agree with the literature that
important parameters chelating agent treatment design
are:53-59
• Product concentration. The higher the concentration,
the greater the capacity to dissolve scale (up to a
point--about 40% product concentration). At concen-
trations much higher than this, the capacity actually
diminishes because there is not enough water to hold
the dissolved material in solution.
• Soak time. Sufficient time must be allowed for the
reaction to complete. We usually allow a 1-day con-
tact time, but longer may be necessary in some cases.
• Temperature. The reaction rate increases significantly
with temperature. It is preferable to have a tempera-
ture above 150°F. We allow several days for soak time
at Virden because the reservoir temperature is only
80°F.
• Agitation. The dissolution rate increases substan-
tially with agitation.
• Surface area. The treatment is more effective if the
scale has a large surface area. This makes it much
easier for the chemical to come in contact with and
rapidly dissolve the scale. Consequently, dissolvers
can effectively remove gypsum in the formation
matrix (high surface area), but they rarely remove
gypsum on tubing. The ideal application is the re-
moval of a small quantity of scale near the production
wellbore that is causing severe formation damage.

• Dilution water. We want to dilute the chelating
solution with a low-hardness water because the
calcium and magnesium in the treatment brine will tie
up some chelant. Where convenient, even brines
containing as much hardness as seawater may be
used if the amount of scale dissolver is increased to
compensate for this effect. Potassium chloride brines
could be used as the dilutent for reservoirs suscep-
tible to clay swelling.
Another way to dissolve calcium sulfate chemically is to
use converters. These products react with the scale and
Beside chelators, “convert” it to an acid or water-soluble sludge. This
converted product then is removed in a second step.60,61
converters are another
Inorganic converters are usually carbonates or hydrox-
option to remove gypsum. ides that react with calcium sulfate to form calcium
carbonate or calcium hydroxide. A good example of this
type of chemical is ammonium carbonate. The reaction is
CaSO 4 + (NH 4 )2 CO 3 → (NH 4 )2 SO 4 + CaCO 3

(12)
(soluble)
The calcium carbonate is then dissolved with HCl:
CaCO3 + 2HCl → H2 O + CO 2 (g) + CaCl 2 (13)
The CO2 liberated by the acid reaction helps to dislodge
any remaining deposit mechanically.
We also use organic converters. Examples include so-
dium citrate, potassium glycollate, and potassium ac-
etate. These materials react with calcium sulfate deposits
so that they swell and become soft. We then remove
them with a water flush. These chemicals are relatively
expensive and require several hours of contact time to
work on thick deposits.
Other treatment options include using caustic solutions
(a 10% solution of NaOH will dissolve up to 12.5% of its
weight of gypsum) or salt water. Gypsum solubility
increases with salinity up to about 15% NaCl.
Barium Sulfate
Barium sulfate is very difficult to remove chemically and
until recently was removed only by mechanical means.

Two vendors (Unichem and Baker Performance Chemi-
cals) now market proprietary scale dissolvers. These
dissolvers are chelant-type materials, so the general
comments made earlier about the design of a treatment
program apply. In particular, these products are expen-
sive and react slowly with scale. Their best application is
to remove scale in the perforations or the reservoir rock
matrix near the wellbore.56,57
The vendors report successes with removing near-well-
bore formation damage from barium sulfate scale in
some North Sea fields.58 CEPS and our laboratory tests
with these products substantiate that they can dissolve
appreciable amounts of barium sulfate.59,62
Iron Compounds
HCl usually is used to dissolve iron compounds. This
should include a corrosion inhibitor to prevent excessive
pipe corrosion. It should also include an iron-stabilizing
agent to prevent reprecipitation of iron compounds once
the acid spends and the pH increases.
The iron dissolved during acidizing can exist either as the
ferrous (Fe++) or the ferric (Fe+++) ion, depending on the
presence of oxidizing agents (air). As the acid spends
and the pH increases, ferric ions (the less soluble form)
will begin to precipitate as ferric hydroxide [Fe(OH)3] at a
pH of around 2.2. Once the pH rises to 3.2, almost all the
ferric ion will have precipitated.63 Iron stabilizers are
added to prevent this ferric hydroxide precipitation.
There are two types of iron stabilizers63,64:
1. Chelating agents. These products tie up the ferric
ions in a water-soluble complex, thereby preventing
their precipitation. Citric acid, acetic acid, nitrilo-
acetic acid (NTA), and EDTA are common examples.
2. Reducing agents. These chemicals convert ferric ions
to the more soluble ferrous oxidation state. Erythor-
bic acid is perhaps the most common reducing agent
used for this purpose.
Ferrous ions are quite soluble up to neutral conditions.
Precipitation of ferrous ions is less of a problem because
even the spent acid usually has a pH well below 7.

Chelating agents alone may be used as an alternative to
HCl.56 As with calcium carbonate, this scale removal
method probably is less cost-effective but may give a
better-behaved treatment where the well productivity
stays at a higher level for a longer period.
Mechanical Removal
Scale Removal From Surface Lines

Scale is generally removed from surface lines by the
combined use of chemicals and line scrapers, or pigs.
There are two types of pigs:
1. Foam pigs. They are made of an open-cell foam with
a hard scrubber or plastic wrapper. The body will
deform when pumped through to seal against the
pipe and scrape off the accumulated scale. Some have
brushes to allow for bypass.
2. Brush or scraper pigs. These solid devices are
equipped with wire brushes to scrape the pipe walls.
Fluid passes through holes in the pig to disperse the
scraped solids in front and to prevent creating a plug
in the line.
Chemical dissolvers may be included in the pumped
water to help break down the scale. Sometimes gelled
fluids are injected ahead of the line scraper to help trans-
port large volumes of solids.
As part of a scraping or pigging operation, we must
collect the released solids to prevent them from becoming
plugging agents for injection wells.
Downhole Cleanout
In downhole cleanout, scale is removed from the tubing,
perforations, formation face, and sometimes the forma-
tion matrix.
If the scale in the tubing is severe, the tubing may be
pulled and treated on the surface. Chemical means may
suffice for lighter scaling.
A number of downhole tools — casing brushes, surge/
swab tools, and suction and circulation washers — re-
move deposits from the formation face or perforations.

Ref. 35 provides a good description of a water blasting
technique for removing scale at the Rangely field. In
some cases, a combination of mechanical tools and soak-
ing with a chemical dissolver will produce the best re-
sults. In extreme cases, hydraulic fracturing may be only
way to penetrate the scaled interval.

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33. Bsharah, L.: “Test Unit Evaluates Scale Inhibitors,”
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34. Hughes, C. T. and Whittingham, K. P.: “The Selection
of Scale Inhibitors for the Forties Field,” paper
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35. Cruise, D. S., Davis, D. L., and Elliott, R. H.: “Use of
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paper SPE 11853 presented at the 1983 SPE Rocky
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May 23-25.
36. Cramer, R. W. and Bearden, J. L.: “Development and
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37. Collins, P.: “The Scaletreat ESL System, A New Ap-
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38. Shuler, P. J.: “Modeling of Scale Inhibitor Squeeze
Treatments - Ninian Field,” COFRC Technical Memo-
randa TM87000856 and TM89000345.
39. Shuler, P. J. and Jenkins, W. H.: “Prevention of Down-
hole Scale Deposition in the Ninian Field,” paper SPE
19263 presented at the 1989 SPE Offshore Europe
Conference, Aberdeen, Sept. 4-8.
40. Meyers, K. O. and Skillman, H. L.: “The Chemistry
and Design of Scale Inhibitor Squeeze Treatments,”
paper SPE 13550 presented at the 1985 SPE Interna-
tional Symposium on Oilfield and Geothermal Chem-
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41. Przybylinski, J. L.: “Adsorption and Desorption
Characteristics of Mineral Scale Inhibitors as Related
to the Design of Squeeze Treatments,” paper SPE
18486 presented at the 1989 SPE International Sympo-
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42. Hong, S. A. and Shuler, P. J.: “A Mathematical Model
for the Scale Inhibitor Squeeze Process,” SPEPE (Nov.
1988) 597-607.

43. Tomson, M. B. et al.: “Use of Inhibitors for Scale
Control in Brine-Producing Gas and Oil Wells,” paper
SPE 15457 presented at the 1986 SPE Annual Technical
Conference and Exhibition, New Orleans, Oct. 5-8.
44. Carlberg, B. L.: “Precipitation Squeeze Can Control
Scale in High-Volume Wells,” Oil & Gas J. (Dec. 2,
1983), 152-54.
45. Vetter, O. J.: “The Chemical Squeeze Process — Some
New Information on Some Old Misconceptions,” JPT
(March 1973) 339-53.
46. Durham, D. K.: “Equations for Prediction of Scale
Inhibitor Return After Squeeze Treatment,” paper
SPE 11708 presented at the 1983 SPE California Re-
gional Meeting, Ventura, March 23-25.
47. Spriggs, D. M. and Hover, G. W.: “Field Performance
of a Liquid Scale Inhibitor Squeeze Program,” JPT
(July 1972) 812-16.
48. Meyers, K. O., Skillman, H. L., and Herring, G. D.:
“Control of Formation Damage at Prudhoe Bay,
Alaska, by Inhibitor Squeeze Treatment,” JPT (June
1985) 435-46.
49. Shuler, P. J.: “A Mathematical Model for Successive
Scale Inhibitor Squeeze Treatments,” COFRC Techni-
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50. Carlberg, B. L.: “Scale Inhibitor Precipitation Squeeze
for Non-Carbonate Reservoirs,” paper SPE 17008
presented at the 1987 SPE Production Technology
Symposium, Lubbock, TX, Nov. 16-17.
51. Underdown, D. R. and Newhouse, D. P.: “Evaluation
of Calcium Carbonate Scale Inhibitors for Prudhoe
Bay, Alaska,” paper SPE 15658 presented at the 1986
SPE Annual Technical Conference and Exhibition,
New Orleans, Oct. 5-8.
52. Shaughnessy, C. M. and Kline, W. E.: “EDTA Re-
moves Formation Damage at Prudhoe Bay,” JPT (Oct.
1983) 1783-92.
53. Charleston, J.: “Scale Removal in the Virden,
Manitoba, Area,” JPT (June 1970) 701.

54. Schutte, R. W.: “Designing Gyp Scale Removal Treat-
ments Based on Chemical Characteristics to Optimize
Field Performance,” paper SPE 16888 presented at the
1987 SPE Annual Technical Conference and Exhibi-
tion, Dallas, Sept. 27-30.
55. Shuler, P. J.: “Gypsum Scale Removal and Inhibition,
Virden Field, Manitoba,” COFRC Technical Memoran-
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Akzo Chemicals (vendor brochure) (May 1988).
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“The Dissolution of Scales in Oilfield Systems,” paper
SPE 14010 presented at the 1985 SPE Offshore Europe
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Carbonate,” Technical Memorandum PSD 870013 or
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(Aug. 22, 1988), 56-59.
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Dissolvers - Rangely Field,” preliminary report,
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June 1988) 75-78.

GLOSSARY
anhydrite — calcium sulfate mineral or scale that con-
tains no water.
black water — water that contains suspended iron sul-
fide scale.
calcium sulfate converters — chemicals that convert
calcium sulfate scale deposits to a an acid soluble
form.
cathodic protection — a method wherein a metal’s sur-
face is made the cathode of an electrochemical cell
thereby shifting the its corrosion potential towards a
less oxidizing potential and reducing its corrosion
rate.
celesite — name for strontium sulfate mineral.
chelating agent — an organic compound in which atoms
form more than one coordinate bond with metals in
solution.
chelation — the formation of a soluble complex between
an ion and another species. One way to prevent or
remove scale is to tie-up (chelate) the offending cation
with an added chemical.
citric acid — chemical that ties-up (chelates) with iron to
keep it in solution.
corrosion — the deterioration of a material, usually a
metal, and its properties by chemical or electrochemi-
cal reaction with its environment.
crevice corrosion — localized corrosion of a metal sur-
face at, or immediately adjacent to, an area that is
shielded from full exposure to the environment be-
cause of close proximity between the metal and the
surface of another material.
EDTA — ethylenediaminetetraacetic acid. A common
chelating agent that is used to keep iron in solution,
or as a remover agent for scale deposits.
erosion — destruction of materials by the abrasive action
of moving fluids, usually accelerated by the presence
of solid particles.

erosion corrosion — a corrosion reaction accelerated by
the relative movement of the corrosive fluid and the
metal surfaces.
galvanic corrosion — accelerated corrosion of a metal
resulting from the electrical coupling with a more
noble metal or nonmetallic conductor in an electro-
lyte.
general corrosion — a form of deterioration that is dis-
tributed more or less uniformly over a surface. Also
called Uniform Corrosion.
gypsum — calcium sulfate mineral that contains two
waters.
inhibitor — a chemical substance or combination of
substances that, when present in the proper concen-
tration and forms in the environment, prevents or
reduces corrosion without significant reaction with
the components of the environment.
linear polarization — a corrosion rate monitoring
method wherein a voltage is created between two
electrodes immersed in an electrolyte, and the result-
ing current flow, which is proportional to the corro-
sion rate, is measured.
localized corrosion — corrosion at discreet sites, for
example, pitting, crevice corrosion, and stress corro-
sion cracking.
NTA — nitriloacetic acid. A chlelating agent that is used
to keep iron in solution.
passivation — a reduction of the anodic reaction of an
electrode involved in corrosion.
phosphate esters — one class of scale inhibitors. These
are characterized by a carbon-oxygen-phosphorous
bond.
phosphonates — one class of scale inhibitors. These are
characterized by a phosphonate group; this is a phos-
phorous connected to three oxygens, with hydrogens
connected to two of the oxygens.
pigging — use of a scrapping tool which is forced
through a flow line or lines to clean out wax or other
deposits.

pitting corrosion — localized corrosion of a metal sur-
face that is confined to a small area and takes the form
of cavities.
polyphosphates — an older class of scale inhibitors.
These are not commonly used because of their inher-
ent instability. These are solids characterized by
containing phosphate groups.
red water — water that contains suspended iron oxide
solids.
reducing agent — compound that reduces the oxidation
state of a species. The most common example is a
chemical that reduces ferric iron (+3 charge) to ferrous
iron (+2 charge).
saturation index — a measure of the driving force for
scale deposition to occur.
scale inhibitor squeeze — process whereby a scale
inhibitor is applied inside the reservoir.
solubility — the maximum amount of dissolved ions
that will remain in solution.
stainless steel — an iron-based alloy containing at least
10.5% Cr.
supersaturation ratio — the ratio of the product of the
scaling ions concentrations to their solubility product.
A supersaturation ratio greater than one indicates
their is a positive tendency for scale deposition.

APPENDIX

C H A P T E R
Corrosion Effects
Chapter 6: Corrosion Effects 6-1

INTRODUCTION
This chapter is intended to be an introduction to corro-
sion control alternatives available for water treatment
systems. It is not a comprehensive corrosion control
guide. The Chevron Corrosion Prevention Manual, Coat-
ings Manual, and Pipeline Manual provide more specific
information and additional references. Our intent is not
to reproduce here the information available in these
manuals (copies of the Tables of Contents are included in
the Appendix). We strongly recommend that you have
easy access to these manuals, available from Technical
Standards Division, Chevron Research and Technology
Company (CRTC), San Ramon, 510/842-8503.
Other chapters in this handbook discuss the injection of
treating chemicals and corrosion associated with bacteria.
CORROSION AFFECTS WATER QUALITY

Corrosion is usually considered a threat only to the
equipment used in production operations. This chapter
focuses on the effects of corrosion on water quality. The
same techniques are used to control corrosion, but the
objective is to meet not only the design life of the equip-
ment, but also injection or disposal water quality require-
ments.
The presence of dissolved iron resulting from corrosion is
a primary cause of water quality problems in oilfield
water systems. Iron oxides and iron sulfides create a
number of problems in water injection, oil/water separa-
tion, and water treating. Precipitation can increase the
friction along the pipe walls and decrease the carrying
capacity. Precipitated iron compounds may also contrib-
ute to injection well plugging. These corrosion products
are often responsible for underdeposit corrosion. The
iron sulfides and magnetite are also cathodic to iron,
causing increased galvanic corrosion when exposed to
oxygen or oxidizing chemicals such as hypochlorite or
chlorine dioxide (often used as biocides).
Iron solids also interfere with water treatment. They are
good adsorption sites for filming corrosion inhibitors;
high levels of solids increase the inhibitor concentration
required to protect piping, tanks, and injection wells.

Iron sulfides are preferentially oil-wet. When oil-wet,
their densities are near that of produced water, which
discourages gravity separation. Oil-wet iron sulfides
stabilize emulsions. Because these sulfides are compres-
sible, they form very low-permeability filter cakes in
filtration equipment and injection wells.
GENERAL CORROSION
General corrosion occurs over a large area of an exposed
metal and results in gradual thinning. The corrosion
process occurs because refined base metals are thermody-
namically unstable in the presence of oxygen or water.
The corrosion mechanism includes two reactions: a
Corrosion of metals is an cathodic reduction reaction and an anodic metal dissolu-
electrochemical reaction tion reaction. The cathodic reaction in an aerated system
which requires an is the reduction of oxygen to hydroxide ion, which re-
electrolyte, an anodic quires free electrons:
surface, a cathodic 1
2 O 2 + H 2 O + 2e − = 2OH
surface, and a metallic
In the absence of oxygen, the cathodic reaction is the
connection between them. reduction of hydrogen ions to hydrogen gas, which also
requires free electrons:
2H + + 2e − = H 2
The anodic metal dissolution reaction converts neutral
metal atoms to positively charged metal ions, releasing
free electrons:
Me = Me ++ + 2e −
The cathodic and anodic reactions are coupled through
the electrons, so they must occur at the same rate.
Corrosion rates of the more noble metals (e.g., nickel,
chromium, copper alloys) are generally low enough that
dissolved metal ions present no problems to water qual-
ity. Also, dissolved iron is not usually a water quality
problem in itself except in boiler feedwater. The problem
arises when the water contains oxygen or dissolved
sulfides, resulting in precipitation of iron compounds.
The most common iron compounds are iron hydroxides
and iron oxides (magnetite and hematite) and iron sul-
fides (too numerous to list).

In the presence of oxygen, insoluble and nonprotective
ferric hydroxide is formed first. The reaction continues
to form hematite, or red rust. In the absence of oxygen
and sulfide, ferrous hydroxide is formed first. Above
about 120°F, ferrous hydroxide decomposes to slightly
protective magnetite, a black solid. In the presence of
dissolved sulfide, the stable solids are iron sulfides.
Although mackinawite is usually formed first, it evolves
over several days or months through various intermedi-
ates to pyrite, the most stable iron sulfide.
LOCALIZED CORROSION
As the name suggests, localized corrosion occurs at very
localized spots, resulting in rapid penetration of pipe and
vessel walls. As in general corrosion, two coupled reac-
tions occur. The anodic reaction is localized while the
cathodic reaction may occur over much larger areas of
the surrounding surface, with electron flow through the
connecting metal.
Localized corrosion rarely causes water quality problems.
The extent of the corrosion is very small compared with
general corrosion. We address localized corrosion here
because, if not controlled, it places very real limits on the
operating life of water treating equipment. Here we
discuss the types of localized corrosion seen most often in
produced-water treating systems. For information on the
less common types (stress corrosion cracking, intergran-
ular corrosion, corrosion fatigue, selective dealloying) see
the Corrosion Prevention Manual, Sections 120 and 300.
Pitting
Mild steel in oilfield brines will usually show a com-
bination of general and pitting corrosion. Stainless steels
show predominantly pitting corrosion.
Pitting occurs when a protective film (a passive layer, an
applied coating, or an inhibitor film) breaks down in
localized areas. The presence of halides, sulfides, or
deposits often causes passive layers to break down.
Coatings breakdown may be caused by holidays in the
manufactured coating, mechanical damage, or physical

or chemical degradation. Breakdown of inhibitor films
may result from an interruption of inhibitor injection,
dissolved ions, deposits, erosion, or abrasion.
Pitting is favored by stagnant solutions, such as at the
bottom of tanks or under deposits. In a pit, the electro-
lyte develops increasingly low pH and high chloride
concentration, even though the bulk electrolyte concen-
tration is constant. The solution in the pit becomes more
corrosive as a result of the corrosion process. Flow past
the pit improves mass transfer, lowers chloride concen-
tration, and raises pH, resulting in lower corrosion rates.
The exception occurs when localized turbulence removes
a protective film from the metal surface. This is often
seen on mild steel in the presence of CO2, where turbu-
lence removes a passivating iron carbonate film. This
type of corrosion is common at the pin end of production
tubing, on the outside radius of an elbow, or downstream
of welds with high profiles.
Crevice Corrosion
Crevice corrosion results from local differences in the
environment seen by the metal — e.g., under washers,
under deposits, or in other areas where small stagnant
volumes exist. Crevice corrosion is enhanced by tighter
crevices, higher temperatures, higher chloride levels, and
traces of oxygen. Crevice corrosion occurs more readily
than pitting corrosion. We must consider the prevention
of crevice corrosion when designing and constructing
treating equipment.
Galvanic Corrosion
Different alloys generate different potentials when im-
mersed in an electrolyte. If the potentials developed by
two alloys that are electrically connected are sufficiently
different, galvanic currents may flow between the alloys.
One alloy becomes cathodically polarized and is pro-
tected; the other becomes anodically polarized and is
sacrificed.
Galvanic series have been published for materials in
several environments to show the materials in electrical
contact that will be protected or sacrificed. In general,

the material with the lower corrosion rate is the more
noble material and will be protected by the less noble, or
more active, metal. A protected alloy may be connected
to a sacrificed alloy only if the sacrificed alloy has a much
greater area to distribute the resulting corrosion. Even
with a favorable area ratio, if the conductivity of the
corrosive brine is low (e.g., in a fresh water), the corro-
sion will be concentrated at the junction between the
dissimilar metals.
In oilfield treating equipment, stainless steel fixtures are
often used in a mild steel vessel. The more active mild
steel protects the more noble stainless steel. If the area of
mild steel is much greater (>50 to 100 times) than that of
the stainless steel, galvanic corrosion is unlikely.
In any case, the more active metal should not be coated.
The anodic reaction on a coated surface is concentrated at
any holiday, leading to rapid penetration and failure.
CORROSION RATE
Corrosion rates in water treating systems range from
negligible to hundreds of mils per year (1 mpy = 0.001
in./yr). Corrosion allowances vary but almost always
refer to acceptable general corrosion rates. When pitting
is considered, maximum allowable measured corrosion
rates should never exceed 5 mpy and should normally be
1 mpy or less. The penetration rate by localized cor-
rosion is generally 5 to 20 times greater than a measured
general corrosion rate.
Effect of Dissolved Gases

• Oxygen — Oxygen increases the corrosion rates of all
metals except alloys such as aluminum and low
chromium stainless steels. These alloys cannot form
stable passive films in reducing (oxygen-free) atmo-
spheres, but they do passivate in the presence of
oxygen. The high-chromium stainless steels and
high-performance aluminum alloys can passivate in
mildly reducing environments, so corrosion rates are
generally lower than in oxygenated solutions. The
corrosion rate of mild steel alloys always increases
with increasing oxygen content.

The solubility of oxygen from air at 1-atm pressure
Although oxygen into distilled water at room temperature is about
solubility is low, water 10 ppm. The solubility decreases with increasing
temperature and salt concentration. In seawater at
treatment facilities handle
60°F, solubility is about 7 ppm. In oilfield water
large volumes of water, so systems, target oxygen concentrations to prevent
the total amount of corrosion are 50 ppb (0.050 ppm) or less.
oxygen available to In water treating systems, oxygen should be rigor-
corrode equipment can be ously excluded. The usual oilfield corrosion inhibi-
significant. tors are not effective against oxygen corrosion. Oxy-
gen causes iron oxides, which degrade water quality,
to precipitate. In the presence of H2S, extremely
corrosive sulfoxy intermediates are formed, leading to
high corrosion rates and iron sulfide precipitation.
• Hydrogen Sulfide — H2S contributes to pitting corro-
sion of mild steels and to pitting and stress corrosion
cracking of high-strength stainless steels. The corro-
sion rate of mild steel in distilled water increases with
H2S concentration from 2 to 150 ppm. The rate stays
constant from 150 to 400 ppm and then drops owing
to the formation of a protective sulfide film until the
concentration reaches 1,600 ppm. The rate is constant
from 1,600 to 2,640 ppm.
In distilled water, the corrosion rate resulting from
H2S decreases with time. In a brine, the rate increases
with time, but the presence of small amounts of CO 2
may moderate the effect, giving essentially constant
corrosion rates with time.
With mild steel alloys, the iron sulfide corrosion
product is cathodic to iron, forming localized galvanic
corrosion cells and leading to high pitting rates. The
iron sulfides are readily oxidized by oxygen, hydro-
gen peroxide, and chlorine dioxide, which can gener-
ate transient corrosion rates as high as 2,000 mpy.
• Carbon Dioxide — CO2 is corrosive at moderate
temperatures and above 7-psi partial pressure. Corro-
sion is more extensive above about 30-psi partial
pressure. The corrosion rate increases with tempera-
ture. CO 2 corrosion is typified by “mesa” corrosion —
wide, flat-bottomed pits with smooth edges sur-
rounded by unattacked steel. Corrosion rates depend

heavily on flow conditions. At little or no flow, corro-
sion rates are high in stagnant areas. At moderate
flow rates, iron carbonate films are deposited. These
films are protective to some extent but may cause
localized corrosion. At high flow rates, iron carbonate
films are removed, and corrosion rates increase.
CO2 often enhances corrosion by other species, such
as oxygen, chloride, and H2S. CO2 also contributes to
sulfide stress corrosion cracking.
Effect of Dissolved Solids

• Chlorides — Chlorides attack passive layers on mild
and stainless steels. They promote pitting and crevice
corrosion, and are often to blame for alloy cracking.
Chloride is generally found in high concentrations in
oilfield waters, so it also contributes to corrosion by
increasing the brine conductivity. The more conduc-
tive the brine, the higher the corrosion rates.
• Carbonates — Calcium carbonate alkalinity is often
beneficial in controlling corrosion. Under some
circumstances, carbonate films may be deposited as
protective layers on the metal surface. In addition,
cathodic protection relies to some extent on the depo-
sition of carbonate films to help protect a structure
and to reduce the current required to maintain a
protective potential.
• Sulfates — Sulfate ion is rarely considered a
corrodent in oilfield brines. However, high sulfate
concentrations are often of concern in water systems
contaminated with sulfate-reducing bacteria (SRB’s)
when sulfate is converted to corrosive sulfide.
Effect of Oil and Grease

Suspended oil and grease generally provide some (up to
about 80%) corrosion protection. Suspended organics are
also thought to act synergistically in filming amine corro-
sion inhibitors to further protect metal surfaces.

Effect of Flow and Suspended Solids
In stagnant or low-flow conditions, general corrosion
rates are low but pitting rates are high. In moderate flow,
pitting rates are low and general corrosion rates are
moderate. Turbulence usually causes high general corro-
sion rates and high pitting rates. In oxygen-free brine,
areas of high flow are anodic (more likely to corrode) to
areas of low flow. In aerated water, differential aeration
cells cause low-flow areas to become anodic to high flow
areas.
Copper is relatively immune to quiescent seawater. At
flow rates above 3 to 4 ft/sec, copper corrodes more
easily. Cuprou-nickel (90% Cu, 10% Ni) is more resistant
to flow. It is used at design velocities of 5 to 12 ft/sec. If
small amounts of H2S are present, the nickel content
provides no increased protection over pure copper.
Higher nickel content (to 30%) provides more protection
at higher velocities but may pit under stagnant condi-
tions.
Suspended solids can cause erosion/corrosion by con-
tinually exposing fresh metal to a corrosive fluid. Sus-
pended gas bubbles also cause erosion/corrosion.
Effect of Water Treating Chemicals

• Oxygen Scavengers — Common oxygen scavengers
API RP-14E is commonly are sodium sulfite, sulfur dioxide, and sodium bisul-
fate. If used in a system that has low natural sulfate
used to predict
content, these scavengers may provide a sulfate
erosiveness in flowing source for SRB, leading to H2S generation and in-
systems. This procedure creased corrosion rates. Otherwise, there is little
has been found to be only interaction with corrosion inhibitors.
roughly applicable to • Biocides — There are two kinds of biocides: oxidizers
oilfield systems and and organics. Organic biocides are very similar to
(sometimes identical to) corrosion inhibitors and
several recent projects are therefore present no corrosion problems. Oxidizing
in progress to improve (chlorine, chlorine dioxide, etc.) biocides are often
erosion prediction. more reactive than oxygen. Corrosion from oxidizing
biocides is generally seen as pitting. Organic cor-
rosion inhibitors are of little use against this corrosive

agent. Oxidizing inhibitors, such as manganate or
zinc nitrite, can sometimes be used, but high concen-
trations are required.
• Scale Inhibitors — Oilfield scale inhibitors are usually
phosphorous-containing compounds that have little
effect on corrosion rates. However, they may be
incompatible with corrosion inhibitors. Chapter 5
gives more information.
• Chelating Agents — Corrosion rates can be extremely
high in the presence of chelating agents, such as
EDTA (often used in scale removal). Chelants remove
protective films from the surface of metals by
complexing with the cations.
Effect of pH
• Pourbaix Diagrams — Pourbaix diagrams show the
thermodynamic stability of various metals in various
environments. The diagrams say nothing about the
rates of corrosion reactions; they show only tenden-
cies. They also show regions of stability of a metal
and its oxides. Areas where the metal and its oxides
are not stable are generally regions of high corrosion
rates. With iron, the oxides are more stable at a
higher pH, so corrosion rates are generally lower
from pH 7 to 13. Above pH 13, corrosion rates again
increase. Corrosion rates increase with decreasing pH
below 7.
• pH Buffering — Weak acids, such as carbonic acid and
acetic acid, provide a pH buffering capacity that often
leads to higher corrosion rates than could be expected
from the solution pH alone.
Effect of Temperature
Increasing temperature (in the normal range of water
treating systems) generally increases corrosion rates,
particularly in corrosion caused by dissolved acid gases.
Although oxygen solubility decreases with temperature,
corrosion rates in open systems increase with tempera-
ture. If the temperature is not uniform, hotter areas are
generally anodic to cooler areas.

Effect of Deposits
• Adherent Deposits — Adherent deposits often form
protective barriers to corrosion. The best example is
the polarization (reduction in current requirement)
that occurs on cathodically protected steel in seawa-
ter. At high initial current densities, a dense layer of
adherent calcium carbonate, which helps protect the
metal, is deposited.
• Nonadherent Deposits — Nonadherent deposits, in
many instances formed from corrosion products,
provide stagnant areas that can lead to rapid pitting.
Pigging is used primarily to remove deposits and to
allow uniform access from the environment to the
metal. Nonadherent deposits also provide protection
for bacteria, which increase pitting tendencies.
Nonadherent iron sulfide deposits are cathodic to
iron, especially in the presence of oxidizers. The
galvanic cell created can cause rapid penetration of
pipes and vessels.
Periodic scrapping (pigging) to remove these deposits
from within pipelines is an important part of effective
corrosion control in water handling systems. Pigging
minimizes the stagnant areas, removes bacteria colo-
nies, and allows chemical inhibitors to come in con-
tact with the metal surface.
MONITORING
The monitoring methods can be characterized by the time
required for measurement and the type of corrosion
detected. The monitoring methods are useful for detect-
ing significant changes in corrosion rates, but they should
not be used to determine exact corrosion rates. More
than one monitoring method should always be used to
overcome the limitations of each method. Coupons should
always be included in the monitoring program.
For more information on specific equipment and for
ordering information, see the Corrosion Prevention
Manual, Section 400.

Inspection
The most reliable corrosion monitoring method is peri-
odic inspection. All parts removed from a water treat-
ment system should be inspected. If possible, the parts
should be sandblasted to reveal hidden pitting. For
cracking or fracturing, failure analysis should be used to
determine the cause and cure. (Successful failure analy-
sis depends on a failure expert’s prompt study of failed
parts that have not been altered in any way.) A
boroscope can be used to inspect piping in place. In a
large pipeline, electronic inspection pigs can be used.
Note the type of corrosion product. For example, a red
corrosion product on an iron-containing alloy is probably
hematite. Hematite indicates that oxygen may be enter-
ing the system. Black deposits are usually either magne-
tite or iron sulfides. A drop of HCl will cause iron sul-
fides to bubble and evolve H2S. Magnetite is attracted to
a small magnet. If wet magnetite is removed from a
system and exposed to air, it will rapidly convert to
hematite, so parts must be inspected immediately. Iron
sulfides also oxidize rapidly, and large quantities can
spontaneously ignite upon drying under some condi-
tions.
Coupons and Spools

Weight-loss coupons and in-line spools are used as long-
term corrosion monitoring tools. Coupons are usually
exposed for 1 month, while spools may be inspected after
6 months or longer. Coupon placement will affect the
measured corrosion rates. Flush-mounted coupons
reproduce the conditions along the surface of a straight
run of pipe; in-line coupons approximate the turbulence
that may be seen at bends, valves, tees, and pumps.
Methods of mounting coupons are specified in NACE
Standard RP-07-75, Preparation and Installation of Corrosion
Coupons and Interpretation of Test Data in Oil Production
Practice specifies methods of mounting coupons. (See the
listing of NACE publications at the end of this chapter.)
Coupons are usually installed on electrical insulators to
prevent galvanic interaction with precorroded piping.

The disadvantage of using coupons and spools is the
long time required. An advantage is that we can see
what type of corrosion is predominant.
Iron Counts
The dissolved iron concentration in a water stream can
sometimes be correlated to the corrosion rate upstream.
The surface area of corroding pipe and the flow rate are
used to calculate a general corrosion rate. This method is
of little use in streams containing oxygen or sulfides
because iron compounds will precipitate.
Organic corrosion inhibitors contain surfactants and act
as detergents. These inhibitors will clean fouled surfaces,
so initial iron counts after a treatment starts will be quite
high.
Electrical Resistance
Electrical resistance probes, such as the Rohrbach-
Cosasco Corrosometer, measure the gradual increase in
electrical resistance of a thin wire as it loses metal by
general corrosion. The probes are usually designed for a
response time of at least a few hours and a probe life of
several months or even years. The probes generate an
electrical signal, providing a continuous record of corro-
sion rates.
Pitting corrosion cannot be distinguished with a single-
probe instrument. Various types of probes are available
that respond to pitting in different ways. Wire-loop
probes are more sensitive to pitting damage than cylin-
drical probes are. Wire-loop and tube-loop elements are
also subject to being electrically shorted by a bridge of
iron sulfide deposits.
Most resistance probes include a coated reference ele-
ment to compensate for temperature changes. In rapidly
changing temperatures, the reference element tempera-
ture will not be able to track the test element, leading to
errors in readings.

All-welded cylindrical probes have no seals at the con-
nection end, so they are less likely to leak. They also are
always in electrical contact with the pipe wall, possibly
leading to galvanic interactions. The welds may be
preferentially attacked in some systems.
Because the resistance probe is expected to corrode, the
body itself and the backup seals must be corrosion-
resistant to prevent leaks when the probe fails.
Linear Polarization
Tretolite’s PAIR and Rohrbach-Cosasco’s Corrater mea-
sure instantaneous corrosion rates using the linear polar-
ization method. These instruments also generate a con-
tinuous record of corrosion rates. They have a response
time of minutes, but the probes should not be used for
more than about a week and readings should be corre-
lated to exposure time. Again, pitting corrosion is not
well detected.
These electrochemical instruments are limited to conduc-
tive electrolytes. At a corrosion rate of 2.5 mpy, the
solution conductivity must be at least 100 to 250
micromhos/cm for accurate readings. In low-conductiv-
ity brines, a three-electrode instrument should be used,
while either two- or three-electrode systems are suitable
for high-conductivity brines. The probes are easily
fouled by high oil concentrations.
Galvanic Probes
The Fincher galvanic probe system is similar to the linear
polarization instruments, except the driving voltage is
derived from the galvanic interaction between two dis-
similar metals. The same concerns apply to these instru-
ments as to linear polarization probes, but they have the
advantage of not requiring power. The usual metals are
mild steel and brass. The same technique is used by the
Tretolite’s Zero Resistance Ammeter oxygen monitoring
instrument.

Hydrogen Monitors
Hydrogen patch probes and finger probes are used in
sour systems to measure the rate of evolution of atomic
hydrogen. The patches are installed on the external side
of pipes or vessels. As atomic hydrogen diffuses through
the pipe, it recombines and generates a high pressure of
molecular hydrogen. Finger probes, constructed of thin-
walled tubing, are inserted into the flow stream. The
finger probe is more rapid because the hydrogen perme-
ates a smaller distance.
The hydrogen can be detected by measuring the pressure
buildup, by applying a vacuum and measuring the
hydrogen at a titanium cathode, or by electrochemical
A new form of hydrogen methods. The principle disadvantage of these probes is
patch probe, the Beta Foil, that temperature, flow rate, metal composition, scales,
has been generating and other factors influence the hydrogen permeation
interest because of rate. Experience in several fields has shown that hydro-
gen probes are erratic and difficult to interpret.
claimed improvements in
ease of use and in Ultrasonic Surveys
accuracy. In this method, an ultrasonic source is connected to the
outside of a pipe or vessel, and the time required for a
reflection from the other side is measured. Generally,
several points in a system are clearly marked so that the
same point is tested in each of a series of surveys. The
disadvantages of this method are that only a very small
fraction of the piping or vessel may be tested and that
severe pits may be missed entirely.
CORROSION PREVENTION
Corrosion prevention should begin in the early design
stages of a water handling facility with the proper choice
of materials of construction. In terms of installed cost,
ease of installation, and temperature and pressure re-
quirements, the construction material of choice is usually
mild carbon steel. Coatings, cathodic protection, and
chemical treatment are then used to control corrosion. In
most water injection systems, however, the volume of
water handled is quite large, so chemical treatment for
corrosion control becomes very expensive.

Tanks and vessels are usually protected internally by a
combination of coatings, cathodic protection, and chemi-
cal treatment (including inhibition and oxygen removal).
Coatings, chemical treatment, and material selection
(alloys or plastics) provide internal protection for piping.
Tanks, vessels, and piping are protected externally by
paints or coatings above grade and by coatings and
cathodic protection below grade.
Plastics should be considered for low-pressure, low-
temperature systems. At somewhat higher pressures,
fiberglass-reinforced plastics (FRP) may be appropriate.
For seawater treatment plants, copper/nickel alloys may
be required. When selecting materials, we must consider
the materials for use in valves to avoid galvanic corro-
sion problems. We must also consider the cost of coat-
ings, cathodic protection, or corrosion inhibition over the
life of the project. Pig launchers and catchers should be
included where appropriate to keep the system clean.
Once we have selected materials and other corrosion
prevention methods, we should review the design to
eliminate obvious corrosion problems. For example,
small dead volumes are often preferentially corroded.
Intermittent flow is sometimes more corrosive than
constant flow. Extremely high velocities should be
avoided. For some materials, a minimum flow velocity
may be required. Elbows in series that rotate flow out of
a plane create swirling turbulence and should be
avoided. Sources of oxygen contamination can be par-
ticularly troublesome.
We should consider corrosion monitoring methods and
equipment early in the design. At the very least, all
water treatment facilities should be designed with liberal
access for installing and removing weight-loss coupons.
In addition, some electrochemical or electrical resistance
monitoring should be included for rapid corrosion
assessment. Chemical injection points should be re-
viewed to ensure that incompatible treatments are not
proposed.
Of equal importance is specification of fabrication meth-
ods, such as welding, bolting, flanges, and coatings
application. On-site inspection during fabrication is

recommended for large projects involving highly alloyed
steels, for critical components, for coatings, or for compo-
nents requiring postfabrication heat treatment.
Inhibitors
• Organic Inhibitors — Organic corrosion inhibitors
almost exclusively have nitrogen-containing func-
tional groups. Several classes of chemicals may be
used, including low-molecular-weight amines for
vapor-phase inhibitors, filming tertiary and quater-
nary amines for water service, and imidazolines for
sour applications. The nitrogen-containing organic
inhibitors are rarely useful in oxygenated waters.
Vapor phase inhibitors, such as morpholine and
cyclohexylamine, have boiling points near that of
water. Thus, wherever water condenses, the inhibitor
condenses. The inhibitor acts by neutralizing acid
gases, such as CO2 and H 2S. Because these neutraliz-
ing inhibitors react stoichiometrically, treatment levels
may be quite high in some systems.
Water-phase inhibitors may be either water-soluble or
water-dispersible. Intended for systems with no oil
phase, water-soluble inhibitors generally are some-
what less effective than water-dispersible inhibitors.
Water-dispersible inhibitors, formulated with a hy-
drocarbon carrier, are only slightly soluble in water.
These chemicals tend to have better film persistency
than water-soluble chemicals.
• Inorganic Inhibitors — In oxygenated freshwater
systems near neutral pH, inorganic inhibitors are used
to promote the formation of passive films on steel
surfaces. These chemicals include chromates,
manganates, phosphates, sulfates, borates, vanadates,
and nitrites. Applications for inorganic inhibitors are
rare in the oil field; most systems should be main-
tained in an oxygen-free condition.
Alloys
This section is intended only as an introduction to the
wide variety of corrosion-resistant alloys. For more
information, consult the Corrosion Prevention Manual.

• Cast Iron — Cast irons may be used in specialized
applications to take advantage of specific properties.
Some cast irons may be harder or more resistant to
abrasion than mild steels. Cast iron is often used in
potable water systems, where corrosion is controlled
by calcium carbonate hardness.
• Stainless Steels — A minimum of 11% chromium in
iron alloys will spontaneously form a stable passive
film in the presence of water, resulting in a stainless
steel. Chromium/iron alloys with no other alloying
metals fall into two groups. At high chromium con-
centration, these steels have a ferritic crystal structure
and cannot be hardened by heat treatment. At low
chromium concentration, these steels may have an
austenitic structure that can be hardened by heat
treatment. The concentration boundary between
these two groups depends on carbon content but
varies from 12% to 18% chromium.
Nickel promotes the stability of the austenite struc-
ture and improves toughness, ductility, and weld-
ability. Molybdenum is often added to improve
resistance to pitting and crevice corrosion. It also
improves strength. Small quantities of other elements
may be added to improve specific properties.
Corrosion resistance results from the passive oxide
film. Stainless steels typically perform poorly in
reducing environments (where the passive film may
be reduced) and in erosive environments (where the
film may be abraded). The kinds of attack more likely
in other environments are pitting, crevice corrosion,
chloride stress corrosion cracking, and intergranular
corrosion.
There are five kinds of stainless steels (alloys of iron
with chromium, nickel, molybdenum, and minor
components).
1. Austenitic stainless steels are nonmagnetic chromium
and nickel-containing alloys. They can be hardened
by cold working but not by heat treatment. Most are
readily weldable. AISI designations are in the 200 and
300 series. Types 304 and 304L are 18Cr-8Ni. These
are generally the most corrosion-resistant alloys, with

resistance increasing with nickel content. Molybde-
num containing alloys (316, 317) have improved
resistance to chlorides and crevice corrosion.
2. Ferritic stainless steels are magnetic chromium- contain-
ing alloys produced by slow cooling. They can be
moderately hardened by cold working but not by heat
treatment. These metals are usually resistant to chlo-
ride cracking. AISI designations are, for example, 405,
430, and 446.
3. Duplex alloys are mixtures of austenite and ferrite.
Thirteen percent They are tougher than ferritics. Their cracking resis-
tance is intermediate and decreases with cold
Chromium stainless steel
working. Crevice and pitting corrosion resistance is
has achieved widespread generally less than that of austenitic or ferritic alloys.
use in the oil industry. Welding reduces the resistance to pitting in the heat-
Chevron has extensive affected zone on older alloys. Newer alloys contain
0.15% to 0.25% nitrogen, which improves the corro-
experience with this
sion resistance in a properly welded heat-affected
material. zone. Some common examples of newer alloys are
SAF2205 (also called AF22) and Ferralium 255.
4. Martensitic alloys are typically hard magnetic alloys
produced by rapid quenching. They can be hardened
by heat treatment. AISI designations are, for example,
403, 410, 414, 416, 420, 431, and 440. These materials
are often used for pump shafts, valves, and bearings.
5. Precipitation-hardened steels are chromium/nickel alloys
with such precipitating elements as copper or alumi-
num. Hardness comes from reprecipitation along
grain boundaries during postquenching heat treat-
ment. A common type is 17-4PH.
• Nickel Alloys — Nickel is resistant to nonoxidizing
acids and atmospheric corrosion. It is less resistant to
oxidizing acids, seawater, or sulfur containing reduc-
ing environments at high temperature.
Monel (70%Ni/30%Cu) passivates in moving seawa-
ter and is resistant to pitting. In stagnant seawater,
Monel is susceptible to pitting. It is also susceptible
to wet Cl2, sometimes used as a biocide. Inconel
(76%Ni/16%Cr/7%Fe) has good oxidation resistance
at elevated temperature. Hastelloy B (60%Ni/
30%Mo/5%Fe) is resistant to all but oxidizing acids.

Hastelloy C (54%Ni/15%Cr/16%Mo/4%W/5%Fe) is
resistant to oxidizing media and mixed acids. It has
outstanding resistance to pitting and crevice corro-
sion.
• Copper Alloys — Copper is resistant to corrosion in
oxygen- free water but is susceptible to high-velocity
(>5 ft/sec) water containing oxygen. It is also suscep-
tible to complexing agents like ammonium ions that
can cause rapid stress corrosion cracking. Copper is
resistant to seawater, and alloys above 60% copper do
not biofoul. Copper is not resistant to oxidizing acids
and will react with H2S. Brasses (copper/zinc alloys)
show more resistance to flowing water (up to 8 ft/sec)
but are subject to dezincification (selective leaching of
zinc), especially in stagnant areas and under deposits.
• Aluminum Alloys — Aluminum forms a tightly
adherent passive oxide layer that is resistant to sul-
fides and CO2. Aluminum is an amphoteric metal;
this passive film is stable near neutral pH but dis-
solves in either acids or bases. It is susceptible to
pitting in the presence of chlorides, crevice corrosion
and underdeposit attack, and attack by dissolved
copper that plates out and forms galvanic cells. Sev-
eral aluminum alloys are available with superior
resistance to chlorides.
Plastics and FRP’s

A wide variety of noncorroding plastic materials are
useful in low-temperature, low-pressure applications.
Various plastics may be reinforced with fiberglass to
improve their mechanical strength. Among the com-
monly used plastics are polyesters, vinyl esters, and
epoxies. The corrosion resistance of FRP is determined
not only by the plastic used but also by the curing agent,
fabrication method, and liner (if present). For more
information, see the Chevron Pipelines Manual and the
Chevron Corrosion Prevention Manual.
Cathodic Protection
Internal cathodic protection is often used in tanks and
vessels. Cathodically protecting the inside of pipes is
impractical. Protective current may be derived from

galvanic anodes or from impressed current rectifiers.
Galvanic systems are preferred for small-current-demand
systems requiring small driving voltages, such as the
inside of most tanks and vessels. Impressed current
systems are necessary when current requirements or
driving voltage requirements become too great. Care
must be taken when protecting coated surfaces to pre-
vent cathodic disbondment. Cathodic protection is often
used with coatings to protect the external side of buried
piping and tank bottoms.
For more information on cathodic protection, see the
Corrosion Manual, Part 2.
Removal of Dissolved Gases

• De-Aerators and Degasifiers — Vacuum de-aeration
and gas stripping (or pressure de-aeration) will re-
move volatile gases - including oxygen, CO2, H2S, and
ammonia - from a water stream. We usually follow
de-aeration by oxygen scavenging to remove the trace
of remaining oxygen. The amount of acid gas (CO2
and H2S) that can be removed depends on the pH of
the water: at low pH, almost all can be stripped; at
high pH, the gases are present as nonvolatile ions.
The reverse is true for ammonia, which is a basic gas.
Commonly used stripping gases are natural gas and
its combustion products, steam, or nitrogen. Com-
bustion products of natural gas are produced in a
special burner, leaving no residual oxygen, or in an
inert-gas generator. The advantage is that the volume
of gas produced by combustion is about nine times
that of the burned gas, and pipeline gas often contains
some oxygen. Steam stripping is often used for boiler
feedwater because the heat is not wasted (only a small
amount of steam is vented). The solubility of oxygen
decreases with temperature. In vacuum de-aeration,
no stripping gas is added. The pressure is reduced in
a packed tower until the unheated water phase begins
to boil, removing dissolved gases.
Packed towers, tray towers, and spray towers are
used for degasifying. The stripping gas must be
chosen with care. For example, CO2 may be stripped
along with oxygen, resulting in a higher pH and the

possibility of calcium carbonate scaling. If the strip-
ping gas contains CO2, the pH may be lowered
enough to cause corrosion. If the stripping gas con-
tains H2S, corrosion rates may be affected. The pH
should be kept low when H2S is stripped. The best
way is to use a stripping gas with a high con-
centration of CO2. Steam stripping is limited to wa-
ters with low total dissolved solids to prevent scaling.
Steam stripping can reduce oxygen levels to 6.5 ppb.
Vacuum de-aeration generally leaves 0.33 to 0.65 ppm
oxygen.
For further information, see NACE Standard RP-02-78,
Design and Operation of Stripping Columns for Removal
of Oxygen From Water or Chapter 3 of this handbook.
• Oxygen Scavengers — The three most common oxy-
gen scavengers are sulfite ion (from sodium sulfite,
sulfur dioxide, or ammonium bisulfite), hydrazine,
and sodium hydrosulfite (dithionite). All three re-
quire a catalyst and at least several minutes of reac-
tion time. The catalyst is a transition metal ion, such
as nickel or cobalt, at about 0.1 mg/L. Theoretically,
7.88 ppm of pure sodium sulfite is required to remove
1 ppm of oxygen. The residual level of scavenger is
maintained at 1 to 10 ppm. Hydrazine is usually
limited to high-temperature systems (above 200°F);
sulfite may decompose to sulfur dioxide and H2S.
Hydrazine is a toxic liquid with a flash point of 35°F.
It is usually supplied as a less explosive 35% solution.
In practice, 1.5 to 2.0 ppm of hydrazine is required per
1 ppm of oxygen, with residuals of 0.1 to 0.5 ppm.
Required residence time becomes very long below 150
to 200°F.
The catalyst may be inactivated by precipitation with
sulfide ion or complexing with a chelant. The pres-
ence of alcohols, phenols, or amines can slow the
reaction by reacting with intermediate free radicals.
Corrosion inhibitors may interfere with the reaction
by either mechanism. In some cases, adding sulfite
results in sufficient sulfate to increase the activity of
sulfate reducing bacteria.

Ammonium bisulfite is often used in place of sodium
sulfite. Its lower molecular weight means that only
6 ppm needs to be added for each 1 ppm of oxygen to
be removed. Ammonium bisulfite is also more
soluble that sodium sulfite, so more concentrated feed
solutions can be used. Sulfite ion may also be formed
in solution by bubbling sulfur dioxide.
• Sulfide Scavengers — Small concentrations of H2S can
be removed by oxidation or precipitation. Chlorine
and chlorine dioxide will react to produce either
elemental sulfur or a sulfur oxide. Iron sponge will
remove H2S by forming insoluble iron sulfide.
Coatings
Coatings provide barriers to corrosion. A large variety of
coating materials, application systems, and curing tech-
niques are available. The Chevron Coatings Manual
covers the options in great detail.
Because no coatings are perfect, small holidays exist that
may be the site for accelerated pitting. Cathodic protec-
tion is often used to protect these holidays. The coating
protects most of the metal and significantly reduces the
protective current required. In congested areas or high-
resistivity electrolytes, coatings are necessary to reduce
current requirements sufficiently that interference is not a
problem.
Surface preparation is essential in applying a good coat-
ing. If the surface is not prepared correctly, the coating is
wasted and may cause more harm than good (localized
corrosion, flaking, etc.). The coating must be properly
mixed and applied according to manufacturer’s speci-
fications. The coating must cure under the proper
temperature and humidity conditions for the proper
length of time. Inspection at each stage is recommended.
Linings
Two types of linings are common.
1. Concrete-lined pipe has been used successfully in CO2
floods and in flowlines and larger water service. For
more information on concrete linings, see the Piping
Manual.

2. Plastic linings are often used to repair severely cor-
roded pipe. The old pipe serves as an installation
guide for new plastic pipe pulled through the line.
For more information on plastic liners, see the Corro-
sion Prevention Manual and the Pipelines Manual.
Pigging and Scraping

Pigging is used to remove deposits from the inside walls
of pipes, to improve flow, or to prevent underdeposit
corrosion. Pigging can be performed on pipes of any size
but requires launchers and catchers. In addition, facilities
should be provided to collect the solids knocked loose by
pigging to prevent them from degrading the water qual-
ity if the water is used for injection. Pigs fall into three
categories, each having a different purpose.
1. Cup or disk pigs usually have at least two cups, leading
and trailing. More cups, scrapers, and brushes can be
installed between the two cups. This type of pig is
generally designed for one pipe size only and can
accommodate out-of-roundness. Large dents or
buckles in the pipe may stop these pigs. This type of
pig can also be used to apply inhibitor treatments or
internal coatings.
2. Foam pigs are made from an inner core of open-cell
foam that may be covered with a harder material for
abrasion resistance. These pigs can pass through
restrictions, can traverse sharp bends and tees, and
can be used in several sequential line sizes.
3. Spherical pigs are round plastic or rubber balls, either
hollow or solid. They are useful for lines with several
tight bends within a short distance. This type is used
more for separating fluids than for cleaning.
Typical upstream pressures for four-cup pigs are 50 to
200 psi for 2-in. pipe, 35 to 140 psi for 6-in. pipe, 15 to
100 psi for 10-in. pipe, and 10 to 60 psi for 18-in. pipe. It
may take up to three times the moving pressure to start a
pig, either from the launcher or after sticking. Pigs
should move at 3 to 6 ft/sec for most cleaning applica-
tions.

GENERAL REFERENCES
NACE Publications
1. Corrosion Data Surveys.
2. Standard RP-01-69, Control of External Corrosion on
Underground or Submerged Metallic Piping Systems.
3. Standard RP-01-75, Control of Internal Corrosion in
Steel Pipelines and Piping Systems.
4. Standard RP-04-75, Selection of Metallic Materials to
be Used in All Phases of Water Handling for Injection
into Oil Bearing Formations.
5. Standard RP-05-75, Design, Installation, Operation,
and Maintenance of Internal Cathodic Protection
Systems in Oil Treating Vessels.
6. Standard RP-07-75, Preparation and Installation of
Corrosion Coupons and Interpretation of Test Data in
Oil Production Practice.
7. Standard RP-02-78, Design and Operation of Strip-
ping Columns for Removal of Oxygen From Water.
8. Standard RP-01-81, Liquid Applied Internal Protective
Linings and Coatings for Oil Field Production Equip-
ment.
9. Standard MR-01-75, Sulfide Stress Cracking Resistant
Material for Oil Field Equipment.
Books
1. BETZ Handbook of Industrial Water Conditioning, J.J.
Maguire (ed.), Betz Laboratories, Trevose, PA (1980).
2. Munger, C. G.: Corrosion Prevention by Protective
Coatings, NACE, Houston (1984).
3. Corrosion Inhibitors, C.C. Nathan (ed.), NACE, Hous-
ton (1981).
4. CO2 Corrosion in Oil and Gas Production - Selected
Papers, Abstracts, and References, L.E. Newton and R.H.
Hausler (eds.), NACE, Houston (1984).
5. Ostroff, A.G.: Introduction to Oilfield Water Technology,
NACE, Houston (1979).
6. Uhlig, H.H.: Corrosion and Corrosion Control, John
Wiley and Sons Inc., New York City (1971).

APPENDIX A
INDEX TO CHEVRON
CORROSION PROTECTION MANUAL

APPENDIX B
INDEX TO CHEVRON COATINGS
MANUAL

APPENDIX C
INDEX TO CHEVRON PIPELINE MANUAL

C H A P T E R
Microbiological Problems in
Production Operations
Chapter 7: Microbiological Problems in Production Operations 7-1

INTRODUCTION
Microbiological and bacterial activity can have beneficial
or detrimental effects on producing operations. Ex-
amples of beneficial effects in reservoir engineering are
seen in microbially enhanced oil recovery (MEOR) pro-
cesses. In MEOR, bacterial activity (1) produces gases
that increase reservoir pressure and/or reduce oil viscos-
ity, (2) breaks down heavier crude oil fractions to affect a
lower viscosity, or (3) forms in-situ surfactants to lower
interfacial tensions and improve recovery.
In microbial profile modification (MPM), bacterial activ-
ity within the reservoir is deliberately augmented to form Beneficial Effects —
biofilms and extracellular polymeric substances (EPS). Microbially enhanced
These substances can plug watered-out zones or adjust
permeability profiles for improved sweep efficiency and oil recovery — MEOR
oil recovery. Microbial profile
In producing operations, though, most of the effects of modification — MPM
bacterial activity are detrimental. This activity can be Detrimental Effect —
within the reservoir or in downhole and surface equip- Plugging and fouling
ment for production, treating, or injection. These detri-
Corrosion chemical
mental effects range from shorter operating lives for
equipment to increased costs for oil production and Consumption damage.
water treatment; from loss of reserves to degradation of
crude oil and natural gas quality and value. This chapter
discusses (1) the detection of microbial activity as the
cause of, or at least a contributing factor to, production
problems, (2) control procedures to eliminate or reduce
microbial activity, and (3) monitoring procedures to
determine the efficacy of control procedures.
MICROBIOLOGICAL ACTIVITY CAUSES

PROBLEMS
During their growth and multiplication, bacteria produce
additional cells, EPS (biofilms), and metabolic products.
These materials contribute, directly or indirectly, to
problems in producing operations. Table 1 lists the types
of problems encountered.

Table 1 Bacterially Related Problems
Plugging and Fouling
Microbiologically Influenced Corrosion
Reservoir Souring
Environmental Concerns
Chemical Consumption
Water Chemistry
Formation Damage
Plugging and Fouling

Actively growing bacteria usually are 1 to 2 µm. The
production of additional bacterial cells during growth
and multiplication can cause plugging in a porous forma-
Growth of bacteria and
tion, particularly when the formation has a low perme-
production of biofilms by ability. When bacteria grow and multiply, they also
bacteria can plug a porous produce an EPS called biofilm. (As discussed later,
formation and lead to loss aerobic bacterial reactions tend to produce more biofilm
than anaerobic reactions.) This polymer has several
of recoverable oil.
beneficial effects for the bacteria: (1) it provides a con-
centrating mechanism to remove nutrients from the
water, (2) it stores nutrients for future use, and (3) it
protects the bacteria from adverse environmental factors,
such as biocides.
Biofilms contain large amounts of water (usually more
than 80%) and have low permeabilities. They act as glue
for other particulate matter that might be in the system
(scale particles, corrosion products, formation fines, etc.).
By fouling the surfaces of vessels and piping and plug-
ging porous media (filters, ion exchange beds, formation
rock), biofilms restrict flow and increase pressure drops.
In extreme cases, they can even plug and block off por-
tions of the reservoir, resulting in loss of oil reserves.
Microbial Reservoir Souring

In addition to loss of production and reserves from
plugging and fouling, microbial activity within the reser-
voir can degrade the quality and value of produced
hydrocarbons and increase capital and operating costs
through microbial reservoir souring. In many producing

fields, produced fluids have changed from sweet to sour
because of hydrogen sulfide (H2S) produced within the Formation of hydrogen
reservoir by sulfate-reducing bacteria (SRB). Prominent sulfide by sulfate
examples include the Ninian field in the North Sea, the
reducing bacteria is a
Prudhoe Bay and Kuparak fields on Alaska’s North
Slope, and the Wilmington field in southern California. major cause of reservoir
souring.
Souring usually occurs when SRB are introduced into the
reservoir or the injection and producing wells. This can
occur during drilling, completion, or workovers from the
use of bacteria-contaminated fluids. It can also occur
during a waterflood from injection of inadequately
treated produced water, source water, or seawater. SRB
can convert inorganic sulfate ions in the produced or
injection water to H2S using organic compounds as the
reducing agent.
The amount of sulfide produced by a single sulfate-
reducing bacterium has been estimated to be 1.0 x 10-16
moles of sulfide per day.1 Although the amount of H2S
produced by an individual bacterium is low, the number
of SRB in a single milliliter of water or on a square centi-
meter of surface may be in the millions or even billions.
Microbially produced H2S concentrations may reach
hundreds of parts per million in the gas phase of the
produced fluids. Biogenic (produced by bacteria) H2S
degrades the quality of the produced hydrocarbons. H2S
has other detrimental effects that are discussed in the
following sections.
Microbiologically Influenced Corrosion

Extreme localized (pitting) corrosion that quickly pen-
etrates the walls of tubulars, production vessels, Hydrogen sulfide and
flowlines, and pipelines frequently occurs when bacteria
organic acids, both
and biofilms are present. The direct or indirect participa-
tion of bacteria and other microorganisms in the corro- metabolic products of
sion reaction has not been definitely and conclusively bacterial activity, increase
established. However, the increased corrosion in their the corrosivity of
presence has. This is one reason why this phenomenon
produced fluids.
has undergone changes in names from bacterial corrosion
to microbially induced corrosion to microbiologically
influenced corrosion (MIC).
Possible reaction mechanisms or interactions of bacteria
in the corrosion processes include:

1. Depolarization of the cathode reaction in the corro-
sion process because of intensified consumption of
hydrogen by bacteria.
2. Formation of patchy biofilms that enhance corrosion
through differential corrosion cells.
3. Generation of H2S that depolarizes the anode in the
corrosion reaction.
4. Formation of iron sulfide surfaces that increase the
rate of one or more of the corrosion reactions.
5. Formation of organic acids that are corrosive in them-
selves, provide an additional source of hydrogen ions
for the cathode reaction, destroy protective films, or
provide usable organic carbon sources of other micro-
Microbiologically bial reactions.
influenced corrosion
With MIC, the corrosion problem is enhanced because
(MIC) is particularly invariably the corrosion process is localized. Pit penetra-
harmful because it is a tion can cause equipment failures within a very short
form of localized time period. MIC frequently occurs where the corrosive
agent is generated. It can also occur away from the
corrosion and causes
generation site where the corrosive agent has migrated.
rapid pit formation. H2S produced by SRB and/or low-molecular-weight
organic acids produced by acid-producing bacteria (APB)
are the metabolic products usually involved in MIC. The
actions of SRB and APB are discussed in detail later.
Environmental Concerns
Like reservoir souring, the cause of environmental prob-
lems is the production of H2S by bacteria. However,
unlike souring, environmental problems can occur wher-
ever SRB are present - in the reservoir, production string,
separating and treating system, or injection system.
Hydrogen sulfide, formed
Environmental and safety concerns are related to the
by sulfate reducing extreme toxicity of H2S. The threshold limit value (TLV)
bacteria, is extremely for H2S is 10 ppm for 8-hour time-weighed-average
toxic and flammable. exposure. H2S is extremely flammable with flammability
limits of 4.3% to 45.5%. It is heavier than air and tends to
accumulate in low areas. H2S is easily recognized in low
concentration by its characteristic rotten egg smell. High
concentrations deaden the olfactory senses and can cause
unconsciousness and death before its odor is noticed.

H2S is very corrosive to carbon steel, particularly in the
presence of small amounts of oxygen. Attack is usually
localized, with rapid pitting and penetration of the walls
of vessels and pipelines. Leaks follow penetration, in-
cluding the release of H2S and environmentally sensitive
produced fluids. Corrosion and leaks can occur any
place in the system where H2S is present, even remote
from the point where the H2S is microbially produced.
Chemical Consumption
Bacterial activity can increase operating costs by consum-
ing or degrading treatment chemicals. Treatment chemi-
cals may stimulate bacterial activity. Some bacteria use
treating chemicals as a carbon and/or energy source for Operating costs for
metabolism. application of treating
Polymers used for scale control, diverting agents, or chemicals increase when
fracture fluid thickeners are frequently biodegradable. bacterial activity
Phosphorus-containing scale inhibitors and nitrogen-
containing oxygen scavengers may provide the trace consumes or degrades
nutrients required for bacterial growth. Biomass formed chemicals.
by bacteria may absorb treating chemicals or prevent
such chemicals as corrosion inhibitors and biocides from
reaching the surfaces they are designed to protect.
Larger dosages or more expensive formulations that can
penetrate the biofilms are required.
The metabolic products of bacterial activity may react
with or deactivate chemicals. Examples include con-
sumption of chlorine and other oxidizing biocides, deac-
tivation of aldehyde-type biocides, and the formulation
of gunking polymers by H2S. Oxygen scavengers that
rely on cobalt catalysts are nonreactive when the cobalt
reacts with sulfide. The formation of corrosive H2S or
organic acids will increase the need for more effective
(and probably more expensive) corrosion-inhibitor for-
mulations.
Water Chemistry
Bacterial activity affects water chemistry in a number of
ways. The formation of acids (e.g., CO2 and H2S) can
lower the pH and decrease the buffer capacity of the
solution. The concentrations of these two species also
increase in the associated gas phase. On the other hand,

the action of SRB on organic material usually causes a net
Bacterial activity can increase in alkalinity. Bacterial production of CO2 can
change produced water change the problems in a producing system, ranging
from carbonate scaling to CO2 corrosion. Sometimes the
chemistry by the
presence of “black water” resulting from the reaction of
formation of acid gases, dissolved iron and microbially generated H2S is the first
such as hydrogen sulfide sign of bacterial problems. SRB activity can change the
or carbon dioxide, and concentration of dissolved sulfate to such an extent that
the concentration change can be used as a diagnostic tool.
organic acids.
Formation Damage
Formation damage is usually indicated by a decrease in
porosity or permeability that modifies the amount or
pattern of fluid flow through the reservoir. Bacteria and
biofilms can plug a porous formation directly. The sticky
biofilms act as a cementing agent or glue for other par-
ticulates (scale particles, corrosion products, and forma-
Bacterial growth and tion fines) in the water. Some types of bacteria produce
biofilm production can organic acids that act as chelants or complexing agents
plug a formation. Organic for aluminum and silicon, thereby increasing the appar-
ent solubility of formation minerals. If the pH changes
acids formed by bacterial
later, the solubilized material may reprecipitate, causing
activity can dissolve some pore blockage. The biogenic acids can dissolve carbonate
minerals and cause minerals that may be acting as cementing agents and
formation damage. thereby liberate fines. Bacteria can decrease the amount
of dissolved sulfate materially, thus increasing the disso-
lution of sulfate minerals. Biogenic H2S readily reacts
with dissolved iron to form oil-wetted iron sulfide, which
is an excellent plugging material for porous formations
and a stabilizing agent for oil/water emulsions. This
plugging can reduce oil recovery by modifying the injec-
tion profile or blocking off flow in portions of the reser-
voir.
MICROBIOLOGICAL ENERGETICS
Bacteria require energy to Like all living things, bacteria require energy and certain
live and grow materials to live and grow (dissimilation) and to multiply
(dissimilation) and to by the synthesis of cell material (assimilation). The energy
source is usually an organic carbon compound (het-
multiply by the synthesis
erotrophic bacteria), although some bacteria can use gas-
of cell material eous or dissolved hydrogen as an energy source
(assimilation). (lithotrophic bacteria). The carbon source required for

cellular material may or may not be the same organic
carbon compound as the energy source, although some
bacteria can use CO2 (autotrophic bacteria). Additionally,
bacteria require other trace elements and nutrients (nitro-
gen, phosphorous, vitamins, and trace metals) to func- Bacteria derive energy by
tion. combining organic
Many bacteria derive their energy by combining organic materials or hydrogen
materials or hydrogen (reducing agents or electron do- (reducing agents) with
nors) with suitable electron acceptors (oxidizing agents) suitable oxidizing agents
in a microbiological oxidation/reduction reaction. Other
types of bacteria derive their energy and carbon needs by in oxidation-reduction
converting complex organic compounds to simpler ones reactions or by breaking
by disproportionation or fermentation reactions without down complex organic
external electron acceptors. Table 2 shows these two materials to simpler ones
reactions. The values for the free energy of formation at
pH 7, ∆Go’, were calculated with Brock and Madigan’s2 in fermentation reactions.
method and values. We adjusted free energies from
standard values at pH=0 to pH=7, a value more likely for
microbiological reactions.
Table 2 Typical Microbial Reactions

Oxidation-Reduction Reaction
Aerobic — Glucose
C 6 H 12 O 6 + 6O 2 = 6CO 2 + 6H 2 O ∆G° ′ = −687 kcal
;
Aerobic — Acetate
CH 3 COO − + 2O 2 = 2CO 2 + 2H 2 + 2H 2 O ; ∆G°′ = −204 kcal
Anaerobic — Acetate
CH 3 COO − + SO 24 − + 3H + = 2CO 2 + H 2 S ; ∆G° ′ = −38.0 kcal
Fermentation Reaction
Glucose
C 6 H 12 O 6 + 4H 2 O = 2CH 3 COO − + 2HCO 3− + 4H + + 4H 2 ; ∆G° ′ = −66.7 kcal
Note: ∆G° ′ = ∆G° @ pH = 7

In Table 2, for the aerobic oxidation/reduction reactions,
glucose (C6H12O6) or acetate (CH3COO ) is oxidized by
oxygen to CO2 and water (aerobic means in the presence
of oxygen; anaerobic means in the absence of oxygen). In
the anaerobic oxidation/reduction reaction, acetate is
oxidized by sulfate ( SO 2−
4 ) to bicarbonate. The sulfate, in
turn, is reduced to H2S. In the fermentation reaction, the

organic substrate, glucose (C6H12O6), is broken down to
acetate (CH3COO- ), bicarbonate ( HCO −3 ), and hydrogen.
The wide variance in energetics for oxidation/reduction
reactions vs. fermentation reactions is readily apparent.
Microbiological processes
Acetate and hydrogen, the fermentation products of
using oxidation/reduction glucose, possess considerable energy that can be released
reactions yield more by further oxidation to CO2 and water. If the fermenta-
energy and biomass than tion products would undergo the further oxidation that
occurs in the aerobic oxidation of acetate and the oxida-
fermentation reactions.
tion of hydrogen to water, the total free energy change
would be the same.
Another consideration is the effect of the electron accep-
tor (oxidizing agent) in the oxidation/reduction reactions
on the amount of energy released. The most energy is
liberated when oxygen is the electron acceptor as in the
aerobic reactions. In Table 2, compare the aerobic oxida-
tion of acetate (∆Go’ = -204 kcal) and the anaerobic oxida-
tion where sulfate is the electron acceptor (∆Go’ = -38.0
kcal). As before, the difference in energy released is the
energy content of the reaction product (H2S in this case).
These considerations are important. The sign of the free
energy change determines whether the reaction is ther-
modynamically possible — i.e., whether it will occur as
written. Only reactions with negative free energy
changes will proceed spontaneously without external
energy sources. The magnitude of the free energy change
is also important. When the changes are small, not much
energy is released in the reaction. Bacteria need most of
this energy just for cell maintenance and growth; little
energy is available for EPS production.
On the other hand, where large amounts of energy are
liberated, bacteria can produce large amounts of EPS. In
typical aerobic processes, large amounts of energy are

produced and 50% or more of the substrate may be
converted to cell material and EPS. In anaerobic pro-
cesses, the amount of energy released is small, and only
about 10% of the substrate is converted to cellular and
polymer material. Thus, aerobic reactions produce more
bacterial slime and create more plugging and fouling
problems than anaerobic reactions do.
MICROORGANISMS INVOLVED IN
MICROBIAL PROBLEMS
Bacteria are scientifically classified by genus and species.
The genus refers to a group of related bacteria; the spe-
cies refers to different bacteria within a genus. The types
of bacteria and microorganisms that contribute to or
influence problems in producing operations are de-
scribed here in a functional sense in terms of activity or
metabolic products, rather than by strict microbiological
classifications. Particular bacterial species are given
sometimes. The bacterial classifications are written in
italics.
In the field, a number of different types of bacteria are
usually involved; laboratory studies frequently focus on
one type. The differences in behaviors of bacterial con-
sortia vs. pure cultures are also discussed in this section.
Finally, a distinction in bacteria and microbial activity
and processes dependent on the location of the bacteria -
free floaters in the water stream or attached bacteria - are
addressed.
Sulfate-Reducing Bacteria — SRB

SRB are the most familiar type of bacteria, primarily
because of their implication in MIC. They derive their Sulfate reducing bacteria
name from their ability to reduce inorganic sulfate ions (SRB) produce hydrogen
( SO2−
4 ), present in most waters, to H2S or bisulfide ions
sulfide by reducing
(HS-). They use an organic compound or hydrogen as the inorganic sulfate ions in
reducing agent. In addition to the formation of toxic and water with organic
corrosive H 2S, SRB plug producing formations and foul material or hydrogen.
equipment. They do this directly by forming biofilms
and indirectly by forming iron sulfide corrosion prod-
ucts.

SRB are classified as obligative anaerobes — i.e., they
require an anaerobic environment with a low redox
potential to grow and multiply and to actively produce
H2S. They are not killed by aerobic (oxygenated) environ-
SRB are deactivated, but ments, but they do become inactive. Partially oxidized
not killed, by oxygen in organic compounds, such as organic acids and alcohols,
are usually the carbon and energy sources for the het-
the water.
erotrophic SRB. They cannot use petroleum hydrocar-
bons directly. Some species of SRB can use hydrogen
directly as an energy source. These SRB still need a
carbon source for cell material to grow and multiply.
Their other nutritional requirements phosphorous,
nitrogen, iron, vitamins are usually low and readily
satisfied in most oilfield waters. There is concern that the
phosphorous and nitrogen requirements may be satisfied
by treatment chemicals, such as scale inhibitors and
oxygen scavengers, that are added to the produced fluids
and stimulate SRB activity.
SRB are active over a wide range of conditions:
• Temperature: 40°F to 180°F (4°C to 85°C).
• pH: 5 to 9.
• Pressure: to 14,500 psi.
• Salinity: zero to saturation.
Some SRB can survive even higher temperatures by
converting to a spore form.
SRB can also be classified into one of two groups, de-
Some SRB incompletely pending on their action upon the organic substrate used
as an energy/carbon source. Bacteria in the first group
oxidize a substrate only to
incompletely oxidize the substrate to acetate and no
acetate. Other (“acetate further. Higher-organic-acid anions are the food source
utilizers”) can oxidize a for these bacteria; acetate is the metabolic product. These
substrate completely to bacteria grow relatively rapidly. Under optimum condi-
tions, their doubling time is about 3 hours.
carbon dioxide and water.
The second group of SRB completely oxidize organic
substrates to CO2. Because these bacteria can use acetate
as a substrate, they are frequently called “acetate utiliz-
ers.” They grow much more slowly than the incomplete
oxidizers; their doubling times usually exceed 15 hours.
Frequently, the completely oxidizing SRB coexist with the

incomplete oxidizers. In this consortium arrangement,
they use the metabolically produced acetate of the incom-
plete oxidizers as an energy source for their metabolism.
Table 3 summarizes the SRB species that have been
characterized into the two groups. Data for Table 3 came Culture media must
from Cord-Ruwisch et al.,3 Postgate,4 and NACE TPC3.5
consider that some SRB
The table also indicates the optimum temperature for
growth (and culturing) and the compounds used by the are “acetate utilizers” and
SRB as an energy source. Many SRB that use acetate do cannot use lactate as a
not use lactate. Many of the standard culture media that carbon or energy source.
are published use lactate as the sole energy source; they
do not use acetate. These media cannot detect the com-
plete oxidizers that do not use lactate. Such media will
not indicate all the SRB present. Many species of SRB
found in oilfield waters have not been completely charac-
terized and do not appear in Table 3. This is true for
many SRB in North Sea oil fields.
Sulfate is the most common type of reducible sulfur used
in the biogenic production of H2S. Some bacterial strains Hydrogen sulfide can be
can use other oxidized sulfur compounds — e.g., sulfites produced by sulfate
( SO 2−
3 ). Bacteria that use other sulfur sources are some- reducing bacteria or by
times called sulfide-producing bacteria (SPB). Some sulfide producing
media for detecting SRB contain sulfite as a reducing
bacteria.
agent to establish the required redox potential. If SPB are
present in the sample, a false positive indication for SRB
will be produced. In the sampled system, the sulfite
levels may be so low that SPB are inactive. Therefore
sulfite-containing media will give a false indication of
SRB problems.
Representative equations for SRB using lactate, acetate,
or hydrogen as the substrate or reducing agent are shown
in Table 4. Lactate, although not usually present in
oilfield waters, is used as the organic carbon source in
many standard media formulations. It is representative
of higher-molecular-weight fatty acid substrates. The
majority of incompletely oxidizing SRB use lactate, so it
is a good choice when incomplete oxidizing SRB are
present. Acetate is frequently a metabolic product of
these bacteria. The large amount of energy produced per

Table 3 Characteristics of Representative SRB
Compounds Oxidized
Optimum Fatty
SRB Species Temp., °C Hydrogen Acetate Acids Lactate
Incomplete Oxidizers
Desulfovibrio
desulfuricans 30 + - - +
vulgaris 30 + - - +
gigas 30 + - - +
salesigens 30 + - - +
sapovorans 30 - - C4 – C6 +
thermophilus 70 + - - +
africanus 30 - +
baculatus 30 - +
Desulfotomaculum
orientis 30–35 + - - +
ruminis 37 + - - +
nigrificans 55 + - - +
antarticum 30 - +
Desulfobulbus
propionicus 30–38 + - C3 +
Complete Oxidizers
Desulfobacter 30 - + - (+)
postgatei
Desulfovibrio
baarsii 30–38 - (+) C3 – C18 -
Desulfotomaculum
acetoxidans 35 - + C4, C5 -
Desulfococucus
multivorans 35 - (+) C3 – C14 +
niacini 30 + (+) C3 – C14 -
Desulfosarcina
variabilis 30 + (+) C3 – C14 +
Desulfobacterium
phenolicium 30 - (+) C4 -
Desulfonema
limicola 30 + (+) C3 – C12 +
Symbols: + = utilized; (+) = slowly utilized; - = not utilized

Table 4 Reactions of Sulfate Reducers
Sulfate Reduction
Lactate Substrate
2CH 3 CHOHCOO − + SO 24 − + 2H + = 2CH 3 COO − + 2CO 2 + H 2 S + 2H 2 O
∆G° ′ = −39.9 kcal
Acetate Substrate
CH 3 COO − + SO 24 − + 3H + = 2CO 2 + H 2 S + 2H 2 O
∆G° ′ = −13.6 kcal
Hydrogen Substrate
4H 2 + SO 24 − + 2H + = H 2 S + 4H 2 O
∆G° ′ = −36.3 kcal
Respiration
Acetate Substrate
CH 3 COO − + 2O 2 + H + = 2CO 2 + 2H 2 O
∆G° ′ = −204. kcal
∆G°′ = ∆G° at pH = 7. Thermodynamic values from Reference 2.
mole of sulfate reduced and per mole of H2S produced

even without complete oxidation is the result of the large
energy content (heat of formation) of the lactate.
The reaction of acetate is representative of the completely
oxidizing SRB. Note that the acetate is completely oxi- Acetate may be a
dized to CO2. Acetate is found in many produced-water
samples and therefore is an important substrate for SRB metabolic product of
in oilfield operations. However, we cannot always deter- bacterial activity or it may
mine whether the acetate in the water was formed origi- be a substrate for
nally from the crude oil or resulted from bacterial activ- bacterial activity.
ity. The incomplete oxidizers and complete oxidizers are
frequently both present in the same system. The incom-
plete oxidizers use the higher-molecular-weight acids
and convert them to acetate. The complete oxidizers, in
turn, covert the acetate to CO2 and water. This is one
example of bacteria consortium acting together to derive
the most energy from the system.

The third substrate for sulfate reduction listed in Table 4
Hydrogen, a substrate for is hydrogen. The large amount of energy released in the
SRB, may be present in reaction indicates the strength of hydrogen as a reducing
agent. In oilfield fluids, hydrogen is usually present in
small amounts in
very low amounts, but it can be dynamically formed in
produced fluids or it may the corrosion of ferrous metals or the microbial fermenta-
be formed by corrosion tion of organic material.
reactions or Small amounts of energy are released in the anaerobic
microbiological oxidation of acetate with sulfate compared with the
fermentation. aerobic oxidation with oxygen. The reaction product of
the anaerobic oxidation, H2S, still contains a large amount
of energy that can be released in subsequent oxidation
(either chemically with oxygen or microbiologically with
sulfur-oxidizing bacteria).
Slime-Forming Bacteria
Slime-forming bacteria do not represent any single group
or genus of organisms. They represent a general group-
ing of aerobic or facultative (can grow without oxygen)
bacteria. These bacteria are characterized by the produc-
tion of slimy bacterial cells and extracellular polymeric
substance that lead to plugging and pitting corrosion
Slime-forming bacteria
problems. They enhance pitting corrosion by shielding
produce large amounts of portions of the surface, depleting oxygen, and forming
extracellular polymeric differential oxygen concentration cells.
substances that lead to In addition to their plugging and fouling capabilities,
plugging and pitting they stimulate the growth and activity of SRB (1) by
corrosion. providing protective biofilms, (2) by reducing oxygen
concentrations and providing anaerobic regions in the
biofilms, and (3) by providing usable carbon/energy
sources.
Specific bacterial types of slime formers are Pseudomonas,
Flavobacterium, Micrococcus, Aerobacter, Aspergillus, and
Nocardia. They are usually detected by culturing meth-
ods like total plate count, plate count, or total count
(discussed later). When detected by culturing methods,
they are identified as “general bacterial count” in
API RP 38.6

Acid Producing Bacteria — APB
Bacteria in this classification produce acids as part of
their metabolic products. Bacteria can produce many Acids are the metabolic
different types of acid — from H2S, carbonic acid, and product of acid producing
short-chained fatty acid to sulfuric acid. A large number
bacteria. These acids may
of bacterial species is involved. Bacteria that produce
H2S were discussed as SRB; those producing sulfuric acid be corrosive or provide a
will be discussed as sulfur-oxidizing bacteria. This sec- substrate for other
tion focuses on the bacteria that produce short-chained bacteria.
fatty acids (also called volatile fatty acids) such as formic,
acetic, propionic, butyric, etc. These APB are usually a
subclass of the slime-forming bacteria.
Until recently, the primary concern about APB was that
they can convert complex organic compounds into sim-
pler organic acid that would serve as the carbon and
energy sources for SRB. Now we recognize the biogenic
organic acids as corrosive agents. The APB produce low-
molecular-weight aliphatic acids from higher-molecular-
weight acids and other complex organic substrates. In
aerobic environments, acid production is an oxidation/
reduction reaction; in anaerobic environments, the reac-
tion is fermentative. Some autotrophic species can use
hydrogen and CO2 to produce acids.
Iron Bacteria
These heavy slime formers can oxidize soluble iron
[Fe(II)] to insoluble iron [Fe(III)] using dissolved oxygen Iron bacteria oxidize
as the oxidizing agent. The insoluble iron (1) contributes
soluble iron (II) to
to plugging and fouling; (2) provides anaerobic niches for
other bacteria, including SRB; and (3) enhances corrosion insoluble iron (III) and
from differential oxygen concentration cells. These produce large amounts of
bacteria are aerobic but can grow with <0.5 ppm oxygen. slime.
They are usually found in fresher waters and in open
systems. Types of iron bacteria commonly encountered
are Siderocapsa, Gallionella, Crenothrix, and Sphaerotilus
(also called filamentous bacteria). Iron bacteria are diffi-
cult to culture. Direct microscopic techniques are recom-
mended for detection.

Sulfur-Oxidizing Bacteria
Sulfur-oxidizing bacteria are either aerobic (colorless
Sulfur oxidizing bacteria sulfide oxidizers) or anaerobic (colored sulfide oxidizers).
The colorless Thiobacillus oxidize sulfide to sulfuric acid.
oxidize hydrogen sulfide
They are active over the pH range of 0 to 4; pH 2.5 is
either incompletely to optimum for growth. Sulfuric acid is very corrosive to
sulfur or completely to steel and concrete. Beggiatoa are aerobic bacteria that
sulfuric acid. oxidize H2S to sulfur. The anaerobic types, Chlorobium
(green) and Chromatium (purple) require sunlight to
function.
Sulfur-oxidizing bacteria are usually of little concern in
water injection systems. In open waste systems, they can
be troublesome because the sulfuric acid they produce is
very corrosive to concrete.
Planktonic vs. Sessile Bacteria

All the bacteria discussed so far may exist in a system as
free floating bacteria or as bacteria attached to surfaces
(see Table 5). Each location or position causes specific
problems in producing systems.
Table 5 Categories of Bacteria

By Location
Planktonic — floaters
Sessile — attached
By Habitat
Monocultures — single species
Consortia — mixed cultures
Planktonic Bacteria
Planktonic bacteria are the free floaters. They are found
Planktonic bacteria are in the bulk water stream. They move with the flowing
stream and frequently contaminate the downstream
free floating in the liquid
portion of treating and injection systems. These bacteria
phase. usually are introduced into the system through inad-
equately treated water input streams.

Sessile Bacteria
Sessile bacteria are attached to surfaces. They are respon-
sible for most problems encountered in oilfield opera- Sessile bacteria are
tions. These bacteria may attach to metallic surfaces attached to surfaces.
(piping, tanks, tubing, casing), nonmetallic surfaces
(plastic pipe), or minerals (filter media or formation
material).
Surface attachment is an ideal way for bacteria to obtain
the necessary nutrients for their activities. When bacteria
are attached to surfaces, the nutrients are brought to
them in the flowing stream. Nutrients tend to concen-
trate at surfaces where the sessile bacteria are attached.
Thus, attachment forms a concentrating mechanism for
bacteria, a phenomenon particularly important in most
water systems that are relatively low in nutrients. Sessile
bacteria have protective layers of EPS (biofilms) to pro-
tect them from harmful materials like biocides that might
be in the flow stream. In any given system, the number
of sessile bacteria per unit of surface area may be hun-
dreds or thousands times the number of planktonic
bacteria per unit volume.
The process of bacterial growth and biofilm formation in
water systems is dynamic. Planktonic bacteria are con-
stantly attaching to surfaces where they grow, multiply,
and produce EPS. The biofilm and incorporated bacteria
grow and thicken with time. Depending on water flow
velocities and shear stresses, portions of the biofilm may
detach from the surfaces and move downstream with the
flow to contaminate the system further. Introducing
biocides frequently intensifies this sloughing and detach-
ment process.
Bacteria Classified According to Habitat

In producing operations, bacteria are rarely present as a
pure monoculture (single bacterial species). Invariably, Bacteria may exist as a
they exist as mixed cultures or consortia of several types
single species (pure
of bacteria, all contributing to the well-being of the con-
sortia. A classic example of such a consortia is facultative monoculture) or multiple
aerobes working with SRB. The aerobes use traces of species in a cooperative
oxygen to oxidize petroleum hydrocarbons or complex consortium.
oxygenated organics to simpler, lower-molecular-weight

acids and alcohols. In their metabolism, they create the
anaerobic environment and usable carbon sources re-
quired by SRB, along with large amounts of biomass to
Many biocide tests are protect the consortia from harmful components in the
liquid stream.
invalid because they have
been performed with Many early attempts to specify biocides for oilfield op-
erations were performed in the laboratory with pure
pure cultures of
cultures of well-nourished planktonic bacteria. It is not
planktonic bacteria. Such surprising that field results did not agree with laboratory
bacteria are particularly studies. This practice led to specification of special bio-
susceptible to biocides. cides at low concentrations that were effective with pure
cultures of planktonic bacteria in a laboratory environ-
ment but had no effect on the sessile, biofilm-protected
bacterial consortia encountered in the field.
DETECTION OF BACTERIA
The objective of this part of water quality monitoring is
to determine the following:
1. Are bacteria present?
2. What types of bacteria are present?
3. How many bacteria of each type are present?
4. Are the bacteria present as planktonic (floating)
bacteria or as sessile (attached) bacteria?
This type of monitoring is first used to determine
whether bacteria are present and could be contributing to
production problems. If they are present, monitoring
should help determine whether the control methods
being used effectively eliminate or reduce the bacteria.
The techniques for sampling and analyzing bacteria
Microbiological sampling differ considerably from those used for chemical analysis
(Table 6). Assistance from someone trained or experi-
and analysis require enced in microbiological procedures may be necessary to
technique, equipment, obtain reliable data. Frequently, the chemical service
and experience that is companies are better qualified and have the necessary
uniquely different from equipment to determine whether bacterial problems are
present, to prescribe treatment and control procedures,
chemical sampling and and to train operating personnel in further bacterial
analysis. monitoring. The ideal situation is to have trained and
experienced operators working with the chemical suppli-
ers.

Table 6 Microbiological Analysis
Sampling Methods Determine
Planktonic Bacteria — Liquid Samples
Sessile Bacteria — Solid Surfaces
Analytical Procedures Determine

Type of Bacteria
In general, the sampling method determines whether

planktonic or sessile bacteria are counted. The analytical
or culturing procedure determines the type of bacteria
enumerated or determined. In some cases, the analytical
procedure only indicates that bacteria are present; in
other cases, the procedure estimates the number of bacte-
ria detected. Because most procedures have low recover-
ies, the number of bacteria detected is usually less than
the number present.
Sampling Methods for Bacteria

For microbiological samples, all the precautions for
chemical sampling listed in Chapter 2 must be followed.
In addition, special precautions must be taken to avoid
contaminating the sample with extraneous bacteria and
other microorganisms. Therefore, sterile sample contain-
ers and sampling tools are required. Also, we must
ensure that an environment suitable to the bacteria to be
determined is maintained. For most oilfield samples, this
means maintaining an anaerobic environment while
maintaining the temperature at or below the system
temperature at the point of sampling.
Sampling of high-
The sampling of high-temperature or high-pressure
systems requires special precautions that are beyond the temperature or high-
scope of this chapter. In such a situation, it is best to rely pressure systems can be
on a reputable chemical supplier or service company dangerous and requires
with relevant experience in sampling and analysis of
special equipment and
high-pressure, high-temperature systems for microbio-
logical activity. techniques.

The following instructions are only a guideline. They
will probably have to be modified for a particular situa-
tion.
Planktonic Bacteria
1. Withdraw a liquid sample from the flow stream with
a sterile syringe and place it in a sterile container.
2. Culture or examine this sample at the time of sam-
pling or as soon as possible afterward by techniques
described in following sections. Maintain anaerobic
conditions when sampling for SRB.
Sessile Bacteria and Biofilms

1. Allow bacteria and biofilms to grow on a surface
sampling device, such as Robbins Device, Petrolite
Sample Probe, Caproco Biofilm Probe, or corrosion
coupon.
2. Attach sterile coupons or biostuds of known area to
the sampling device and place the sampling device in
a flowing stream.
3. After exposure for 2 to 6 weeks (or for as long as it
Since this chapter was takes to develop a representative biofilm), remove the
first written, NACE has biofilm and bacteria from the surface or stud and
disperse in sterile sampling solution. Remove the
published a standard test deposit by scraping it off with a sterile scalpel and
method for sampling sonicating it with sterile sample water. Or sonicate
bacteria. NACE Standard the stud and some glass beads along with a known
TM 0194-94 “Field volume of sterile sample water in a plastic test tube or
container.
Monitoring of Bacterial
4. Treat or analyze a portion of the solids suspended in
Growth in Oilfield
liquid with the same techniques used for the liquid
Systems.”16 sample of planktonic bacteria.
Sampling devices and procedures for sessile bacteria are
discussed in detail in a NACE publication.7

Test Procedures for Bacterial Types
The culturing protocol or the analytical procedures used
will determine the type or species of bacteria identified
and/or enumerated. Tests are usually run for the follow-
ing types of bacteria: aerobes (general aerobic bacteria),
anaerobes, SRB, APB, and iron bacteria (Table 7).
Table 7 Test Procedures for Bacteria

Types of Bacteria Identified
General Aerobic Bacteria
Anaerobes
Sulfate Reducing Bacteria
Acid Producing Bacteria
Iron Bacteria
Test Methods
Culturing Procedures
Direct Methods
Test methods can be classified as culturing or direct

methods. In culturing methods, bacteria from the sample Culturing methods —
are grown in a specific nutrient broth (culture medium) bacteria are grown in a
and identified and counted by changes occurring in the
specific nutrient broth.
broth following a specified culturing protocol. These
changes include darkening, visible colony formation, Direct methods — count
turbidity, and color change. bacteria directly or
In direct methods, the presence of bacterial cells, essential detect the presence or
chemical cell components, or metabolic chemical reac- the consumption of
tants or products are observed directly. some chemical
Culturing Methods compound that is
uniquely associated
A special preparation of carbon and energy sources,
nutrients, and salts in sterile water is inoculated with the with the bacteria or
sample. Active bacteria or bacterial colonies, if present, their metabolism.
cause some measurable change (e.g., cloudiness, turbid-
ity, or color change) in the culture medium as the bacteria
grow and multiply under proscribed environmental
conditions. By varying the type of media and protocol,

we can identify and enumerate many types of bacteria.
SRB have received the most attention. Many of the
published studies and procedures are directed toward
their detection and enumeration. The probable role of
APB in corrosion reactions and in the production of a
carbon source for SRB is now being recognized, and more
attention is being directed toward identifying APB.
Most culturing methods (Table 8) give relative numbers
Culturing methods do not of bacteria present rather than absolute numbers; i.e.,
detect all of the bacteria recoveries of bacteria are less than 100%. Therefore,
consistency and reproducibility in procedures, reagents,
present, i.e., recoveries are
and personnel are essential to obtaining reliable results.
less than 100%. Equally important is maintaining sterile conditions
during sampling and culturing to avoid accidental con-
tamination of the sample. To obtain reliable results, the
culturing media and conditions must match system
conditions in terms of carbon and energy sources, salin-
ity, and temperatures. This can be particularly important
for SRB. Many original media formulations used lactate
as the carbon and energy source.
Table 8 Culturing Methods

Broth Bottles
Solid Culture Media
Pour Plate
Spread Plate
Agar Deep
Melt Agar Tube
Many SRB in oil fields are “acetate utilizers” and grow

Many SRB encountered poorly, if at all, on a lactate medium. We should always
use separate media containing lactate, acetate, and mix-
in oil fields are “acetate
tures of the two until we determine the carbon source
utilizers.” Culture media used by the bacteria in the sampled system. Negative
must be adjusted results are often obtained, especially in new circum-
accordingly by stances, because improper culturing procedures were
used and the bacteria in the sample could not grow and
incorporating some
multiply in the culture media. Assuming sterile condi-
acetate. tions in sampling and culturing, positive results indicate
only that bacteria present in the sample could grow in the
media. They do not necessary indicate that the sampled

bacteria were active in the sampled system. Culturing
methods can detect the presence of live, viable bacteria
only.
Broth Bottles
Culturing with broth bottles (bug bottles) is probably the
most common method in oilfield situations. The cultur- Broth bottles are the most
ing medium is made up and enclosed in a small bottle
common culturing
sealed with a rubber septum. A sterile, disposable sy-
ringe is used to introduce the sample into the sealed method used in oilfields.
bottles. By using different broths, we can observe the
different types of bacteria.
For oilfield use, API RP 386 has been the standard for
media for SRB and general bacteria counts. This stan-
dard is now considered outdated and greatly deficient in
formulations and practices. RP 38 does not consider
sessile bacteria and uses a lactate-based medium for SRB
detection and enumeration. As discussed earlier, some
SRB that are complete oxidizers can utilize acetate but
not lactate. These SRB would not be detected by the
media specified in RP 38. Also, these media can give a
false positive reaction for SRB if Clostridia are present.
Clostridia can produce H2S from the yeast extract in the
media.
Many advances in media have been made since RP 38 API has a revised version
was published. RP 38 is currently being revised; reissue of RP 38 that has not been
is on hold, pending possible publication of a NACE released as of June 1994.
standard or test method.
Broth bottles can be made up and prepared by the user or
are available from a number of suppliers. In either case,
experience has shown that using a sterilized portion of
the test water as the background solution and augment- The new NACE Test
ing this with additional nutrients and chemicals specific Method TM 0194-9416 also
to the bacteria being studied provide the most suitable contains compositions for
media. Postgate’s4 monograph is the standard for tech- standard media for SRB,
niques and media for SRB. Another useful reference is
Mittleman and Geesey’s8 book. It contains a number of APB, and GAB.
media for bacteria of interest, as well as sampling and
culturing techniques for planktonic and sessile bacteria.
Some suppliers can provide assembled kits with various

media for a variety of bacteria. The suitability of these
preparations for bacteria other than SRB is still under
investigation.
The extinction dilution (or serial dilution) method in
RP 38 is frequently used to detect and enumerate bacte-
ria. This dilution and reporting procedure (Table 9) is
summarized below.
Table 9 Extinction Dilution Method

Bacteria/mL
in Original Sample
Bottle Number Dilution Factor Number Log Number
1 1/10 1–10 1
2 1/100 10–100 2
3 1/1000 100–1000 3
4 1/104 1000–10,000 4
5 1/105 10,000–100,000 5
6 1/106 100,000–1,000,000 6
1. Mix 1 mL of sample with 9 mL of sterile culturing

solution.
2. Dilute 1 mL of this mixture again with another 9-mL
portion of sterile culturing solution.
3. Continue these 1:10 dilutions a total of 5 or 6 times.
4. Incubate each dilution at the recommended tempera-
ture and time and look for positive results. The dilu-
tion (bottle number) at which no visible activity
occurs gives an estimate of the number of bacteria (in
powers of ten) in the original water samples. Fre-
quently, the results are reported in terms of powers of
10 for the number of bacteria found.
Solid Culture Media

In this procedure, the nutrient is incorporated in solidi-
fied agar to hold it in a solid or semisolid condition. The
liquefying point of the agar is low, so the procedure is not
suitable for culturing thermophilic bacteria. This method
is not as widely used or as readily available as broth
bottles for oilfield situations; it may present difficulties

for field sampling. In any case, all the concerns about
media nutrient composition and salinity discussed previ-
ously apply to solid media.
Pour-Plate Method
The sample, or dilutions thereof, is mixed with molten
agar containing the desired media. The temperature of
the molten agar (45°C) may inactivate some mesophilic
bacteria.
Spread-Plate Method
The sample is inoculated onto the surface of a solidified
media containing agar. Microbiologists use this method
in laboratories. It requires an anaerobic tent and an
incubator for SRB and other anaerobic bacteria. Because
of the low melting temperature of agar, the method is not
suitable for thermophilic bacteria. It also is usually not
suitable for field culturing.
A variation of the spread-plate method is the agar deep
method furnished by Bioscan Laboratories. This method
uses an RP 38-type agar media inoculated with a pipe
cleaner wetted with the sample. The sample may be
diluted before it is incorporated into the agar to simulate
the serial dilution method with broth bottles. The
Bioscan broth contains sulfite as a reducing agent (to give
a media with a low pH for anaerobic bacteria). There-
fore, it may give false positive tests for SRB from sulfite-
reducing bacteria that would not be active in a sample
that does not contain sulfite.
Melt Agar Tube Method

This method, used by Nalco Chemical, is similar to the
pour-plate method except that the inoculated media are
kept in capped test tubes. Tryptone is used as the sole
nutrient, and sodium sulfite is used as an oxygen scaven-
ger and reducing agent. See the comments on the agar
deep method for the effect of sulfite on test results.

Direct Methods
Direct methods count bacteria directly or detect the
presence or consumption of some chemical compound
that is uniquely associated with the bacteria or is in-
volved in the microbiological metabolism.
Table 10 lists the methods discussed in this section.
Table 10 Direct Methods

ATP Assay
Epifluorescence/Cell Surface Antibody
APS Reductase Antibody
Phospholipid Signature
Radio-Respirometry
Chemical Analysis
ATP Assay
This method measures the amount of adenosine-5'-
triphosphate (ATP) obtained from bacterial cells. ATP, a
carrier of chemical energy in metabolism, is a component
ATP Assay uses the firefly
of all living bacteria. Therefore, ATP assay does not
luciferose enzyme to specify the type of bacteria present. ATP is extracted
detect all living bacteria. from the bacterial cells and detected by reacting with an
It cannot differentiate enzyme (firefly luciferase) in the presence of oxygen and
measuring the amount of emitted light with a special
between types of bacteria
photometer. ATP is quickly lost from bacterial cells when
or detect dead bacteria bacteria die, so the method detects only live bacteria.
that have lost ATP. Samples for analysis must be processed and preserved at
the sampling point to retain ATP. The method is rela-
tively insensitive; i.e., ATP from a large number of cells
must be present to be detected. Samples with high solids
content or high levels of sulfides or biocides require
pretreatment to reduce interferences. The method also
requires specialized reagent, equipment, and standard-
ization procedures performed by experienced personnel.

Epifluorescence/Cell Surface Antibody
Methods
These methods cover several specific microscopic tech-
niques. In the epifluorescence method for total cell
counts, a fluorescent dye such as acridine orange (AO) or
4,6-diamino-2-phenylindole (DAPI) combines with the
nucleic acid in bacteria cells. For viable counts, fluores-
cein diacetate (FDA) reacts with the esterase enzyme in
living cells producing fluorescein. In the cell surface
antibody methods, fluorescent-tagged antibodies are
attached to specific sites on the target bacteria.
Bacteria are counted microscopically by exciting the
fluorescent chemical with light of a suitable wave length.
Total numbers of bacteria can be obtained within 2 to 3
hours of sampling. The method requires expensive
equipment (epifluorescent microscope) and staining or
attachment procedures performed in a clean laboratory.
Also, counting bacteria by microscopic techniques can be
tedious. The AO and DAPI procedures do not distin-
guish between live and dead bacteria; therefore, they
cannot be used to measure effectiveness or time-kill
relationships of biocides. Tagged antibody procedures
are not very sensitive (minimum 103 to 104 cells) and
require extensive development effort for antibody identi-
fication and preparation. Large amounts of suspended
solids in the sample cause interferences by partial absorp- The RapidChek test kit is
tion of the fluorescent chemical. a rapid, field-oriented kit
that is specific for SRB.
APS Reductase Antibodies Method
This method is commercially available as the Conoco
RapidChek kit. The method detects the adenosine-5'-
phosphosulfate (APS) reductase enzyme found in all
SRB. The intensity of color developed in tagged antibod-
ies that attach to the APS enzymes is used to determine
the number of SRB present. This method is rapid (results
within 15 to 20 minutes of sampling) and specific for all
SRB. The method has been adapted for field sampling of
liquids, sludges, or biofilms and other surface samples.
The method does not depend on culturing or growth of
bacteria, so it can detect “difficult to culture” strains of
SRB. The sensitivity of the RapidChek method is nomi-

nally 103 bacteria/mL, but this can be increased to 10 to
As of December 1993, the 100/mL by modifying sample size and color develop-
RapidChek SRB test kit is ment procedures.
available from Strategic The method does not differentiate between live and dead
Diagnostics, Inc. of bacteria as long as the APS is retained within the bacterial
cells. Small kits are available that have a 6-month shelf
Newark, Delaware rather
life if refrigerated. Performance is degraded by tempera-
than Conoco Specialty ture extremes (<32°F or >90°F).
Products, Inc. Horacek9 compared the RapidChek kits with several
standard SRB growth media under field situations. He
found that the method detected common SRB strains that
culturing media methods did not detect. At a sensitivity
of 1,000 actual SRB counted/mL, the reductase enzyme
method was comparable to media methods detecting 10
to 100 times fewer SRB because the latter “media meth-
ods routinely underestimate SRB populations.”6 Because
the APS reductase enzyme is unique to SRB, the kits
could distinguish sulfate reducers from sulfide produc-
ers.
Phospholipid Signature
This procedure identifies the distinct signature of phos-
pholipids unique to each strain of bacteria. It uses diffi-
cult procedures and expensive equipment in a controlled
laboratory environment. The method is good for qualita-
tively identifying bacterial types and strains but is not
calibrated for quantitatively measuring numbers of
bacteria. Its use is confined to research studies for identi-
fying bacteria.
Radio-Respirometry
This method measures the rate of biogenic production of
Radio-respirometry CO2 from a radioactive carbon source or H2S from a
measures bacterial radioactive sulfate source in the culture media. It is an
extremely sensitive way to detect and measure bacterial
activity rather than activity. Unlike most other methods of bacterial detec-
bacterial numbers. tion, the radio-respirometric method measures bacterial
activity (i.e., the rate at which CO2 or H2S is produced)
rather than the number of bacteria present. Bacterial
activity in the culture media may or may not match
activity in natural surroundings, especially if carbon and
energy sources and concentrations are different. The

method uses radioactive materials and specialized equip-
ment (scintillation counter). It also requires specialized
procedures to obtain reproducible results.
Chemical Analysis
The presence and activity of bacteria can sometimes be
inferred by changes in water chemistry, i.e., the appear-
ance of products of bacterial metabolism or the disap-
pearance of compounds used by bacteria. Thus, the
presence and activity of SRB can be inferred by a de-
crease in sulfate levels, an increase in sulfide levels, and a
decrease in low-molecular-weight fatty acids, such as
acetate, propionate, or butyrate across the system.
Table 11 gives an example of this method from the Minas
field in Indonesia. The characteristics of the produced
water at the Central Gathering Stations where oil and
water are separated are compared with those at selected
injection wells remote from the stations. Although it is
impossible to assign the water from any one station to a
particular injection well, trends in chemical levels are
apparent. H2S levels are generally low at the stations but
increase as the water flows to the injection wells and
becomes cooler. The exception is Well 2D24, where the
water temperature remains high (82°C). Sulfate levels
follow an inverse relationship, decreasing from stations
to wells.
Table 11 Chemical Analyses for Minas Produced Water

Central Gathering
Station GS-I GS-II GS-III GS-IV GS-V GS-VI
H2S, mg/L Trace 0.3 0.1 <0.1 0.15 0.4
SO2−
4 , mg/L
27.8 26.4 17. 35. 55. 26.
pH 7.5 7.6 7.5 7.2 7.3 7.3
Temperature, ºC 81 85 82.5 79 81 78
Water Injection
Well 6F52 3E86 2D24 10D15 6A59 7B89
H2S, mg/L 2. 3. nil 5. 3.4 7.7
SO2−
4 , mg/L
14. 19.8 23. 13. 24.4 16.4
pH 7.3 7.4 7.4 7.3 7.6 7.6
Temperature, ºC 77 78 82 78 72 78

One possible conclusion is that SRB, though present, are
relatively inactive (produce little H2S because of the high
temperatures) at the stations. As the water flows to the
remote injection wells, cooling occurs, SRB activity in-
creases, sulfate is reduced, and H2S is produced. The
critical temperature for SRB activity in this case seems to
be about 77 or 78°C. Of course, these conclusions should
be supported by microbiological analyses to determine
the number and activity of SRB under field conditions.
Hydrogenase Enzyme Detection

This test method, developed and produced by Caproco
The hydrogenase enzyme Ltd., detects the presence of the hydrogenase enzyme
detection method detects required by bacteria that utilize and oxidize hydrogen as
an energy sources. The method was developed specifi-
an enzyme involved in cally to detect bacteria involved in MIC through the
some MIC reactions. It is cathodic depolarization mechanism. Bacteria detected
not specific to all SRB. include some SRB, some SPB, and some methanogens.
In this method, the sample containing suspected hydro-
genase-containing bacteria is treated with a special solu-
tion to extract the enzyme, protect it from oxygen, and
increase its reactivity. The extract is then placed in an
anaerobic chamber, oxygen is removed, and hydrogen is
added. The electrons released in the hydrogenase-cata-
lyzed hydrogen oxidation are transferred to a redox
indicator. A color change in the redox indicator shows
the presence of hydrogenase. Currently, the method only
indicates the presence or absence of bacteria containing
extractable hydrogenase. It does not give a numerical
value for the number of such bacteria present or the
amount of hydrogenase extracted. The method is rela-
tively fast (test results obtained in <4 hours) but is diffi-
cult to use in field situations without laboratory facilities.
Sulfur Isotope Differentiation Method

Measurement of the
This method can indicate whether the H2S in the system
sulfur isotope ratio can was formed by a microbiological reaction or by a chemi-
determine if hydrogen cal reaction. As such, it indirectly indicates past or
sulfide was produced by a present bacterial activity. The sulfur in naturally occur-
microbiological or a ring compounds is a mixture of isotopes (atoms of the
same chemical element with different atomic masses).
chemical reaction. The major components are S32 (sulfur with an atomic

weight of 32) 95% and S34 4.2%. The lighter isotope, S 32,
is more reactive in microbiological reactions. Thus, in the
biogenic production of H2S by SRB, the H2S product is
enriched in S32 and the remaining unreacted sulfate is
enriched in S34. In practice, to increase precision, the
amount of each isotope is determined by a mass spec-
trometer and the results are presented as a δ S34 ratio, in
parts per thousand, ‰, defined as
δS =  34 32
34 ( )
 S 34 S 32 sample 
− 1 × 1000
( )
 S S standard 
(1)
where the standard is troilite (FeS) from the Canon

Diablo meteorite. H2S produced by bacteria will be lower
in S34 than the remaining unreacted sulfate, or the δ S34 for
the biogenic H2S will be lower than that for the residual
sulfate. Orr10 reported that biogenic H2S in produced gas
has δ S34 values 15 ± 5 ‰ lower than the associated
sulfates.
Comparison of Field Kits for SRB

The NACE Unit Committee T3-J on Biological Corrosion
conducted a test program that compared the results of six
commercially available methods for enumerating SRB
activity in real field situations.11 Methods included kits
for culturing and kits for detecting enzymes (hydroge-
nase and APS reductase). The results of this survey on
different types of samples in a number of field situations
can be summarized as follows.
1. Among the six methods tested, there was no “best”
method.
2. Since there was no independent estimate or determi-
nation of the number of SRB actually present in any of
the samples, no estimate of the “accuracy” of the
individual test kits was possible.
3. The number of bacteria found in the samples varied
widely and randomly from one kit to another.
4. The recommended process for field use was to deter-
mine which kit gave the best results in a specific
application and then “stick with it.”

5. The value of microbiological testing lies in detecting
trends in the number of bacteria found with time or
location within the system rather than with the abso-
lute number of bacteria found in any one sample.
CONTROL OF BACTERIAL ACTIVITY

The ideal for a water treating and handling system is for
that system to be designed, constructed, and operated to
prevent bacterial contamination. In field operations,
however, this ideal is impractical and economically
impossible. In new facilities, bacterial contamination can
be minimized or controlled; it cannot be eliminated
completely. In existing facilities, the system may already
be contaminated and experiencing bacteria-related prob-
lems. In these cases, the practical approach is to mini-
mize additional bacterial contamination from outside and
to mitigate established microbiological growth inside.
These two objectives can be achieved through combina-
tions of mechanical design, physical cleaning, and chemi-
cal treatment. Mechanical design usually focuses on
minimizing outside contamination and establishing
conditions to minimize bacterial growth within. Physical
cleaning and chemical treatment focus on removing and
controlling established microbiological systems.
For existing facilities that are already contaminated and
Steps in controlling experiencing problems, the first step is to culture to deter-
mine:
bacteria in a contaminated
system: 1. Are bacteria present that could be causing the prob-
lems?
• culture
• clean 2. What type(s) of bacteria are present?
• kill 3. How many bacteria are present?
4. Where are they located?
The next step is to clean. Bacteria are usually protected
by biofilms and other deposits. For a control procedure
to be effective, as much of these protective layers as
possible must be removed before a biocide or other
treatment chemical is applied.
Chemical treatments (acids, oxidants, solvents) and
mechanical processes (brushing, scrapping, pigging,
thermal shocks) can be used for cleaning. Combined

chemical/mechanical treatments are frequently more
effective than one treatment alone.
The third step is to kill the residual bacteria. Biocides are
commonly used for this step. Ultraviolet radiation and
heat sterilization have also been used. For the latter two
techniques to be effective, they must be applied directly
to the residual bacteria.
Bacterial Control by Mechanical Design

A good mechanical design includes features to reduce the
number of bacteria entering the system and to minimize Good mechanical design
or reduce the conditions favoring bacterial growth. is essential to minimize
Suitable practices include: and control bacterial
1. Maintaining inert gas blankets on tanks and vessels to contamination upon start-
minimize bacterial contamination and entrance of up and in operation.
oxygen that promotes the growth of aerobic, slime-
forming bacteria.
2. Using biocide-treated fluids to hydrotest new or
rebuilt equipment.
3. Eliminating fluid dead zones and areas of low flow
that favor bacterial growth.
4. Using smooth surfaces and reducing crevices at joints,
seams, and gaskets to minimize attachment points for
bacteria.
5. Filling vessels and pipes with sterile (biocide-treated)
water when they are shut in for extended periods.
6. Providing pigging and cleaning capabilities on pipe-
lines and vessels.
Making all these changes in a particular system may not
be possible. In all cases, a balance should be sought
between the capital costs of incorporating these design
practices and the operating costs of cleaning, and per-
haps replacing, a bacteria-contaminated system.
Physical and chemical
Bacterial Control by Physical Cleaning cleaning of all surfaces is
Before performing any chemical treatment operation, a prerequisite for all
remove as much of the solid and semisolid contaminants
chemical treating
and sludges in the system as possible. This is necessary
for biocide treatments and all other chemical treatment operations.

operations (e.g., scale and corrosion inhibition) affected
by surfaces that may absorb or adsorb the treating
chemical.
Pigging and scraping are frequently used to clean
flowlines and pipelines mechanically and to remove
debris. These processes require the design and construc-
tion of appropriate facilities for inserting, transporting,
and retrieving the pig or scraper and for collecting and
disposing of the removed debris.
High-flow-rate flushing, with or without surfactants, can
be used on suitably designed pipelines. Backflowing
injection wells, particularly when combined with chemi-
cals like oxidizers and/or inhibited acids, can very effec-
tively remove contaminants and restore well injectivity
and profile. Process equipment containing materials
with large surface areas, such as media filters and ion
exchange resins, frequently acts as bioreactors. They
provide regions for bacterial growth that can detach and
contaminate the downstream system. Frequent
backwashing — with and without surfactants, oxidizers,
or biocides — at rates high enough to remove bacteria,
suspended solids, and biofilms but low enough to mini-
mize media washout can be very effective.
As mentioned, mechanical cleaning is frequently com-
bined with such chemicals as surfactants, oxidizers, and
biocides to improve the cleaning operations. In all cases,
provisions must be made for removing the debris from
the cleaned system. Injection wells are very expensive
trash collectors.
Bacterial Control by Chemical Cleaning

Biocides are, by far, the most extensively used chemical
for bacteria control. The next section covers biocide
selection and application. This section focuses on using
chemicals to affect or augment surface cleaning and
removal of biofilms and other deposits. These films
reduce the efficiency and increase the cost of chemical
treatment through chemical reactions and/or physical
shielding. Removing these films is essential to a practi-
cal, cost-effective bacteria control program.

Oxidizers (e.g., chlorine, hypochlorite, chlorine dioxide,
hydrogen peroxide, and ozone) readily attack and de-
compose much organic material, including bacteria and
biofilms. In addition, the oxidizers are biocides. Oxidiz-
ers, used either alone or before other chemical treat-
ments, break down protective films and help establish
contact between the treating chemicals and the bacteria.
However, the oxidizers readily and nonselectively react
with a large number of reducing agents that may be
present in oilfield waters. Typical reducers include
dissolved sulfide, soluble iron, iron sulfide, and oxygen
scavengers. The oxidant demand of the water must be
satisfied before the oxidant can attack organic films and
biomass.
Oxidants, by their very nature, are corrosive to steel. For
example, to maintain corrosion control in mild steel Oxidizers are very
systems, free chlorine residuals should be kept below 0.5 effective biocides but
to 1.0 ppm. Many oxidants (including dissolved oxygen)
react with sulfides to form an intermediate sulfur com- they can cause increased
pound that is more corrosive than oxygen or sulfide corrosion.
alone. Some processes for generating chlorine dioxide
use excess amounts of HCl. The acid/chlorine dioxide
combination is very corrosive to steel. Hydrogen perox-
ide can decompose liberating molecular oxygen. Besides
being corrosive, the liberated oxygen can form explosive
mixtures with hydrocarbon vapors. Ozone is very reac-
tive and has a short life. Therefore, it is not effective for
treating problem areas that are remote from the genera-
tion and injection point.
Inhibited acids are frequently used in combination or
alternating with oxidants to dissolve and remove iron-
containing corrosion products and inorganic scale depos- Properly designed biocide
its, such as calcium carbonate. Since acids are usually
treatment can increase oil
less expensive than oxidizers, this can be a cost-effective
way to reduce the oxidant demand and the amount of production.
oxidizer needed. Clementz et al.12 discussed how injec-
tion wells were treated alternately with bleach (hypochlo-
rite) and HCl to stimulate injection wells, improve injec-
tion profiles, and increase oil production.
Films and deposits frequently contain hydrocarbon
materials, like crude oil components, that are inert to the
oxidants and minimize or restrict contact with the treat-

ing chemicals. Washing with appropriate hydrocarbon
solvents can remove the oily material and permit oxidant
or acid attack of the remaining film.
Bacterial Control by Ultraviolet Radiation

Ultraviolet (UV) radiation is nonselective and kills bacte-
Ultraviolet radiation is rial cells by preventing cell division. The UV light must
touch the bacteria to kill them; it does not impart
effective only at the point
bacteriocidal properties to the irradiated water. The
of application. It does not effectiveness, or percent kill, depends on the exposure
impart any residual time and the intensity of the UV light that the bacteria
biocidal properties to the see. In high-flow-rate systems, then, high-intensity UV
light is needed.
water.
Anything that prevents exposure of bacteria to the UV
light or decreases the intensity of the light decreases
treatment effectiveness. This includes suspended solids,
dispersed oil, soluble materials that absorb the UV radia-
tion, biofilms, and opaque films on the UV lamp sources.
UV radiation is particularly suitable for treating plank-
tonic bacteria in clean water at the point of irradiation. It
has no residual effect and is not effective for bacteria
downstream of the source. UV radiation is readily ab-
sorbed by biofilms and thus is not effective for sessile
bacteria.
Bacterial Control by Biocides

The most common way to control bacterial activity and
The most common way to bacteria-related problems in water treating facilities is to
use biocides to kill bacteria or biostatic chemicals to
control bacteria is to use
control bacterial growth. Biocides and biostatic com-
biocides to kill bacteria pounds are usually applied with or after chemical and
and biostatic chemicals to physical cleaning of the facilities. This section discusses
control bacterial growth. the types of chemicals used as biocides or biostats and
the procedures for selecting and applying effective bio-
cides.
Types of Biocides
A variety of organic and inorganic chemicals and chemi-
cal combinations have been used or proposed as biocides.
Table 12 lists some classes of chemicals and the specific
chemicals that used as biocides. The most widely used
are the oxidizing biocides typified by chlorine, hypochlo-

rite, chlorine dioxide, ozone, and hydrogen peroxide.
Chlorine (or hypochlorite, the chemical compound actu-
ally present in aqueous solutions) is the most widely
used biocide. Gaseous chlorine can be added directly to
the water, where it reacts to form hypochlorous and
hydrochloric acids according to the equation:
Cl 2 + H 2 O → HOCl + HCl (2)
Table 12 Types of Biocides

Oxidizing
Chlorine, hypochlorite, chlorine dioxide, bromine,
hydrogen peroxide, ozone
Inorganic
Copper, mercury, silver, and arsenic compounds,
chromates
Aldehydes
Formaldehyde, glutaraldehyde, acrolein
Organics
Amines, chlorinated phenols, quarternary
ammonium compounds, carbamates, guanides,
isothiazolins, phosphonium salts
Hypochlorite as either sodium or calcium hypochlorite

can also be added directly. To avoid the hazards of han-
dling gaseous chlorine or large amounts of oxidizing
hypochlorites, we frequently generate chlorine at the At pH above 7.5, most of
point of application by electrolysis of water containing
the chlorine is present as
high concentrations of chloride ions. Hypochlorous acid
(HOCl) is actually the active biocide component. At the hypochlorite ion, a
pH above 7.5, most of the acid ionizes to the hypochlorite less effective biocide.
ion (OCl-), which is not as effective a biocide as the
unionized acid. Hypobromite (OBr-) is more effective
than hypochlorite at high pH. Hypobromite can be
generated in situ by the action of chlorine or hypochlorite
on soluble bromide ions if present in the water. General
properties of the other oxidizing biocides were discussed
earlier.

Oxidizing biocides are nonselective; they attack all types of
Oxidizing biocides are bacteria and are usually effective at low (ppm) concentra-
effective at low tion levels. Their oxidizing power means that they are
effective in penetrating and breaking up biofilms and
concentrations and will
thereby reaching the bacteria to be treated. In addition to
attack and penetrate their biocidal action, their oxidizing power is useful for
biofilms. cleaning the system. By the same token, they are con-
sumed by oxidizable material in the system, including
sulfides. Many water systems use chemical oxygen
scavengers (sulfite) to remove residual oxygen and re-
duce corrosion. Oxygen scavengers will also consume
the oxidizing biocides. If there is residual scavenger in
the system, there will be little or no biocide residual. For
any system, the oxidant demand, whether it is provided
by oxidizable material like sulfides or reducing agents
like oxygen scavengers, must generally be satisfied
before there is sufficient biocide residual to be effective.
Oxidizing biocides, by their very nature, are corrosive, so
excessive concentrations must be avoided.
The inorganic biocides include chemicals containing toxic,
heavy metals (copper, mercury, silver, lead, arsenic, and
chromates). They are no longer used to any great extent
because of severe environmental consequences.
One type of organic biocides are aldehydes. Aldehydes
commonly used as biocides are formaldehyde, acrolein,
and glutaraldehyde. Formaldehyde is losing favor be-
cause of its carcinogenic properties. Acrolein (or
propenal), an unsaturated aldehyde, is a very effective
biocide, chemical cleaner, and H 2S scavenger. Because of
its reactivity (it can detonate in the presence of oxidizers),
it is difficult to administer. Glutaraldehyde is probably
the second most widely used biocide after chlorine in
oilfield situations. It works by crosslinking amino
groups of protein present in all bacterial cells. Glutaral-
dehyde is nonspecific and is effective for many bacterial
types. Bacteria have many different types of proteins
with differing functions that are affected by glutaralde-
hyde.
Because of this massive attack on its cell structure, bacte-
ria find it very difficult to build up a resistance or toler-
ance to glutaraldehyde. It is also said to possess biofilm-
penetrating properties. It usually must be used in high

concentration (hundreds of ppm) to be effective. Glut-
araldehyde is frequently blended with quaternary ammo-
nium compounds to increase biocide effectiveness. All
aldehydes are reactive with and consumed by sulfides.
Systems with high sulfide concentrations would have
high chemical consumption.
A wide variety of organics and combinations of organics
are used as biocides. Most organic biocides contain
nitrogen, sulfur, phosphorous, or halogens atoms within
their structures. Common organic biocides include
quaternary ammonium compounds, amines, chlorinated
phenols, and isothiazolin. Biguanides, nitrogen-contain-
ing compounds, are effective at low to medium tempera-
tures (<170°F). They are widely used in West Africa and
Papua New Guinea.
A relatively new biocide based on a phosphonium sulfate
formulation and produced by Albright & Wilson, Ltd.15 Phosphonium sulfate
has been used against sulfate reducers in the North Sea. biocides are available for
The chemical supplier is registering the compound with
use in Australia.
the U. S. Environmental Protection Agency for use as a
biocide in the United States.
Most organic biocides are blends or mixtures of a number
of chemicals. They are formulated for specific applica-
tions or types of bacteria. Tests of effectiveness of some
representative organic biocides are discussed later.
Biocide Selection
We should consider four guiding principles when select-
ing and using biocides to control microbiological activity.
1. The biocide must reach and come in contact with the
bacteria in a high enough concentration and long
enough to achieve an effective kill.
2. Apart from the protective aspects of the biofilm,
sessile bacteria may be inherently less susceptible to
biocides than the corresponding planktonic bacteria.
3. Biocide effectiveness varies from one bacterial type to
another.
4. Any chemical used as a biocide must be compatible
with all other chemicals present in the system or
added as a treatment chemical.

Sessile bacteria, attached to surfaces and sheltered by
overlying biofilms and other deposits, are of primary
concern in water treating facilities. These films and
deposits, at the least, offer a diffusional barrier to slow
down contact between the biocide in the bulk liquid
phase and the sessile bacteria on the solid surface. At the
other extreme, components of the films may consume or
deactivate the biocide and decrease its concentration to
an ineffective level when it finally does reach the sessile
bacteria.
Sessile bacteria associated with biofilms are substantially
more resistant to biocides than planktonic bacteria of the
Sessile bacteria are more same species. This increased resistance appears to be
resistant to biocides than related both to restricted transport of the biocide through
planktonic. Biocide tests the biofilm and different physiological properties of
sessile bacteria. Biocide testing with planktonic bacteria,
with planktonic bacteria
particularly laboratory testing with pure cultures or
are useless for field single species, is useless. Laboratory tests may give
applications. harmful information about biocide dosages and effective-
ness. To be meaningful, biocide testing must be per-
formed under field conditions with sessile bacteria and
their associated biofilms.
Many different types of bacteria are present in all water
treating facilities. Tolerance or resistance to biocides
usually varies from one type of bacteria to another.
When a facility is treated with just one type of biocide,
the least resistant strains are affected more than the more
The selectiveness of
resistant strains. With time, the least resistant strains are
biocides can lead to a killed off, but the more resistant strains now flourish
“survival of the fittest” because of the decreased competition for the limited
mode of bacterial growth amounts of nutrients in the system. In popular terminol-
ogy, it is said that the bacteria have developed a resis-
in a water treating system.
tance to the biocide. In reality, the environment has been
changed to favor the more resistant bacterial species at
the expense of the least resistant. The usual remedy for
this situation is to alternate different biocides with differ-
ing effectiveness so that one species of bacteria does not
become dominant.
To be effective, biocides, like all treating chemicals, must
be compatible with the chemical components normally
present in the system and with other treating chemicals
added to the system. Classic examples of incompatibility

include using oxidizing biocides in sour systems that
have high oxidant demand; using oxidizing biocides that Biocides must be
react with sulfite-containing oxygen scavengers to pro- compatible with all other
duce sulfate that stimulates SRB activity; and deactivat-
treating chemicals.
ing diamine acetate biocides by phosphate scale inhibi-
tors with the formation of fouling and plugging
precipitates.
Factors to be considered in selecting biocides and their
treatment or application methods are:
1. Economics or cost of biocide treatment vs. the cost
savings realized.
2. Location, types, and distribution of bacterial species.
3. Climate, weather, and their effect on the chemical
formulation and application procedure. Some biocide
formulations may freeze or become viscous in cold
weather and require diluents that could alter their
effectiveness.
4. Environmental and safety concerns - all biocides have
some degree of toxicity. In the U. S., all chemicals
used as biocides must be registered with the Environ-
mental Protection Agency.
Important questions concerning the use and application
of biocides are:
1. Has the material been approved for use as a biocide?
2. Can it be applied with minimum hazards to personnel
who might come in contact with it?
3. What are the possible environmental effects of the
biocide?
4. Is the compound or formulation effective at reason-
able concentrations for the sessile bacteria and
biofilms present in the particular facility?
5. Is it compatible with the chemistry of the system and
with other treating chemicals?
6. Is it persistent in the system? How far downstream of
the application point is it effective?

Time-Kill Procedure for Biocide
Effectiveness
The time-kill procedure as outlined in API RP 386 is
frequently used to evaluate and rank biocides. Bacteria
samples are exposed to various concentrations of the
The time-kill procedure biocide being tested. After specific exposure times,
samples are removed, the residual biocide is neutralized
for biocide effectiveness
or diluted until it is no longer effective, and the remain-
has been revised and ing viable bacteria are counted. The number of living
updated in NACE bacteria after biocide exposure is compared with the
TM 0194-94.16 number originally present. We can also compare that
bacteria with the bacteria in an untreated control to
determine the biocide effectiveness at a particular time-
concentration situation. Effectiveness can be reported in
terms of the percent kill:
 Sample Number 
Percent Kill = 1- × 100 (3)
 Control Number 
where control number and sample number are the num-
ber of viable bacteria in the unexposed control and the
exposed sample, respectively. The results can also be
expressed as the log reduction of bacteria defined as
 (Control Number) 
Log Reduction = log10  
 (Sample Number)  (4)
If the serial dilution culturing method discussed in the
Broth Bottles section is used, the log reduction is numeri-
cally equal to the number of bottle reductions defined as
Bottle Reduction = (Number of Control Bottles) − (Number of Sample Bottles) (5)

where the number of bottles is the greatest dilution that
gave a positive test for viable bacteria. Table 13 com-
pares the three reporting methods. (A log or bottle
reduction of 6 is generally considered a complete kill in
biocide evaluation.)

Table 13 Definitions of Biocide Effectiveness
Percent Kill Log Reduction Bottle Reduction
90 1 1
99 2 2
99.9 3 3
99.99 4 4
99.999 5 5
99.9999 6 6
By using different culturing media and protocols to

detect and enumerate bacteria, we can estimate the effec-
tiveness of the biocide for various bacterial types. Effec-
tiveness for planktonic bacteria is measured by exposing Biocide effectiveness is
bacteria-containing liquid samples of known volumes to frequently measured in
various combinations of biocide type, concentration, and terms of percent kill.
contact time; counting the remaining viable bacteria; and
comparing the numbers to those of the same volume of a
control sample that has not been exposed to the biocides.
Effectiveness for sessile bacteria is measured by growing
bacteria and biofilms under fixed conditions on metal
coupons or studs of known area; exposing the coupons to
various combinations of biocide type, concentration, and
contact time; scraping off a known area (or mass) of
biofilm; dispersing it in sterile culturing media; counting
the remaining viable bacteria in the dispersed biofilm;
and comparing the numbers to those from the same area
of a biofilm-fouled control coupon that has not been
exposed to the biocides.
As the names suggest, results are usually expressed in
terms of biocide concentration and contact time neces-
sary to achieve a certain degree of kill or control. Higher
biocide concentrations require shorter contact times, but
the product of concentration and contact time is not a
constant. In general, lower biocide concentrations re-
quire longer contact times than those predicted by a
constant time-concentration product. In practice, there is
a lower biocide concentration below which the biocide is
ineffective even with continuous injection (infinite con-
tact time). This is particularly true for dirty systems
where contaminants may consume or deactivate the

biocide. It is also true for sessile bacteria where the
biofilm may deactivate the biocide or restrict its transport
to the bacteria.
Estimation of Biocide Batch Frequency

The measurement of biocide effectiveness, in terms of log
or bottle reduction, can be used to estimate the frequency
of batch or slug treatment to maintain bacterial control.
The minimum time for sessile bacteria to recover (to
grow back to the same number) after a biocide treatment
is
(Log Reduction) × (Doubling Time, hours)
(Recovery Time, hours) = (6)
log 10 2
where the log reduction, defined in Eq. 4, is experimen-
tally measured during a series of time-kill tests, and the
doubling time is the time required for the specific bacte-
The doubling time for a rial species to grow by a factor of two. Table 14 shows
the minimum time needed for bacteria to recover from
bacterial species is various degrees of kill imposed by application of biocides
important for estimating when the sessile bacteria have doubling times of 30
the frequency of batch minutes and 2 hours, respectively. Using the minimum
biocide treatments. recovery time as an estimate of slug frequency, we can
estimate the relative cost-effectiveness of time-concentra-
tion combinations of various biocides. Note that this
comparison is only an estimate; any conclusions drawn
from it should be verified by a field test of the biocides.
Table 14 Recovery After Biocide Treatment

Minimum Recovery Time,
Biocide Effectiveness hours
Doubling Time
Log
Percent Kill Reduction 0.5 hours 2 hours
90. 1 1.7 6.6
99. 2 3.3 13.3
99.9 3 5.0 19.9
99.99 4 6.6 26.6
99.999 5 8.3 33.2
99.9999 6 10.0 39.9

Factors Affecting Biocide Effectiveness
The resistance of sessile bacteria protected by biofilms
and other deposits is becoming increasingly apparent in
water treating operations. For meaningful tests of bio-
cide effectiveness, the types, numbers, and location
(planktonic versus sessile) of bacteria must correspond to
those encountered in field situations.
The physical, chemical, and microbiological properties of
biofilms and deposits are functions of the hydrodynamics
of the system. They also are functions of other conditions
under which the biofilms are developed. For example,
high fluid flow rates bring many nutrients to the biofilm
surfaces and tend to produce thin and compact biofilms
rapidly. Low flow rates have less shear and tend to
produce thicker biofilms over longer times. Suspended
solids in the water are incorporated into the biofilms.
Water composition — the chemical components, micro-
biological nutrients, pH, eH, dissolved oxygen content,
temperature, etc. — affect the nature and properties of
the biofilm and associated bacterial consortia and their
response to biocides. The closer the system for produc-
ing biofilm and testing biocides is to the field situation,
the more meaningful the results of the effectiveness tests
are.
Tables 15 through 17 show the importance of testing
biocides at conditions close to those in the field. Data for
these three tables were taken from published results of
Grab and Theis13. Table 15 gives the composition of the
biocides in Tables 16 and 17. It illustrates two character- Laboratory tests should
istics of commercial biocides. First, commercial products be used only for
are frequently mixtures of complex chemicals. Second,
the concentrations of active ingredients are frequently screening biocides. Field
quite small. In comparing commercial biocides, we must testing is essential to
note whether the indicated concentrations are for the determine actual
commercial products or for the active ingredients. The
performance.
best comparison by far is in terms of the cost of the com-
mercial product per thousand barrels of fluid treated.
Table 16 shows the effectiveness of various biocides for
planktonic vs. sessile SRB. Table 17 shows how low
sulfide concentrations can reduce biocide effectiveness.

Table 15 Biocides Tested
Biocide Composition
ADBAC alkyl (C14 50%, C12 40%, C16 10%)
dimethyl benzyl ammonium chloride, 50%
DBNPA 2,2-dibromo-3-nitrilopropionamide, 20%
formaldehyde aqueous formaldehyde, 37%
Gluteraldehyde aqueous glutaraldehyde, 45%
Gluteraldehyde/ aqueous glutaraldehyde + ADBAC,
quat total 50% active ingredients
Isothiazolone 5-chloro-2-methyl-4-isothiazolin-3-one,
1.15% + 2-methyl-4-isothiazolin-3-one, .35%
Table 16 Biocide Effectiveness

Planktonic SRB Sessile SRB
Log Reduction Log Reduction
Biocide, ppm
Product 3 h. 7 h. 1 h. 4 h.
ADBAC, 40 1–2 2 1 1
DBNPA, 50 0 0 1 1
Glutaraldehyde, 100 2 3 2 4
Glutaraldehyde/ 3–4 5 4 5
quat, 80
Isothiazolone, 200 0 0 0 1
Note: Desulfovibrio desulfuricans, Mid Continent Strain A,
pH 6–8, 25ºC
From Reference 13
Table 17 Effect of Sulfide on Biocide Effectiveness

Log Reduction — Presence
(and Absence) of Sulfide
Contact Time, hours
Biocide, ppm Product 1 7 24
ADBAC, 40 4(4) 6(6) 6(6)
DBNPA, 50 0(3) 1(4) 4(4)
Glutaraldehyde, 100 6(6) 6(6) 6(6)
Glutaraldehyde/quat, 80 6(6) 6(6) 6(6)
Isothiazolone 0(0) 0(0) 0(0)
Note: Escerichia coli (ATCC8739), 25ºC, pH 7.5, 10 ppm
sulfide
From Reference 13

The inherent resistance of sessile bacteria to biocides is
shown in Table 16 and compared with the much lower
resistance of planktonic bacteria. For this comparison,
the biofilms containing the sessile SRB were grown on
steel samples immersed for 7 to 14 days in a suitable
culture medium inoculated with the SRB strain. A flow- Sessile bacteria are
ing system was not used, so the biofilm characteristics
and reaction to biocides may not completely mimic field inherently more resistant
conditions. Biofilmed samples were removed from the to biocides.
medium before contact with the biocide to minimize the
effect of SRB metabolic products on biocide effectiveness.
Table 16 also shows the wide variation in effectiveness
with the chemical composition of the biocide. The data
in Table 16 stress the importance of screening biocides
with sessile bacteria and biofilms from the field under
study.
Table 17 shows how sulfide, the metabolic product of
SRB, can decrease the effectiveness of some biocides. In
this case, planktonic Escherichia coli (E. coli) were used as
the test species. Most biocides were quite effective in the
absence of sulfide (log reduction number is in parenthe- Sulfides in solution can
ses). In the presence of only 10 ppm sulfide, some bio- reduce the effectiveness
cides showed decreases in effectiveness of up to three
of some biocides.
orders of magnitude (log reduction of 3).
The results in Tables 16 and 17 apply only to the system
studies. They should not be extrapolated to other fields
with different types of SRB, other bacteria, and deposits
that make up the biofilm. Specifically, gluteraldehyde
may not always be the most effective biocide for all
applications.
Sessile Samples for Biocide Testing

Three types of systems or devices are used to obtain or to
simulate sessile bacteria and biofilm accumulations.
These devices, in order of similarity to the field are
(1) laboratory recirculating loops, (2) field side-stream
test loops, and (3) in-line probes. These devices are
discussed in detail by NACE7. Although the NACE
report is directed primarily toward SRB, we can test
other types of bacteria in any of these devices by varying
the culturing and enumerating procedures.

Table 18 Devices to Produce Biofilms for Biocide
Selection
Laboratory Recirculation Loops
Field Side Stream Test Loops
Field In-Line Probes
Laboratory Recirculation Loops

These loops are the simplest to construct and use. They
usually operate by recycling test water over or through a
number of test sections. Nutrient composition and water
chemistry are maintained by a feed-and-bleed technique.
In this way, shear forces (flow velocities) can be varied
independently from the residence time of the water in the
loop. We can achieve identical flow conditions by con-
necting test elements in series; varying flow conditions,
by connecting test elements in a parallel, flow-controlled
arrangement.
Principle advantages of the laboratory rigs are (1) tight
control over fluid compositions and process variables
and (2) ready access to equipment and instruments for
accurate measurement of chemical, physical, mechanical,
and microbiological properties. Major disadvantages are
the inability to duplicate completely field water chemis-
tries and hydrodynamics, which may have a pronounced
effect on biofilm properties and thereby on biocide effec-
tiveness. Laboratory rigs are used primarily to provide
biofilm samples for biocide development and formula-
tion, initial biocide screening studies, and fundamental
programs in MIC and biocide mechanisms.
Field Side-Stream Test Loops

A small volume of field water is passed through a side-
stream device with suitable test surfaces for bacterial
attachment and biofilm growth. The loop may be oper-
ated in a once-through or recirculating feed-and-bleed
mode. Fluid is discharged from the loop to waste or is
pumped back into the water treating facility (Fig. 1). By
using a parallel arrangement with pumped, flow-con-
trolled recirculating loops and flow-controlled bleeds, we

Figure 1 Side Stream Test Loop

can vary flow rate and residence time independently
within any one loop and from one loop to another. We
can test a number of biocide types and concentrations
simultaneously in either batch or continuous addition
modes by incorporating provisions for chemical addition
in each loop.
Principle advantages of the side-stream loops are:
1. Actual process water is used without the need for
definition of water composition.
2. We can test several flow conditions and biocides
simultaneously.
3. The overall process is not disrupted if the side-stream
fluid is discharged to waste or is small enough to be
pumped back into the treating system.
Disadvantages include difficulties in matching fluid
velocities and hydrodynamic properties in a small-diam-
eter side stream and difficult operating procedures and
controls, particularly in side-stream devices with recircu-
lation.
Field In-Line Probes

A number of commercially available high-pressure fit-
tings for inserting test probes do not require system
shutdown and depressurization. The probes usually
have five or six coupons (or studs) of known surface
compositions, properties, and areas. The probes are
placed in the process flow stream so that the coupon
surface is in line with the pipe wall (flush mounted) to
simulate pipe surface wall conditions. The devices can be
used to provide biofilmed surfaces for measuring biocide
effectiveness and for screening biocides. They are rarely
used for in-situ measurement for biocide selection. Be-
cause these probes are directly in the full flow process
stream, large amounts of chemical are required for tests,
with the possibility of system upset if the chemical is not
effective. Once a biocide has been selected, perhaps with
a side-stream loop, the devices can be used to monitor
the performance of that biocide in the full stream.

Principal advantages of using these probes are that
biofilms are formed under actual process conditions and
the surface characteristics of the coupons in terms of
metallurgy, roughness, and pretreatment can be varied in
the same probe. Disadvantages are the limited number
of coupons available in each probes, and the expense,
weight, and handling difficulties of the probes and the
insertion device needed for high-pressure applications.
Biocide Treatment Procedures

Biocides can be applied continuously or in batch treat-
ments. Continuous treatment is expensive and is usually Types of biocide
used with biocides effective at low dosages (e.g., chlorine, applications:
hypochlorite, or chlorine dioxide) after the system is
• continuous
cleaned up. Other biocides are commonly used in slug
(or batch) treatment. • batch
In the batch mode, high concentrations of biocide are
applied over several hours at regular intervals, ranging
from several times a day for severely contaminated
systems to several times a month for systems exhibiting
good microbiological control. In this method, the objec-
tive is not complete elimination of bacteria and biofilm
formation; the goal is economical control with minimized
costs to control and rectify microbially induced damage.
Good batch treatment requires effective determination of
biocide dosage rates, contact times, and treatment fre-
quencies. It also requires adequate follow-up monitoring
in the field system.
Biocide Toxicity
By their very nature, biocides must be toxic to bacteria
and other microorganisms. However, their toxicity to Toxicity is the potential or
higher life forms is of prime importance in protecting the capacity of a test material
environment. This is true whenever water is discharged.
It is also important whenever there is a spill, a leak, or to cause detrimental
accidental contact with biocide-treated water. effects on living
Before discussing the toxicity of specific biocides, we organisms.
should define a few important terms. Toxicity is the
potential or capacity of a test material to cause detrimen-
tal effects on living organisms. Toxicity may be acute as
the result of a relatively short-term exposure (2 to 4 days

for most toxicity testing) or may be chronic if the expo-
sure is for relatively long times (times of up to 10% or
more of the lifetime of the test species).
An aquatic toxicity test (also called a bioassay) is used to
assess the potential for damaging toxic effects of a test
material on specific aquatic organisms:
• Lethal concentration, median (50%) (LC50; concentration
of a toxic material estimated to cause death in 50% of
the exposed organisms after a specified time of expo-
sure (usually 96 hours).
• Effective concentration, median (50%) (EC50; toxicant
concentration estimated to cause a specified effect in
50% of the test species after a specified exposure time
(usually 96 hours).
• No-observed-effect concentration (NOEC; highest toxi-
cant concentration where the measured response of
the test system shows no statistically significant
difference from the control system.
• Lowest-observed-effect concentration (LOEC; lowest
toxicant concentration that shows a measured re-
sponse difference that is statistically significant from
that of the control.
The simplified procedure for aquatic toxicity testing is to
expose the test species to various concentrations of the
discharge water or chemical under evaluation for a set
time and observe the effects on the test species. The
specific protocol to be used (test species, concentrations,
temperature, dissolved oxygen levels, exposure times,
dilution water composition, etc.) are usually specified in
the discharge permit. Variations in protocol can materi-
ally affect the test results. Strict attention to following the
specified protocol and establishing traceable quality
control procedures is essential for obtaining meaningful,
credible results. Certified contract laboratories almost
Various instrumental always perform toxicity testing for discharge purposes.
procedures have been The aquatic toxicity test is difficult to perform and obtain
reproducible results, expensive, and time-consuming
proposed as substitutes
(usually 96 hours is needed to determine whether com-
for the time-consuming pliance has been achieved). Some alternative procedures
bioassay procedure. have been proposed. The most popular one is the

Microtox device produced by Microbiotics Corp.,
Carlsbad, CA. The test measures the amount of light
produced during metabolism of certain ocean-going
bacteria. The amount of light produced is a measure of
bacterial metabolic activity and is usually calibrated by
comparing it to the light emitted by the bacteria in a
control situation. Less light means lower bacterial activ-
ity — i.e., more dead or inactive (damaged) bacteria.
Light-producing metabolism is much more sensitive to
damage than is growth, thereby giving a faster response
time that the aquatic testing.
The primary advantage of the Microtox is rapid (30
minute) on-site results. The principal disadvantages are
that correlations with aquatic tests are difficult and the
method is not usually acceptable for discharge permits.
Hudgins14 reviewed the toxicity of a large number of
treating chemicals, including biocides, used in offshore
oil and gas production, primarily in the Gulf of Mexico.
Participating chemical suppliers furnished all the data.
Concentrations refer to the chemical as supplied, not to
the amount of active ingredient.
As expected, LC50 values depended on water salinity
and on the test species. LC50’s, for representative bio-
cides, varied from 0.2 to >1,000 ppm, with 90% of the
biocides having LC50’s >5 ppm. Interestingly, water-
soluble corrosion inhibitors were more toxic, with LC50’s
ranging from 0.2 to 5 ppm with 90% >1 ppm. For the
biocides, amines and amine salts were generally the most
toxic. Quats with glutaraldehyde were the least toxic of
the biocides listed. Isothiazolin has about the same
toxicity as glutaraldehyde. The phosphonium sulfate
biocide produced by Albright & Wilson15 was reported to
be considerably less toxic to freshwater species than
glutaraldehyde and to be “inherently biodegradable.”
MONITORING METHODS FOR MICROBIAL

ACTIVITY
The key to effective control of microbial problems is
adequate monitoring of bacterial activity and biofilm
development in all parts of the water treating facilities.
For planktonic bacteria, any of the test procedures for

bacterial types listed previously can be used. Numbers
of planktonic bacteria are measured as a function of time
and location in the facilities. Increases in numbers indi-
cate lack of control and the likelihood of downstream
contaminations; no change in numbers indicates control;
and decreases in numbers indicate system cleanup. In-
line probes are best for monitoring sessile bacteria and
biofilms, followed by the field side-stream loops. Labora-
tory recirculating rigs should not be used to monitor field
situations.
All monitoring devices for bacteria and biofilms measure
bacterial number or activity only at the location of the
monitor. Indirect methods, such as chemical analysis for
compositional changes or the appearance of planktonic
bacteria, can indicate bacterial activity somewhere up-
stream of the sample point.
Consider the case of a seawater injection facility where
the sulfate for SRB activity comes from the seawater but
the carbon source for SRB and biofilm activity is only in
the reservoir. Surface monitoring before the injection
wells will indicate no SRB activity because the requisite
combination of sulfate and carbon source is not present
until the injection water mixes with the produced (con-
nate) water in the reservoir. In this case, monitoring
sulfide levels in the produced fluids can indicate reser-
voir souring (SRB activity) in the reservoir. However, the
method is not very sensitive because initial sulfide pro-
duction in one part of the reservoir is diluted by all the
produced fluids. Sulfide usually appears at the produc-
ing wells after souring begins in the reservoir because
distribution of sulfide between the reservoir fluids and
absorption on and reaction with rock minerals act as
large sinks for H2S. Once the reservoir is soured, enough
sulfide is stored in the reservoir that sulfide continues to
appear in the produced fluids even after all SRB activity
is eliminated.
In a seawater injection system, surface monitoring for
bacterial activity is still recommended to minimize prob-
lems from bacteria other than SRB and to indicate SRB
control indirectly. If other bacterial species are con-
trolled, there is a good chance that SRB are being con-
trolled to some degree.

REFERENCES
1. Jórgensen, B. B.: “A Comparison of the Methods for
the Quantification of Bacterial Sulfate Reduction in
Coastal Sediments. III. Estimation from Chemical and
Bacteriological Field Data, “ Geomicrobiol. J. (1978) 1,
11.
2. Brock, T. D. and Madigan, M. T.: Biology of Microor-
ganisms, fifth edition, Prentice Hall, Englewood Cliffs,
NJ (1988).
3. Cord-Ruwish, R., Kleintz, W., and Widdel, F.: “Sul-
fate-Reducing Bacteria and Their Activities in Oil
Production,” JPT (1987) 39, 97.
4. Postgate, J. R.: The Sulfate-Reducing Bacteria, second
edition, Cambridge University Press, Cambridge
(1984).
5. NACE TPC Publication 3, Microbiologically Influenced
Corrosion and Biofouling in Oilfield Equipment, Natl.
Assn. of Corrosion Engineers, Houston (1990).
6. RP 38, Recommended Practice for Biological Analysis of
Subsurface Injection Water, American Petroleum Insti-
tute, Philadelphia (March 1982).
7. NACE Item #54278, Review of Non-Conventional and
Supplementary Methods for the Detection of Sulphate-
Reducing Bacteria in Oilfield Waters, Natl. Assn. of
Corrosion Engineers, Houston (1989).
8. Mittleman, M. W. and Geesey, G. G.: Biological Fouling
of Industrial Water Systems: A Problem Solving Approach,
Water Micro Associates, San Diego, CA (1987).
9. Horacek, G. L.: “Field Experience with an SRB Rapid
Detection Test Kit,” SPEDE (Dec. 1992) 275.
10. Orr, W. L.: “Geological and Geochemical Controls on
the Distribution of Hydrogen Sulfide in Natural Gas,”
Advances in Organic Geochemistry 1975, Proc., Intl.
Meeting on Organic Geochemistry Madrid (Sept. 16-
19, 1975).
11. Scott, P. J. B. and Davies, M.: “Survey of Field Kits for
Sulfate-Reducing Bacteria,” Materials Performance
(1992) 31, 64.

12. Clementz, D. L. et al.: “Stimulation of Water Injection
Wells in the Los Angeles Basin Using Sodium Hy-
pochlorite and Mineral Acids,” JPT (1982) 34, 2087.
13. Grab. L. A. and Theis, A. B.: “Comparative Biocidal
Efficacy vs Sulfate-Reducing Bacteria,” Materials
Performance (1993) 32, 59.
14. Hudgins C. M. Jr.: “Chemical Treatments and Usage
in Offshore Oil and Gas Production Systems,’ JPT
(1992) 44, 604.
15. “THPS Biocides for Industry,” Albright & Wilson,
Ltd., product brochure.
16. NACE Item No. 21224, Standard Test Method — Field
Monitoring of Bacterial Growth in Oilfield Systems,
TM 0194-94, Natl. Assn. of Corrosion Engineers,
Houston (1994).

GLOSSARY
Abiotic — not produced by bacteria or living organisms.
Acetate utilizers — SRB capable of completely oxidizing
acetate to CO2 and H2O.
Acid producing bacteria (APB) — type of bacteria ca-
pable of breaking down complex organic compounds
to simpler, low-molecular-weight fatty acids, such as
formic, acetic, propionic, and butyric.
Acridine orange — a fluorescent compound used in the
epifluorescent method for total cell counts.
Acute toxicity — toxicity occurring during relatively
short-term (2- to 4-day) exposures.
Adenosine-5'-phosphosulfate (APS) reductase enzyme
— an enzyme specific to SRB used for detection and
enumeration in the Conoco RapidChek kits.
Adenosine-5'-triphosphate (ATP) — a nucleotide that
acts as a carrier of chemical energy in microbiological
reactions.
Aerobe — an organism that grow in the presence of
oxygen.
Aerobic — in the presence of oxygen.
Anaerobe — an organism that grow in the absence of
oxygen.
Anaerobic — in the absence of oxygen.
AO — see acridine orange.
APB — see acid-producing bacteria.
API — American Petroleum Institute.
APS — see adenosine-5'-phosphosulfate (APS) reductase
enzyme.
Assimilation — anabolism, the incorporation or conver-
sion of nutrients into cell material.
ATP — see adenosine-5'-triphosphate.
Autotroph — organism able to use CO2 as the sole carbon
source.

Biofilm — bacterial cells immobilized at a surface and
embedded in an organic polymeric matrix of micro-
bial origin (EPS) and frequently combined with inor-
ganic and abiotic materials.
Biogenic — produced by bacteria or microorganisms.
Consortium — bacterial population composed of two or
more types of organism where the action of one
organism benefits the others.
Biotic — produced by bacteria or living organisms.
Chronic toxicity — toxicity from relatively longer-term
exposures (up to 10% or more of the normal life time
of the test species).
DAPI — see 4,6-diamino-2-phenylindole.
4,6-Diamino-2-phenylindole — a fluorescent compound
used in the epifluorescent method for total cell counts.
Dissimilation — catabolism, metabolism involving the
release of energy within an organism.
Doubling time — time required for a bacterial popula-
tion to increase its number by a factor of two.
EC50 — see effective concentration, median (50%).
Effective concentration, median (50%) (EC50) — toxicant
concentration estimated to cause a specified effect in
50% of the test species after a specific exposure time
(usually 96 hours).
Electron acceptor — an organic or inorganic compound
that accepts electrons in a microbial reaction, an
oxidizing agent.
Electron donor — a compound, generally organic but
may be hydrogen, that provides electrons to affect
reductions in microbial reactions, a reducing agent.
EPS — see extracellular polymeric substance.
Extracellular polymeric substance — highly hydrated,
“slimy” polymers, almost exclusively polysaccha-
rides, produced by bacteria to act as (1) a glue to hold
them to surfaces, (2) a protection from harmful exter-
nal environments, and (3) a concentrating mechanism
to satisfy nutrient requirements.

Facultative — organism is able to grow in the presence or
absence of the specified environment.
FDA — see fluorescein diacetate.
Fluorescein diacetate — a fluorescent compound used in
the epifluorescent method for viable cell counts.
Genus — a group of related species.
Halophile — organism that grow better in high salt
(NaCl) concentrations.
Heterotroph — organism that uses organic compounds
as energy and carbon sources.
Hydrogenase — enzyme used by bacteria in the oxida-
tion of hydrogen to protons and electrons.
Isotope — atoms of the same chemical element that have
different atomic masses.
LC50 — see lethal concentration, median (50%).
Lethal concentration, median (50%) (LC50) — concentra-
tion of a toxic material estimated to cause death in
50% of the exposed organisms after a specified time of
exposure (usually 96 hours).
Lithotroph — organism that uses inorganic compounds
as an energy source.
LOEC — see lowest-observed-effect concentration.
Lowest-observed-effect concentration (LOEC) — lowest
toxicant concentration that shows a measured re-
sponse difference that is statistically significant from
that of the control system.
MEOR — see microbially enhanced oil recovery.
Mesophile — organism that grows best at a temperature
range of about 10 to 40°C.
Methanogens — a group of obligative anaerobes that
convert organic compounds and CO2 to methane.
MIC — see microbiologically influenced corrosion.
Microbial profile modification (MPM) — encourage-
ment of bacterial activity within a producing reservoir
to form plugging biofilms that block off watered-out
zones or adjust permeability profiles.

Microbially enhanced oil recovery (MEOR) — use of
bacteria and microbiological activity within the reser-
voir to improve oil recovery.
Microbiologically influenced corrosion (MIC) — en-
hanced localized corrosion that occurs directly or
indirectly from bacterial action and/or the metabolic
products of bacteria.
MPM — see microbial profile modification.
NACE — National Association of Corrosion Engineers.
No-observed-effect concentration (NOEC) — highest
toxicant concentration where the measured response
of the test systems shows no statistically significant
difference from that of the control system.
NOEC — see no-observed-effect concentration.
Obligative anaerobe — require an oxygen-free environ-
ment with a low redox potential for growth.
Obligative — specified environment is required for
growth.
Oxidizing agent — see electron acceptor.
Planktonic bacteria — bacteria that exist as floaters in a
liquid stream.
Reducing agent — see electron donor.
Sessile bacteria — bacteria that are attached to surfaces.
Slime formers — bacteria that produce large amounts of
biofilm.
SPB — see sulfide-producing bacteria.
Species — a collection of closely related strains.
SRB — see sulfate-reducing bacteria.
Substrate — compound involved in a microbiological
reaction.
Substratum — surface to which bacteria and biofilms are
attached.
Sulfate-reducing bacteria (SRB) — type of bacteria
capable of reducing sulfate ions to hydrogen sulfide
using organic compounds and/or hydrogen as the
reducing agents.

Sulfide-producing bacteria (SPB) — bacteria capable of
producing hydrogen sulfide from oxidized sulfur
compounds.
Sulfur-oxidizing bacteria — aerobic bacteria that oxidize
hydrogen sulfide to sulfuric acid.
Thermophile — organism that grows best at higher
temperatures.
Threshold limit value (TLV) — time-weighed average
concentration for an 8-hour workday and a 40-hour
work week, to which nearly all workers may be
exposed repeatedly, day after day, without adverse
effect.
TLV — see threshold limit value.
Toxic — potential or capacity of a test material to cause
detrimental effects on living organisms.

C H A P T E R
Chemical Injection
Chapter 8: Chemical Injection 8-1

INTRODUCTION
In most oil fields, the water that must be processed in the
water treatment system contains a variety of chemicals
that have been injected into or added to the water:
1. Chemicals added to the water in the treatment system
itself as part of the treatment processes (improving
oil/water separation or filter backwash) or to main-
tain the system (scale, corrosion, and bacteria inhibi-
tors).
2. Chemicals used in general oilfield operations that end
up in the produced water (scale, corrosion, and bacte-
ria inhibitors).
3. Chemicals associated with other field operations that
generate wastewater streams that we often dispose of
by adding them to the feed to the water treatment
system (spent acid, workover fluids, cleaning solu-
tions, tank bottoms, etc.).
Besides injected chemicals, oilfield waters contain natural
components, some dissolved and some suspended. The
result of this mixture of natural components and injected
chemicals is a dynamic water system with constantly
changing chemistry. When changes in water chemistry
are excessive and/or abrupt, as might occur when a
chemical “slug” is injected into the water, the system goes
into an “upset,” the mechanical components of the water
treatment system (filters, oil/water separators, etc.) no
longer function properly, and the quality of the water
coming from the system deteriorates. Because of the
complexities of the water chemistry and the effects of
interactions of chemicals, injected or present in the water,
correcting such upsets may require days.
This chapter discusses the types and functions of chemi-
cals, naturally present or injected, that end up in the
treatment water and their potential interactions. We
suggest ways to minimize the interactions and proce-
dures for avoiding system upsets caused by upsets in
water chemistry.

NATURAL COMPONENTS OF OILFIELD
WATERS
Table 1 categorizes the primary natural components of
oilfield waters as cations (positive charges), anions (nega-
tive charges), neutral components, and dissolved gases.
All four categories are important because all can be
involved in interactions with injected chemicals. Obvi-
ously, the amounts of the various natural components
vary over wide ranges, depending on the water source
and history.
Tab le 1 N atural Com po n ents of O il F ield W aters

Catio ns H yd rogen H+
Sod ium N a+
Po tassium K+
C alcium C a ++
M agnesium M g ++
B ariu m B a ++
Strontiu m Sr ++
Iron Fe ++
A nio ns C hloride C l-
C O =3
C arbonate
H C O −3
B icarbonate
H yd roxid e OH-
SO =4
Sulfate
From o rg anic acids su ch as:
A cetate C H 3C O O -
Prop ionate C H 3C H 2C O O -
N eu tral Com po n ents Silica SiO 2

B acteria
O il
Susp end ed solid s such as:
Fo rm ation fines
Paraffins
A sphaltenes
Scale prod ucts
C orro sion prod ucts
D issolv ed G ases O xy gen O2

C arbon Dio xid e CO2
H yd rogen sulfid e H 2S

TYPES AND FUNCTIONS OF OILFIELD
CHEMICALS
General
Except for a few cases, commercially supplied oilfield
chemicals are not single chemical compounds. They
generally consist of the following:
1. One or more chemical compounds that are the “back-
bone” of the chemical (i.e., the active ingredient)
added to perform the designed function of the chemi-
cal. These chemicals often are produced from petro-
chemical streams or other natural organic materials.
These materials are mixtures of chemical compounds
having a range of molecular weights and different
chemical groups.
2. A solvent or mixture of solvents, required because the
main chemical compounds are viscous or solid in
their 100% active form. In some cases, the solvent
may be water; in many applications, however, refin-
ery cuts, paraffinic or aromatic hydrocarbon mixtures,
are used.
3. Other additives to enhance the activity of the main
chemical compounds, increase their solubility or
dispersibility, increase storage life, or prevent freez-
ing. Chemical suppliers consider these additives
active components of the formulation. Only the
solvent is considered inert.
The method of addition and the chemical concentrations
vary tremendously. Some surfactants to assist oil/water
separation are injected continuously at very low concen-
tration levels (a few ppm). Others, like biocides and filter
backwash chemicals, are injected in slugs of a few hun-
dred to a few thousand ppm. Scale inhibitors and similar
“well squeeze” chemicals are injected into the well at
concentrations of thousands of ppm but are produced
back over long time periods at much lower concentra-
tions. Some corrosion inhibitors are injected continu-
ously at 5 to 100 ppm; others are batch-treated at 1,000 to
5,000 ppm. The most reactive and concentrated chemi-
cals used in oilfield operations are stimulation acids,
which are used at concentrations of up to 30 wt%.

The amount of the injected chemicals in the feedwater at
the treatment plant depends on where the chemicals are
added, the relative solubility of the chemicals in water
and crude oil, and the proportions of the various waters
that make up the feedwater at any particular time. In the
end, the chemicals that affect the water treatment system
end up in the water itself. Their concentrations are im-
portant because they affect not only the operation of the
water treatment system but also the eventual use or
disposition of the treated water. Residual chemicals in
the treated water could have detrimental effects on water
softening, steam generation, EOR chemical addition,
reinjection (disposal, waterflooding, or pressure mainte-
nance), and water quality in terms of environmental
regulations.
In the following discussion, oilfield chemicals are classi-
fied according to their use and the “generic” compounds
that make up the active chemical constituents (remember
that solvents and other additives are also present in the
formulation). This list is by no means complete. Its
length illustrates the broad classes of chemicals that may
find their way into water treating systems. New chemi-
cals continually come into use; others stop being used.
Scale Inhibitors
Three classes of water-soluble compounds are used to
inhibit the formation of scale:
1. Organic phosphonates.
2. Phosphate esters.
3. Polymers (polyacrylates, polyacrylamides, and
phosphino-substituted polycarboxylic acid).
These chemicals are added to the produced water by a
well squeeze or direct addition. Because of their water
solubility, the portion that is not lost by adsorption onto
scale and other solids will show up in a produced-water
treatment system.
Corrosion Inhibitors
The compounds used as corrosion inhibitors in oil pro-
duction operations can be classified as:

1. Amides/imidazolines.
2. Salts of nitrogenous molecules with carboxylic acids.
3. Quaternary nitrogen compounds.
4. Polyoxyalkylated amines, amides, and imidazolines.
5. Nitrogen heterocyclic compounds.
6. Special inhibitors containing phosphorous, sulfur,
and/or oxygen.
The first two classes are the most common; the last is the
least common. The oil/water relative solubilities and
dispersibilities of these inhibitors depend on the group
lengths and types on the molecules, the organic acid used
in the compound formation, and the solvents and surfac-
tants used in the formulation. The oil-soluble (water-
dispersible) corrosion inhibitors find greatest application
in oil-producing operations. Thus, only a small part of
these compounds will end up in the produced water.
Biocides
Two general classes of biocides are used in the oil field:
1. Strong oxidizers, including chlorine, sodium hy-
pochlorite, and chlorine dioxide.
2. Organic-based biocides, including quaternary ammo-
nium salts, aldehydes (formaldehyde, acrolein, and
glutaraldehyde), quaternary phosphonium salts,
thiocarbamate, and isothizaoline.
These biocides are highly water-soluble but very reactive.
The strongly oxidizing chlorine compounds are also very
corrosive and are consumed through a variety of reac-
tions with organic materials, metals, sulfides, etc. The
other biocides, although not as strong oxidizing agents,
are reduced by reactions with organic and inorganic
substances in produced-water systems. In some cases,
these substances are chemicals added to the treated water
for other purposes (e.g., oxygen scavengers).
Emulsion Breakers
These chemicals are added to improve oil/water separa-
tion:

1. Oxyalkylated alkyl phenol formaldehyde resins.
2. Polyglycol esters.
3. Alkyl aryl sulfonates.
4. Oxyalkylated polyglycols.
The formulation generally contains more than one of
these compounds plus a surfactant in an organic solvent.
These compounds are very insoluble in water and end up
in the oil phase of the emulsion.
Reverse Breakers
These chemicals are added to help remove oil droplets
from water. The most common compound classes are:
1. Low-molecular-weight polyamines.
2. Polyamine quaternary ammonium compounds.
These water-soluble compounds are often formulated
with aluminum, iron, or zinc chlorides. About half the
added chemical ends up in the treated water.
Coagulants and Flocculants

These chemicals are similar to the reverse breakers and
can be grouped as:
1. Inorganic metal salts.
A. Zinc.
B. Aluminum.
C. Iron.
2. Organic polyelectrolytes.
A. Nonionic polymers.
1. Polyacrylamide.
B. Anionic copolymers.
1. Acrylamide/acrylate.
C. Cationic polymers and copolymers.
1. Polyamines.
2. Polyquaternaries.
3. Polydiallyldimethylammonium chloride.

4. Acrylamide/dimethyl aminomethyl methacry-
late.
These water-soluble materials often react in the treated
water to form flocs that end up as sludge waste. They are
used most in gas flotation units to separate oil (and
suspended solids) from produced water. They are also
used in media (sand, garnet, anthracite) filtration for
suspended solids removal.
Antifoamers
These chemicals are used to control foam formation in
oil/water separators, de-aerators, and similar units. The
most common are:
1. Silicones.
2. Polyglycol esters.
Their low water solubility causes them to end up mostly
in the oil phase.
Surfactants
Nearly all oilfield chemicals are formulated with surfac-
tants to increase solubility or dispersibility in the carrier
solvent or in water. However, surfactants are generally
are not used alone except for cleaning tanks, vessels, and
decks (particularly offshore). Three common water-
soluble surfactants used for these purposes are:
1. Alkyl aryl sulfonates.
2. Ethoxylated alkylphenols.
3. Ethoxylated alcohols.
Paraffin Treating
Chemicals used to inhibit or remove paraffin deposits are
very water-insoluble. The following inhibitors are used
to prevent the forming and accumulation of paraffin
deposits:
1. Vinyl polymers.
2. Sulfonate salts.
3. Alkyl polyether and aryl polyether mixtures.

Paraffin dissolvers are aromatic and aliphatic refinery
cuts.
Oxygen Scavengers
To control corrosion, dissolved oxygen is generally re-
moved from oilfield waters, including seawater and
other injection waters, by a combination of mechanical
and chemical addition methods. The chemicals usually
are compounds of sulfur:
1. Ammonium sulfite or bisulfite.
2. Sodium sulfite or bisulfite.
3. Sulfur dioxide.
The sulfur part of these water-soluble compounds is
oxidized to sulfate ion by reaction with dissolved oxy-
gen.
Sulfide Scavengers
In some situations, chemicals are used to remove H2S
from produced water. The most common chemicals for
this purpose are:
1. Aldehydes.
A. Formaldehyde.
B. Glutaraldehyde.
2. Strong oxidizers.
A. Chlorine dioxide, gaseous and stabilized liquid.
B. Hydrogen peroxide.
These aldehydes and oxidizers also are biocides. In some
sour water systems where bacteria are a problem, some
of the chemical added to the water is intended to be
consumed in reactions with H2S and some functions as a
biocide. In other situations, the chemical is injected only
to scavenge H2S.

Hydrate Inhibitors
When hydrates are a problem in gas production, chemi-
cals are sometimes added to the associated water to
inhibit hydrate formation. These water-soluble chemicals
can end up in the produced water.
1. Methanol.
2. Ethylene glycol.
Gas Dehydration Chemicals

Natural gas is dehydrated to meet pipeline specifications
and to control corrosion. To remove the water, the gas is
brought into contact with:
1. Triethylene glycol.
2. Diethylene glycol.
3. Tetraethylene glycol.
The wet glycol is dried and recycled. Very little ends up
in the produced water.
Well Stimulation Chemicals

These chemicals find their way into the produced water
and the water treating system as they or their reaction
products flow back from the well with the produced
fluids. They also end up in the produced water if the
well is backflowed following the stimulation job. The
fluids are collected and dumped into a pit or tank, and
the fluids are added to the feedwater to the water treat-
ing system. They often cause severe upsets to the system.
Acids
1. Hydrochloric acid.
2. Hydrofluoric acid.
3. Formic acid.
4. Acetic acid.
5. Fluoroboric acid.
6. Citric acid.

Fracturing Fluids
1. Polymers (natural and synthetic).
A. Hydroxy alkyl celluloses.
B. Guar gums.
2. Alcohols.
3. Kerosene.
4. Emulsifiers (cationic surfactants).
5. Bridging agents.
A. Oil-soluble resins.
Additives
1. Corrosion inhibitors.
A. Substituted acetylenic alcohols.
B. Alkyl pyridine quaternaries.
2. Antisludging agents.
A. Alkyl benzene sulfonate.
3. Anti-paraffin-deposition agents.
A. Vinyl acetate resins.
4. Demulsifiers (see emulsion breakers).
5. Scale inhibitors (see scale inhibitors).
6. Solvents (refinery aromatic and aliphatic cuts).
7. Dispersing agents.
A. Alkylphenol ethoxylates.
8. Flushes.
A. Clay dispersion and swelling-control agents.
(1) Ammonium chloride.
(2) Potassium chloride.
(3) Poly quaternary ammonium compounds.
(4) Hydroxy aluminum.
B. Mutual solvents.
(1) Oxyalkylated alcohols.

(2) Ethylene glycol monobutyl ether.
(3) Other glycol ethers.
C. Solvents (refinery aromatic and aliphatic cuts).
9. Diverters.
A. Oil-soluble resins.
B. Paraffin beads.
C. Benzoic acid.
D. Naphthalene.
Workover Fluids
Like the stimulation chemicals, these chemicals or their
reaction products find their way into the produced water
and the water treating system as they flow back from the
well with the produced fluids. They also appear if the
well is backflowed following the workover and the fluids
are collected, dumped into a pit or tank, and then added
to the feedwater to the water treating system. They also
cause severe upsets to the system.
Weighted Brines
1. Sodium chloride.
2. Calcium chloride.
A. Ammonium chloride.
B. Potassium chloride.
C. Calcium bromide.
D. Zinc bromide.
Corrosion Inhibitors (see list above)
Biocides (see list above)

Oxygen Scavengers (see list above)
Viscosifiers
1. Polymers (natural and synthetic).
A. Hydroxyalkyl celluloses.

B. Guar gums.
C. Polysaccharides.
IONIC CHARACTER OF OILFIELD INJECTED

CHEMICALS
The effect of oilfield chemicals on a water treatment
system depends heavily on the ionic character of the
chemicals in terms of oil/water relative solubility and
reactivity within the water. Ionic properties are impor-
tant with respect to reactions between chemicals and the
surface active (surfactant) properties of the added chemi-
cals. Table 2 groups oilfield chemicals according to the
phase in which the chemical ends up and their ionic
characters (anionic, cationic, and nonionic).
As Table 2 shows, most corrosion inhibitors, emulsion
breakers, antifoamers, paraffin treating chemicals, and
surfactant cleaners remain in the oil phase. We can as-
sume that these chemicals will not show up in the
feedwater in the water treatment system.
However, we can expect that scale inhibitors, biocides,
reverse breakers, coagulants, flocculants, some surfac-
tant cleaners, oxygen scavengers, sulfide scavengers,
hydrate inhibitors, gas dehydration chemicals, stimula-
tion acids, and stimulation fluid additives will end up in
oilfield waters to the extent that they have not been
consumed by their intended use, reactions with other
dissolved or suspended components in the water, or
adsorption on solid surfaces. These, then, together with
the natural components of the water, are potential
sources of chemical interactions within the water treat-
ment system.
CHEMICAL INTERACTIONS
As noted, the ways in which chemicals are used in oil
fields vary greatly. Some are injected continuously.
Others are injected periodically in slugs. Consequently,
chemical interactions may be short term (during and for
a short period following the slug). Or the chemical
interactions may be long term or continuous (during the
continuous injection of one or more interacting chemi-
cals).

Because the chemicals injected in slugs are generally at
much higher concentrations then those added continu-
ously, the short-term interactions are the most devastat-
ing to a water treatment system. An example is “dump-
ing” spent stimulation acid and additives, recovered by
backflowing a well, into the feedwater to a water plant.
On the other hand, interactions of continuously injected
chemicals (low concentrations) may not throw the plant
into an upset. But such interactions can counteract the
purpose for which the chemical is injected. For instance,
an aldehyde injected as a bacteria-controlling biocide can
react with dissolved H2S.
The following discussion presents some possible chemi-
cal interactions in oilfield waters.
Cation/Anion Interactions Resulting in Scale

Formation
A common chemical interaction involves mixing two
oilfield waters that contain dissolved salts in the form of
ions but, when mixed, are incompatible. As a result,
scale-forming salts precipitate. Under specific condi-
tions, each cation in oilfield waters, natural or added, can
combine with any anion to form an insoluble salt. These
conditions may occur because of the mixing of incompat-
ible waters and changes in temperature or pressure. Such
conditions occur in a number of situations. Scales associ-
ated with oilfield water treatment and handling include:
1. Most common scales.
A. Calcium carbonate.
B. Calcium sulfate (gypsum).
C. Barium sulfate.
D. Iron sulfide.
E. Mixtures of the above.
2. Less common scales.
A. Strontium sulfate.
B. Calcium sulfate (anhydrite).
C. Sodium chloride.
D. Iron carbonate.

Table 2 Ionic Character of Oil Field Chemicals
Chemical Phase Ionic Character
Scale Inhibitors
Phosphonate Water Anionic
Phosphate Ester Water Nonionic
Polymer Water Anionic or Nonionic
Amine Oil Cationic
Quaternary Amine Water Cationic
Amide Oil Nonionic or Cationic
Amidoamide Oil Nonionic or Cationic
Biocides
Quaternary Amine Water Cationic
Phosphonium Salt Water Cationic
Aldehyde Water Nonionic
Chlorine Water Nonionic
Thiocarbamate Water Anionic
Isothiazoline Water Cationic
Emulsion Breakers
Phenol Formaldehyde Resin Oil Nonionic
Glycol Esters Oil Nonionic
Alkyl Arylsulfonate Oil Anionic
Oxyalkylated Glycols Oil Nonionic
Reverse Breakers
Polyamine Water Cationic
Polyamine Quat. Amm. Water Cationic
Coagulants and Flocculants

Inorganic Metal Salts Water Cationic and Anionic
Polyacrylamide Water Nonionic
Acrylamide/Acrylate Water Anionic
Polyamine/Polyquaternaries Water Cationic
Antifoamers
Esters Oil Nonionic
Silicones Oil Nonionic

Table 2 (continued) Ionic Character of Oil Field Chemicals
Chemical Phase Ionic Character
Surfactants (cleaners)
Alkyl Aryl Sulfonates Water and Oil Anionic
Ethoxylated Alkylphenols Water and Oil Nonionic
Ethoxylated Alcohols Water and Oil Nonionic
Paraffin Treating
Vinyl Polymers Oil Nonionic
Sulfonate Salts Oil Anionic
Polyethers Oil Nonionic
Oxygen Scavengers
Sulfite Salts Water Cationic and Anionic
Sulfur Dioxide Water Nonionic
Sulfide Scavengers
Aldehydes Water Nonionic
Hydrate Inhibitors
Methanol Water Nonionic
Ethylene Glycol Water Nonionic
Gas Dehydration
Glycols Water Nonionic
Well Stimulation
Acids Water Cationic and Anionic
Frac Fluids Water and Oil Nonionic
Additives
Acetylenic Alcohols Water Nonionic
Surfactants Water and Oil Cationic and Anionic
Mutual Solvents Water Nonionics
Diverters Oil Nonionic and Anionic
Viscosifiers Water Nonionics

E. Iron and calcium silicates.
F. Calcium sulfite.
G. Magnesium hydroxide.
Chapter 5 provides a more extensive discussion of scale
formation and control.
A less common interaction resulting in the formation of
precipitates is the reaction of anionic oilfield chemicals
and inorganic polyvalent cations in oilfield waters (Ca++,
Mg++, Fe++). Only a limited number of oilfield chemicals
are anionic in the water phase. As Table 2 shows, these
include phosphonate and acrylate polymer scale inhibi-
tors, acrylamide/acrylate coagulants, and alkyl aryl
sulfonate surfactants. The concentration of these chemi-
cals is generally low enough in oilfield waters that their
solubility is not exceeded even in the presence of the
inorganic cations listed in Table 1. However, when han-
dling anionic chemicals in their concentrated forms, we
should ensure that they are not mixed with waters con-
taining polyvalent ions.
Surfactant Interactions
The most common interactions between injected oilfield
chemicals involve surfactants (surface active agents).
Many injected chemicals are classified as anionic, cat-
ionic, or nonionic surfactants. We will briefly describe
the chemistry of surfactants here because of their impor-
tance to oilfield chemistry.
With few exceptions, surfactants are molecules made up
of a hydrophilic (water-soluble) segment and an
oleophilic (oil-soluble) segment. The hydrophilic seg-
ment of an anionic surfactant is negatively charged in
water. Examples are carboxylates, sulfonates, sulfates,
phosphates, and phosphonates. Cationic surfactants are
positively charged at the hydrophilic segment of the
molecule. This positive charge is associated with a qua-
ternary nitrogen (i.e., a nitrogen atom covalently bound
to four substituents). Examples are quaternary ammo-
nium salts. As the name indicates, nonionic surfactants
do not have a charged segment. The hydrophilic seg-
ment is a polymer of ethylene oxide.

The degree of surfactant solubility in water is controlled
by the relative size and weight of the hydrophilic and
oleophilic segments of the molecule. Hence, the larger
the hydrophilic segment relative to the oleophilic seg-
ment, the greater the water solubility and vise versa.
The most common interaction between surfactants is
between cationic and anionic surfactants. Mixing a
cationic and an anionic molecule cancels the charges on
the respective hydrophilic segments. The surfactants
drop out of solution (precipitate) as a large, water-in-
soluble molecule.
Demulsifier/Reverse Demulsifier Interactions

An example of the possible interactions between different
surfactant systems used in water treating involves
demulsifiers and reverse demulsifiers. Demulsifiers and
reverse demulsifiers interact in several ways. We will
describe the chemistry of these surfactant systems first.
Description of Demulsifier Chemistry

Demulsifiers typically are blends of chemicals designed
to resolve oil-external emulsions and assist in primary
crude dehydration. The mechanism of “demulsification”
is four-fold. Initially, the demulsifier migrates to the oil/
water interface. Then it ruptures the interface film,
coalesces the water droplets, and finally water wets any
solids present.
The demulsifier chemical usually is a blend of different
components in a variety of solvents. This blend not only
affects how the demulsifier performs but also influences
the compatibility of separated water with other produc-
tion chemicals.
Demulsifier chemistry is complex. Many demulsifiers
contain three or more active components blended in a
solvent cocktail. Typical components include
oxyalkylated phenol formaldehyde resins (nonionic),
oxyalkylated glycols (nonionic), and amines (cationic).
One component of the demulsifier usually is a wetting
agent. This constituent causes most of the incompatibil-
ity problems.

Reverse demulsifiers help remove oil from produced
water. They are also known as “reverse breakers” and
“de-oilers.” They can be surfactants to promote wetting,
coagulants to neutralize surface charge on the oil drop-
lets, flocculants, or true coalescers (making large drops
out of small drops).
Most chemicals available today offer a combination of
properties designed to enhance the operation of oil/
water separation equipment. Of the chemical types
available, cationic polyamines are used most often.
These chemicals have good coagulation/flocculation
capabilities and offer a surface active nature. This surface
active nature is useful in flotation where an oil-rich foam
is the desired waste-stream phase.
Treatment Problems and Interactions

Demulsifiers
Choosing the correct dosage is essential in demulsifier
treating. Underdosing will usually result in high basic
sediment and water (BS&W) in the crude and dirty water.
Overdosing often results in dirty water, stabilized reverse
emulsions (oil in water), and interface buildup in separa-
tion vessels.
Overdosing will also cause problems if a reverse
demulsifier is used downstream of the separators. Excess
demulsifier will be present at the interface of the oil
droplets in the water phase, in essence forming a skin
around the droplets or an agglomerate of a complex oil-
in-water-in-oil emulsion. This will render the reverse
demulsifier ineffective because it cannot neutralize the
surface charge on the droplets to promote flocculation.
Solid particles that are not water-wet may also be present
in the emulsion. This mixture is often a gelatinous floc
that can plate out on separator plates or on the diffuser
baskets of flotation cells. This plating out of solids-
stabilized emulsions is enhanced when excess reverse
demulsifier is present in the water.
To minimize the effects of overdosing and underdosing,
choose demulsifiers that operate on a wide treatment
plateau. Thus, a small change in dosage rate will not

affect the treatment capability of the chemical. Careful
bottle testing and field evaluation of chemicals can
achieve this.
Fig. 1 shows treatment plateaus for good and poor
demulsifier selections. Note the wide treatment range of
the good demulsifier. This gives a flexible treatment
profile that will not cause problems if production rates or
the chemical injection rate vary slightly.
Reverse Demulsifiers
Underdosing reverse demulsifiers usually results in
inefficient operation of separation equipment. In flota-
tion and plate-pack separation, the oil droplets need to be
as large as possible to maximize separation efficiency. If
the reverse demulsifier is underdosed, optimum droplet
coagulation/coalescence will not occur; thus, separation
efficiency is reduced. In a flotation system, the reverse
demulsifier also acts as a foaming agent, which is needed
to minimize the skimmed liquid volume. If the chemical
is underdosed, foaming may not occur and a large vol-
ume of oily water has to be skimmed to maintain oil

removal efficiency. This generates a waste-stream vol-
ume significantly greater than the oily foam skimmed
from an optimized vessel.
Overtreating with a reverse demulsifier can cause a
number of problems. Of primary concern is the forma-
tion of a separated oil stream that is essentially a stabi-
lized emulsion. This stabilized emulsion can be the
skimmings from a flotation cell, the separated oil from a
plate-pack separator, or the reject stream from a liquid/
liquid hydrocyclone (see Chapter 3). Overdosing with
the reverse chemical can make this waste stream virtually
untreatable (see Chapter 10). Inevitably, this waste
stream is not dry oil but an oil/water mixture.
The ratio of water to oil can be 1:1 up to 10:1; hence,
further separation of the phases (additional equipment,
chemicals, and costs) is required to recover the oil and
dispose of the water. If this mixture is stabilized by
excess chemical, it will have to be treated as a separate
stream. Recycling this waste stream into upstream sepa-
ration equipment will cause problems. The mixture will
build up an interface emulsion pad that will eventually
cause primary dehydration problems.
Another problem with overdosing reverse demulsifiers
relates specifically to induced-gas flotation (IGF) systems.
In IGF systems, the gas is induced by a rotor and diffused
into the water by a diffuser basket. The diffuser basket
ensures uniform distribution of gas bubbles into the
flotation cell. The holes in the basket are susceptible to
fouling with corrosion products and scale and must be
cleaned.
Excess reverse demulsifier will increase the fouling
process by acting as a “glue” for solids particles and
stabilized emulsions in the water, which then adhere to
the basket and plug the diffuser holes. This buildup not
only impedes flotation performance but also reduces
efficiency of oil droplet coagulation because the chemical
is expended flocculating solids, not oil droplets. In this
operating mode, determining an optimum chemical dose
is very difficult. At this point, the flotation cell should be
cleaned out and returned to service, and the chemical
should be optimized.

When optimizing reverse demulsifiers in an IGF system,
a good rule of thumb is to increase the dosage of chemi-
cal until foam is generated and then reduce the dosage
rate by 20%. If the foam remains, reduce the rate by an
additional 20%. In many cases, foam generation requires
50% more chemical than foam propagation and adequate
coalescence.
Other Surfactant Interactions

Recycling a waste stream in a water treatment system can
cause problems when the waste stream contains surfac-
tant chemicals that can react with other surfactants added
during water treatment. For example, if the surfactant
added to the filter backwash is anionic (see Table 2) and
is recycled upstream of an IGF oil/water separation unit
that is using a cationic polyamine, an anionic/cationic
interaction will occur. If the treatment plateau is too
narrow, some underdosing problems can occur.
In another example, the initial production from a well
that has been squeezed with an anionic scale inhibitor
contains a high concentration of the inhibitor (>1,000
ppm). If this surfactant is not sufficiently diluted with
the water from other producing wells, an anionic/cat-
ionic interaction could result in the IGF unit to cause an
upset in the system.
As noted, another waste stream that often causes upsets
to a water treatment system is the produced water from a
well that was recently acid stimulated. In addition to
“spent” acid, this water often contains suspended solids,
solids-stabilized emulsions, sludges (paraffins, waxes,
etc.), and various surfactants added to the acid (wetting
agents, demulsifiers, dispersants). The potentials for
surfactant interactions and for the treatment plateaus to
“fall off” in the oil/water separation and filtration equip-
ment are obvious. Such waste streams (including water
from acidized wells, workover fluids, tank bottoms, etc.)
should be neutralized, pretreated, and slowly added to
the water treatment system to minimize their detrimental
effects on the system chemistry.

Biocide Reactions
By their very nature, biocides are very reactive. They are
often used in relatively high concentrations (in the case of
aldehydes) and are very water-soluble.
The strong oxidizers include chlorine and hypochlorite
compounds (both of which function as oxidizing biocides
in water as the hypochlorite ion) and chlorine dioxide.
These compounds are excellent biocides, but their associ-
ated corrosive properties limit their use and concentra-
tion. As strong oxidizers, they will react with organic
material in the water and reducing agents, such as sulfite-
based oxygen scavengers. Oxygen scavengers will be
consumed preferentially by residual chlorine or hy-
pochlorite ions in the water before being available for
reaction with dissolved oxygen.
The aldehyde and amine-type biocides operate by a
different biocide mechanism than strong oxidizers do.
They attack and poison the bacterial cell walls. The
amines also have surface active properties to loosen the
bacteria colonies and byproducts from surfaces. Sulfite-
based oxygen scavengers react with aldehydes, which are
reducing agents. The aldehydes also react with H 2S in
sour water systems. We should consider these interac-
tions when determining where these two types of chemi-
cals will be injected in a water handling or treatment
system.
Another potential interaction involving aldehydes could
occur when acids are dumped into the treatment plant
feedwater. In the presence of strong acids, like hydro-
chloric, aldehydes condense with a variety of compounds
containing the -NH2 group (the functional group of many
corrosion inhibitors).
Strong Acid Reactions

In general, strong acids injected into the feedwater can
cause many detrimental effects in a water treatment
system. A large drop in pH can alter the effectiveness of
many oilfield chemicals. Most are designed to function
in a pH range of about 6.5 to 7.5. In addition, the lower
pH caused by acid will increase the corrosion rate; in-
crease the dissolved iron in the water, which in turn will

precipitate as the pH rises again; and increase the sus-
pended solids in the water by loosening deposits from
the equipment surfaces.
SOME DO’S AND DON’TS WITH RESPECT TO

CHEMICAL INTERACTIONS
1. Understand the “character” of every water going to
the water treatment system. Each water is indi-
vidual. “Water” is not just “water.” Analyze the
waters in terms of inorganic and organic components
(see Chapter 2). This is the fundamental principle for
minimizing interactions between waters and injected
chemicals. Look for potential scaling reactions (see
Chapter 5).
2. Don’t use the water treatment system as a “sewer”
for disposing of the waste streams of the field.
3. Minimize waste-stream recycling within the water
treatment system (see Chapter 10). Know the poten-
tial effect of each waste stream on the overall system
and the individual components that make up the
system.
4. Follow the total system approach in designing the
system chemical requirements. Recognize the inter-
relationships between the system components - i.e.,
how filter operation affects the oil/water separator
and vice versa. Establish a total system chemical
profile. What chemicals are added? Where? What
are the potential interactions? Carefully choose the
chemical injection points.
5. Establish treatment plateaus for all system compo-
nents, filters, oil/water separators, de-aerators, etc.
6. Don’t shock the system with spent acids, workover
fluids, tank bottoms, pit liquids and solids, and
other waste streams. Neutralize and pretreat these
streams before adding them to the water treatment
feedwater.

GLOSSARY
Anionic chemical — a chemical having a negative
charge.
Antifoamer — a chemical used to control foam formation
in oil/water separators, de-aerator and similar units.
Cationic chemical — a chemical having a positive
charge.
Coagulant and flocculant — a chemical used in gas
flotation unit and media filter to separate oil and
suspended solids from produced water.
Demulsifier (emulsion breaker) — a chemical used to
improve oil/water separation or help remove water
droplets from oil.
Gas dehydration chemical — a chemical used to remove
water from the natural gas.
Hydrate inhibitor — a chemical added to the associated
water to inhibit hydrate formation in gas production.
Nonionic chemical — a neutral chemical having no
charge.
Oxygen scavenger — a chemical used to remove oxygen
of the production system.
Reverse Demulsifier (Reverse breaker) — a chemical
used to help remove oil droplets from water.
Stimulation acid — an acid used in well stimulation.
Sulfide scavenger — a chemical used to remove hydro-
gen sulfide of the production system.
Surfactant — a surface active agent.
Viscosifier — a chemical used to control viscosity.

C H A P T E R
Water/Formation
Rock Interactions
Chapter 9: Water/Formation Rock Interactions 9-1

INTRODUCTION
Many formation rocks, particularly sandstones, are
subject to formation damage when they come in contact
with waters having chemical properties significantly
different from the natural connate water of the formation.
Formation damage is usually indicated by a permeability
reduction in the rock owing to chemical and physical
changes of the rock minerals. These changes cause clay
and other particles to swell and/or migrate, some miner- Any operation in which
als in the rock to dissolve, or plugging solids to precip- the formation rock comes
itate. As a result, the small flow channels within the rock
in contact with a foreign
porosity are blocked off. Formation damage may cause
only a small drop in or up to a total loss of permeability. fluid can damage (reduce
Oilfield operations (drilling and completion, workovers, the permeability of) the
stimulation jobs, waterflooding, water disposal) can formation.
damage the formation around the wellbore. Any opera-
tion in which the formation rock comes in contact with a
foreign fluid can damage some formations. While this
chapter focuses on the effects of water injection, the
causes of formation damage and the methods of prevent-
ing water/formation rock interactions generally apply to
other oilfield operations.
Mechanisms of Formation Permeability

Damage
Formation Clay Deflocculation and Migration

Deflocculation of clays (and other fines) in sandstone
reservoirs causes them to become detached, move down-
stream with the flowing fluid, and lodge in pore constric-
tions where they decrease reservoir permeability. A
principal cause of clay deflocculation is the electrostatic
repulsion forces resulting from the clay’s electric double
layer.1
Clay minerals have a net negative charge that is neutral-
ized by cations (positive charged ions) residing in a
cation swarm on and near the mineral surfaces in clay
water systems. When two or more clay particles are close
enough for the ion swarms to overlap, the particles tend
to repulse each other. The thickness and intensity of the
ion swarm determine the magnitude of the repulsive

forces between particles and the tendency of clays to
deflocculate in water. These forces can be greatly affected
by the chemical composition of the pore water. Repul-
sive forces are highest where the pore water has a low
electrolyte concentration (fresh water) and the cation
exchange complex of the sandstone is saturated with
monovalent cations (e.g., sodium ions).2
In addition to the repulsive forces acting on reservoir
fines during injection of water with the chemical compo-
sition described above (low electrolyte concentration),
the movement of pore fluids through flow channels at a
relatively high velocity causes hydraulic drag forces on
the fines.3 Usually, a fines-containing rock has a critical
flow rate above which fines dislodge, move downstream,
and plug flow channels. The critical flow rate for fines
migration is very specific to the individual rock, to previ-
Fresh water promotes ous chemical treatments, and to the chemical composi-
formation damage tion of the flowing fluid.
whether the mechanism is
Formation Clay Structural Expansion
clay deflocculation or
Expanding clays, such as smectites, can adsorb polar
structural expansion.
molecules (like water) between the clay layers. In a
dehydrated state, the distance between repeating struc-
tures (basal spacing) in smectites is about 10 Angstroms
(10-8 cm). Under reservoir conditions, the basal spacing is
perhaps 14 to 20 Angstroms. When the reservoir
smectites are saturated with sodium ions and washed
free of salts, the spacing may increase to 30 Angstroms or
more. The direct effect of this expansion is that the pore
space available for fluid transport is consumed.
The direct effects of these relatively large increases in clay
structure volume are not very important in most reser-
voirs because the expandable clay percentage is usually
<1%. In some rare cases, however, reservoirs contain as
much as 5% to 10% smectite. In those cases, if the clay
volume is doubled or tripled by structural expansion, the
effective porosity and flow capacity may decrease sub-
stantially.
A secondary effect of clay structural expansion usually
has a much greater impact on permeability than the
direct effect of decreasing pore space. That is, the ex-
pandable clays are usually intimately associated with

other types of clays that are far more abundant. When
the smectites expand, the associated nonexpanding clays
(and the expanded clays) tend to destabilize, migrate,
and plug flow channels.
Particle migration is the principal operating damage
mechanism, even in some high-clay rocks where smectite
is the dominant clay type. Evidence for this is in the
following observations. When these smectitic rocks come
in contact with fluids designed to expand but not
deflocculate the clay, their permeability usually declines.
If the damaged rock then comes in contact with a fluid
that causes the clay structure to collapse to its original
spacing, the permeability recovers only slightly. When
fluid that protects the clays against both expansion and
deflocculation passes through this rock, the permeability
is stable. This suggests that the permeability damage
mechanism is largely particle migration, not consump-
tion of pore space by expanding clays, even though the
triggering mechanism is structural expansion.
Mica Alteration
Micaceous minerals, such as micas and illites, are nor-
mally not considered expandable, but they can undergo Injecting non-potassium
alterations that cause their structures to expand.4 Mica-
brines into a mica-rich
ceous minerals are layered, much like smectites, except
the layer charge is substantially higher and the seat of the reservoir can result in
charge is closer to the surface. Thus, the mineral is much formation damage.
more difficult to expand, and the interlayer cations are
nearly nonexchangeable. Interlayer cation sites are filled
almost exclusively with potassium ions. Interlayer sites
are very specific to potassium because potassium ions
have a low hydration energy and fit nicely in the hexago-
nal holes between the layers. This allows the structure to
remain collapsed with a 10-Angstrom basal spacing.
Even though the interlayer potassium ions are relatively
nonexchangeable, micaceous minerals in contact with a
non-potassium-salt solution will slowly lose interlayer
potassium to the solution. The interlayer sites are highly
selective for potassium ions. But when the edges of the
particles are in contact with a solution having an over-
whelming abundance of competing ions and a very low
concentration of potassium ions, some interlayer potas-

sium ions near the particle edges diffuse out of the
interlayer space and competing ions from the solution
diffuse into the interlayer space to replace them. This
continues until the potassium concentration in the solu-
tion increases to a level that tends to curtail the exchange
process. If the potassium concentration in the solution is
somehow continually kept very low, the process contin-
ues until essentially all the interlayer sites are filled with
the competing ions.
The effects of this interlayer potassium extraction on rock
permeability can be serious in reservoirs that contain a
large amount of micaceous minerals. Interlayer potas-
sium ions are usually replaced by sodium ions that are
highly hydrated and cause the mineral structure to ex-
pand and distort at the particle edges during extraction.
This distortion causes the mica particles to break up, with
pieces flowing downstream and plugging flow channels.
In oilfield operations where non-potassium-salt solutions
are injected into formation rocks, the potassium concen-
tration in the flowing solution is kept low in the near-
well region by continual replacement with fresh solution.
Therefore, interlayer potassium is removed continually
and slowly from any micaceous minerals in the rock
while the salt solution is injected. This has caused seri-
ous formation damage problems in some sandstones
during drilling, completion, water injection, and other
operations in formations containing large amounts of
micas and illites.4
Differential Dissolution
Differential dissolution describes a permeability damage
mechanism in which permeability is decreased by less
Differential dissolution is
soluble migrating fines released by the dissolution of
a damage mechanism in more soluble rock components. 3 Most reservoir rocks,
which less soluble particularly sandstones, consist of a mixture of many
migrating fines are different minerals. Each has its own solubility and disso-
lution rate in a given brine solution.
released by the
dissolution of more Temperature, pH, and water composition affect solubility
and dissolution rates. During flow of a particular brine
soluble rock components.
solution through the rock, some minerals may readily
dissolve; others may dissolve very slowly; others may be
essentially insoluble in the solution. If the different

minerals are intimately associated or attached, then
dissolution of the more soluble components causes insta-
bility in the remaining less soluble components. The
resulting loose particles are then free to move down-
stream to plug pores and damage permeability. This
damage mechanism should be of concern whenever the
rock comes in contact with a solution that may dissolve
part of the minerals in the rock, especially during well
treatments with acids, bases, and steam.5
Because of Chevron’s extensive steam EOR operations,
we should note sandstone dissolution during steam
injection.5 The water solubility of quartz and other sili-
ceous minerals (e.g., clays and feldspars) increases rap-
idly at high temperature and high pH. When HCO3 ions
(bicarbonate alkalinity) in steam generator feedwater
decompose to CO2 and OH ions, the CO 2 partitions to the
vapor phase, and the OH ions partition to the liquid
phase (steam quality is usually about 80%). The result is
a rise in pH of the generator liquid effluent dependent on
the HCO3 ion content in the feedwater and the steam
quality. Consequently, during cyclic steam stimulation or
steamdrive operations, hot (500°F), high-pH (11 to 12)
water can reach and dissolve many of the siliceous min-
erals that make up the sandstone rock matrix.
Dissolution and Reprecipitation

When we inject a rock-dissolving brine solution into a
formation, rock dissolves relatively rapidly near the
wellbore.4 But as the solution moves through the forma-
tion, the reactants are used up and products accumulate
in the solution. This continues until the solution is satu-
rated with at least some reaction products.
In simple single-mineral systems, we would predict no
further reactions, but in complex multimineral rocks,
further reactions are likely downstream from the major
dissolution zone. As the solution composition changes,
some reaction products react with each other to form new
insoluble materials, which produce pore-plugging pre-
cipitates. A permeability damage zone immediately
downstream of the dissolution zone results.

A specific example of this type of water/formation rock
interaction is the dissolution of calcium sulfate anhydrite
followed by reprecipitation of the calcium and sulfate
ions as gypsum (CaSO4 . 2H2O) during water injection at
temperatures below 95 to 104°F (35 to 40°C). At this low
temperature, anhydrite is more water-soluble than gyp-
sum. The possible negative effect on permeability from
this precipitate in the rock pore space is compounded by
the lower density of gypsum (it has a greater volume)
than anhydrite.
Another specific example of this type of reaction occurs
when siliceous minerals dissolved during steam injection
precipitate when the water cools and changes pH as it
moves out from the injection wellbore.
Precipitation
In some circumstances, a dissolved constituent in an
injection water can precipitate from the water by reacting
with minerals in the injected formation rock. An example
is the precipitation of dissolved iron ions by reaction with
alkaline minerals, such as calcite and dolomite. The
problem is worsened by the presence of dissolved oxy-
gen in the water. The precipitated iron compounds
(mostly iron hydroxide) may plug the pore space and
damage permeability.
Identifying Potential Formation Permeability

Damage
The permeability of susceptible reservoirs can be dam-
The key to maximizing aged many ways during water injection. The key to
maximizing injection efficiency is to prevent damage,
injection efficiency is to
instead of using remedial treatments after the fact. When
prevent damage, instead planning of each stage of a water injection project, we
of using remedial should consider the risks of formation permeability
treatments after the fact. damage.
Designing preventive methods for a particular formation
is best done with the knowledge and understanding of
the operating damage mechanisms. However, this infor-
mation is frequently unavailable and usually requires
extensive laboratory investigation. In addition to identi-
fying the clay types and other minerals in a formation,

some generally applicable preventive methods markedly
reduce the risk of formation damage in susceptible for-
mations. These preventive methods are based on the
premise that the most frequent cause of formation perme-
ability damage is pore plugging caused by (1) migration
of native clays triggered by deflocculation forces, (2) for-
mation of precipitates from mixing of incompatible
fluids, and (3) injection of fine solid particles from dirty
completion fluids.
Water and Rock Analyses

Analyses should be carried out to characterize the chemi-
cal nature of the formation water and the water or waters
being considered for injection into the formation. Com-
parison of the waters indicates significant differences that
could cause damage mechanisms. Some differences to be
noted are:
1. pH. A large increase or decrease in pH could cause
mineral dissolution and/or precipitation. Analyses should be done
2. Alkalinity. Alkalinity changes could cause precipita- to characterize both
tion and dissolution/precipitation. waters and the formation
3. Sulfate ion. Increases could cause dissolution and/or rock.
precipitation.
4. Salinity. Large changes could trigger damage mecha-
nisms.
5. Temperature. High-temperature waters (steam) could
cause dissolution/precipitation.
6. Principal cations. Large changes in Ca, Mg, Na, and K
ion content could trigger damage mechanisms.
7. Minor cations. Changes in Fe, Si, Sr, and Ba ion con-
tent could indicate potential precipitation reactions.
In conjunction with water analyses and laboratory core-
flood tests (described below), X-ray diffraction analyses
should be carried out to identify the minerals that make
up the formation rock, particularly as they relate to the
damage mechanisms. Of special interest are the types
and abundance of clays.

Scanning electron microscopic analysis can complement
the mineral analysis by indicating where the clays and
other minerals are in the rock fabric and how the rock
grains are cemented together.
Proper Salts and Concentrations

To determine the minimum salt concentration and com-
To determine the position, we must make some laboratory measurements
on representative field cores. Technical Memorandum
minimum salt
TM88000115, “Procedure for Determining Effects of Salt
concentration, make Water Concentration on Permeability of Sands,” is in-
laboratory measurements cluded in the Appendix. This memorandum outlines the
in representative field recommended procedure for conducting these measure-
ments. The laboratory measurements are carried out by
cores.
flowing different concentrations of a particular salt solu-
tion through each of several representative core plugs
and measuring the stable single-phase permeability to
each solution.
We start by flowing the most concentrated salt solution to
a stable permeability. Then we successively flow solu-
tions that are about half the concentration of the previous
solution. In each case, we record the stable permeability
for each solution. Fig. 1 shows plots of typical stable
permeability data for two very different sands.
At the higher salt concentrations, the curves are flat; at
some lower concentrations, however, each curve forms a
shoulder with the permeability declining more steeply as
the salt concentration approaches zero. Using curves for
several representative core plugs, we can select the mini-
mum concentration of salt necessary to prevent damage
in that particular rock. As usual, the smectitic sand
required a much higher concentration of salt to prevent
permeability damage than the kaolinitic/illitic sandstone
did.
Fig. 2 shows similar data obtained on plugs from the
same sands using potassium chloride rather than sodium
chloride solutions. A comparison of the results in Figs. 1
and 2 for potassium and sodium salts shows that lower
concentrations of potassium salts are required to prevent
permeability damage effectively.

Figure 1 Effect of NaCl Concentration on Permeability of Two Different Sands

Figure 2 Effect of KCl Concentration on Permeability of Two Different Sands

Similar laboratory tests are recommended with represen-
tative core samples to identify possible water/formation
rock interactions using actual field waters being consid-
ered in an injection project.
PREVENTING FORMATION DAMAGE IN THE

FIELD
When a program of water and formation rock analyses
and laboratory tests has indicated the potential of forma-
tion damage if a particular water is injected into a forma-
tion, three alternatives are possible to prevent that dam-
age:
1. Select the least damaging water from the available
injection water sources. Three options to
2. Modify the chemistry of a damaging water to make it minimize potential
minimally damaging. damage include selecting
3. Treat the formation rock to make it less susceptible to the least damaging brine,
damage by the injected water. modify injected water
Depending on the degree of damage judged to be accept- chemistry, or treat the
able, the first alternative is the most economical. How- near wellbore formation.
ever, this choice includes the costs necessary to make a
specific water available, such as drilling source wells and
installing flowlines, oil/water separation treatment of
produced water, filtration, etc. Each water has its own
specific treatment requirements.
The second alternative (e.g., adding potassium ion to
prevent mica alteration) usually is not economically
acceptable for water injection projects where continuous
treatment is required. Such treatments may be justified
for waters used for drilling or completion practices.
Lowering the pH of a steam generator effluent water may
be considered if a lower-bicarbonate alkalinity feedwater
is not available.
The third alternative offers two general methods of
pretreating the formation rock around a wellbore before a
water that could cause formation damage is injected:
(1) injection of a CaCl2, KCl, or NH4Cl brine or (2) injec-
tion of a polymeric clay stabilizer. The first method is
less costly. However, treatments by the second method,

unlike the first, are not subject to removal by changes in
the cations in the injected water. Two technical articles
describing these methods are included in the Appendix.
The first article, Sheuerman and Bergersen’s6 paper,
describes a method of selecting a brine pretreatment
based on formation clay type, content, and cation ex-
change capacity, and the injection water total cation
concentration and mass action ratio (the square of the
monovalent cation concentration in meq/mL divided by
the divalent cation concentration in meq/mL).
The second article, by Hesterberg and Reed,7 evaluates
three commercial clay stabilizers in terms of volumetric
treatment efficiencies and cost-effectiveness. Included in
the study were an inorganic aluminum polymer
(hydroxyaluminum), an organic polyquaternary amine,
and an organic quaternary surfactant. Based on a com-
parison of volume treated and cost, hydroxyaluminum
was twice as cost-effective as polyquaternary amine and
eight times more cost-effective than quaternary surfac-
tant.

REFERENCES
1. van Olphen, H.: An Introduction to Clay Colloid Chem-
istry, Interscience Publishers, New York City (1963).
2. Kia, S. F., et al.: “Effect of Salt Composition on Clay
Release in Berea Sandstone,” SPEPE (Nov. 1987) 277-
83.
3. Muecke, T. W.: “Formation Fines and Factors Control-
ling Their Movement in Porous Media,” JPT (Feb.
1979) 144-50.
4. Reed, M. G.: “Formation Permeability Damage by
Mica Alteration and Carbonate Dissolution,” JPT
(Sept. 1977) 1056-60.
5. Reed, M. G.: “Gravel Pack and Formation Sandstone
Dissolution During Steam Injection,” JPT (June 1980)
941-49.
6. Scheuerman, R. F. and Bergersen, B. M.: “Injection-
Water Salinity, Formation Pretreatment, and Well-
Operations Fluid-Selection Guide,” JPT (July 1990)
836-45.
7. Hesterberg, D. and Reed, M. G.: “Volumetric Treat-
ment Efficiencies of Some Commercial Clay Stabiliz-
ers,” paper SPE 18466 presented at the 1989 SPE
International Symposium on Oilfield Chemistry,
Houston, Feb. 8-10.

GLOSSARY
clay stabilizers — chemicals that prevent clays in the
reservoir from migrating and thereby reducing per-
meability.
clays, expanding types — clays that have an ability to
swell and increase in volume. This tendency is pro-
moted by contacting them with fresh water.
deflocculation — the process by which clays dislodge
themselves from the pore walls and become mobi-
lized.
differential dissolution — process in which less soluble
migrating fines are released by the dissolution of
more soluble rock components.
formation damage — decrease in reservoir permeability.
hydroxyaluminum — chemical that is one class of clay
stabilizers.
mica alteration — injecting potassium-free water can
lead to the substitution of potassium in mica minerals
with sodium. This process can destabilize the mica
and cause formation damage from released particles.
migration — the movement of fines and clays. A com-
mon formation damage mechanism.
organic polyquarternary amine — one class of clay
stabilizer chemical.

APPENDIX

C H A P T E R
10
Handling Separated Wastes
Chapter 10: Handling Separated Wastes 10-1

INTRODUCTION
During treatment of oilfield waters — whether for water-
flooding, EOR, steam generation, or just separation of oil
and gas from produced water — waste streams are gener-
ated when unwanted constituents are separated from the
water. These waste streams are generally made up of
multiple phases of water, suspended solids, and oil (and
sometimes gas) in varying proportions. The water and
oil phases contain various dissolved inorganic and/or
organic species. These waste streams, in turn, may re-
quire further processing before disposal. Environmental
regulations and economics are major factors in control-
ling the method of handling, processing, and disposing
of the separated wastes.
This chapter discusses the origin and methods of han-
dling separated wastes from the treatment of oilfield
waters. Note that many of the procedures and much of
the technology presented are not routine oilfield practice.
The procedures are presented as recommendations where
routine practices might be improved, particularly where
they affect oilfield water treatment and disposal of the
resulting waste streams. In addition, this chapter reviews
the environmental aspects of handling the separated
wastes, including the criteria for land and injection well
disposal.
ORIGIN OF WASTE STREAMS

The primary objective of treating oilfield waters is to
remove one or more unwanted constituents (dissolved, Effective oilfield water
emulsified, or suspended) from the water to prepare for treatment must generate
its disposal or utilization (waterflooding, EOR, etc.)
Thus, by its very nature, the treatment of oilfield waters one or more waste
generates waste streams. In fact, effective oilfield water streams.
treatment must generate one or more waste streams.
Fig. 1 shows the overall, but simplified, process of gener-
ating waste streams in a water treating system. The
water to be treated, “water in,” is shown as being made
up of water, oil, solids, and/or gas. The “water out” is
shown as containing oil and solids, presumably of accept-
able concentrations (quality) for the water to be disposed

of or used the field. In treating the water to achieve this
quality, we generate four general classes of waste
streams:
1. Separated solids — streams made up of solids that
also contain some water and oil.
2. Separated oil — streams made up mostly of oil that
also contain some water and solids.
3. Separated gases — streams made up of mixtures of
gases.
4. Separated water — streams made up mostly of water
that contain some oil and solids; these streams usually
require further processing but have a smaller volume
than the treated “water out”.
Note that in most cases these four waste streams require
additional, separate handling and processing before they
can be utilized or disposed of.
Table 1 shows some water treatment waste streams
included in the four types.
Table 1 Waste Streams

Separated Separated Separated
Solids Separated Oil Gases Water
Tank Bottoms Produced Produced Gas Water Softener
Crude Spent Brine
Filter Pit Sludges H2S and CO2 Water from
Backwash Batch Treating
Tanks
Pit Bottoms Oil/Water
Separation
Skimmings
Sand Pan Hydrocyclone
Solids Separated Oil
Hydrocyclone Tank
Separated Skimmings
Solids
Several of these waste streams are “waste” not in the

sense that they have no value, but in the sense that they
must be removed from the treated water to achieve the

desired water quality. Examples of such waste streams
with value are the crude and gas separated from the
water.
Fig. 2 further illustrates the generation of waste streams
for the produced-water treatment. As noted, the pro-
duced water contains oil, chemical additives used in the
field (surfactants, scale and corrosion inhibitors, biocides,
etc.), gases, and solids plus dissolved organic and inor-
ganic constituents. Fig. 2 also shows gas and/or chemi-
cals added to the various processing units of the treating
system as part of their operational requirements. In Fig.
2, six waste streams are generated from the treatment of
produced water.
One waste stream, ”system accumulation,” is very impor-
tant. Any constituent in the produced water that is The “system
separated in the water treating system but does not end
accumulation” waste
up in one of the waste streams exiting the system will
build up within the system in the form of scale, sludge, stream should be
tank bottoms, etc. These become the system accumula- minimized, otherwise
tion waste stream. Such accumulations negatively affect water quality will suffer.
the efficiency of filters, flotation cells, separators, and
other water treating equipment. This declining efficiency
can lead to a situation where the unwanted constituents
of the produced water are not removed effectively, the
quality of the treated water declines, and eventually the
quality of the treated water is similar to that of the pro-
duced water in.
The flow diagram in Fig. 2 emphasizes another extremely
important point about the generation of waste streams in
a water treating system. In water treatment plant design,
It is generally better to
there is a strong temptation, and indeed it is a common
practice, to minimize the number of waste streams by minimize stream recycles
recycling them back into the system. As discussed below, and treat each waste
recycling has a place in a water treatment system. How- stream separately.
ever, waste streams are often recycled without consider-
ation of their impact on the system. For example, filter
backwash, water separated from flotation cell skim-
mings, pit sludges, tank bottoms, backflow from well
workovers, and other oilfield wastes (with all their asso-
ciated chemical additives) are often piped back and
combined with the produced water entering the system.
Often, the result is as illustrated in Fig. 3. As can be seen,

all waste streams except one have been recycled. Only
the system accumulation remains. Eventually, the quality
of the treated water out of the system will be no better
than the quality of the water in. Again, effective oilfield
water treatment must generate waste streams. Designing
a water treatment plant with the overriding objective of
minimizing the number of waste streams does not result
in an effective plant in terms of the quality of the treated
water from the plant. This point is discussed further in
the section on treating separated wastes.
FACTORS IN HANDLING SEPARATED WASTE

STREAMS
Minimizing Arbitrary Recycling
Recycling separated waste streams back into a water
treatment system without proper consideration of their
effects negatively affects the efficient operation of the
system:
1. As demonstrated above, recycling waste streams
causes the unwanted wastes (sludges, scale, sus-
pended solids, etc.) to accumulate in the system
(bottoms of tanks, piping, gas flotation vessels and
others separators, filter vessels, and water softeners)
to the point where these units no long operate effi-
ciently. In addition, the accumulations lead to in- Recycling waste streams
creased scaling, corrosion, solids generation, and causes unwanted wastes
bacterial activity. Effective system cleanliness be- to accumulate, leaves the
comes impossible. entire system vulnerable
2. Recycling waste streams makes the entire water to upsets, and it mixes
treatment system vulnerable to upsets of the indi-
chemical additives from
vidual treating units where the waste streams are
generated. For example, the backwash from sand all parts of the system.
filters is often recycled back into the front end of the
water treatment plant. Consequently, when the filters
suffer an upset, a large slug of solids and sludge enter
the feed water in, and an induced-gas flotation unit
(IGF) upstream of the filters is also upset, which
affects the feed to the filters and further upsets the
filter operation.

3. Recycling the waste streams mixes the chemical
additives from all parts of the system. In the example
above, surfactants added to the filter backwash to
clean the filter media end up in the feedwater to the
IGF, where they mix with the surfactants added to
assist the IGF. One surfactant may be cationic and the
other anionic. Consequently, they interact, possibly
forming a precipitate. Thus, even more chemical
must be added to the IGF feed to react with the filter
backwash surfactant, to counter detrimental effects of
the precipitate, and to maintain the separation of oil
in the IGF. A host of detrimental chemical interac-
tions and incompatibilities can be expected when the
waste streams are arbitrarily recycled.
4. A common practice in many oil fields is “indirect
recycling.” This practice involves the dumping of all
kinds of oilfield waste waters (filter backwash, tank
bottoms, IGF skimmings, workover fluids, acid
wastes, other stimulation liquids, etc.) into a pit or
tank. The waste waters sit in the pit, where they
interact, weather, and form precipitates and organic
skins, sometimes called “animal hides.” During this
time, the water from the pit, containing all sorts of
chemicals, is being recycled to the water treatment
system. Recycling such water can cause all the inter-
actions and system upsets described above. Because
the chemistry and volume of the water vary, we have
little or no chance of controlling the detrimental
effects of this indirect recycling.
Incorporating Point-Source Treating Into the

System Design
As stated above, separated waste streams from a water
Many problems
treatment system generally require additional treating
associated with separated before disposal or use. Many problems associated with
waste-stream handling separated waste-stream handling and water treatment
and water treatment systems can be averted by point source treating. This
concept incorporates two principles: treating the waste
systems can be averted by
as close to its source as possible and keeping the treat-
point source treating. ment volume as small as possible.

These two principles complement each other. The oppo-
site of point-source treating is combining all waste
streams into one large volume and then attempting to
treat the combined wastes together.
Treating a waste stream as close to its source as possible
allows the treatment to be designed specifically for that
stream for maximum treatment efficiency. Effects of
changes in flow rate and water chemistry and interac-
tions with chemical additives in other waste streams are
minimized. Likewise, changes can be monitored and
responded to more effectively.
Keeping the treatment volume as small as possible keeps
the process equipment small. Not all wastes require the
same treatment. One waste stream may require only
chemical treatment with increased residence time in a
tank; another may require filtration or ion exchange.
Mixing the streams could require that the combined
volume be chemically treated and filtered.
In addition, if a single waste stream can be classified as
hazardous, the total combined stream must be classified
as hazardous. Keeping the waste streams small facilitates
monitoring and permits the use of special equipment that
works better on a small scale. For example, plate-in-
frame and cartridge filters are more practical on a small
scale.
Concentration of Separated Wastes

An important step in handling separated wastes involves
their concentration before disposal. In this step, the part Two separation processes
of the waste stream that is truly waste to be disposed of is
to concentrate wastes are
separated from the part that can be recycled back into the
system. This is the proper place for recycling in a water filtration and treatment of
treatment system. emulsions.
One separation process for possible use in handling
separated waste streams is filtration to separate solid
wastes from water. Another is continuous or batch treat-
ment of emulsions to separate oil, water, and solids by
chemicals, heat, and residence time.
Filters for separating wastes generally collect the solids in
a concentrated form for disposal. These include cartridge
and dry-cake filters. In cartridge filters, the separated

solids and filter elements are disposed of together. Dry-
cake filters yield a disposable solid product that, al-
though not totally dry, contains much less water and
hydrocarbons than the backwash from ordinary filters.
The solids in the disposable product are a mixture of the
separated solids and a filter aid, such as diatomaceous
earth or perlite. The water from the filters (the filtrate)
may be recycled back to the water treating system, usu-
ally downstream of other filters and oil/water separation
equipment, if no chemical incompatibilities or other
interactions are caused. If chemical incompatibilities or
interactions could occur, the filtrate must be chemically
treated before being recycled, or it must be disposed of
separately (injection well, etc.).
Continuous or batch treatment of emulsions separates oil,
water, and solids by chemicals, heat, and residence time.
The recovered oil can be added to the crude oil from the
field if its quality is high enough not to affect the basic
sediment and water (BS&W) content negatively. Other-
wise, it could require additional treatment and separate
handling. The solids and water require filtration either
by addition to the feed to the large filters in a water plant
(if the chemicals added to break the emulsion are shown
to not cause problems with the filter operation) or by
separate filtration.
Fig. 4 is a schematic of a generalized waste stream treat-
ment process. The waste stream could be any combina-
tion of water, oil (hydrocarbons), and solid phases, such
as IGF skimmings, filter backwash, tank bottoms, and
sludge. The phases are effectively separated into three
streams by the tailored, continuous, or batch treatment of
the specific waste stream with chemicals, heat, or resi-
dence time.
The treatment is assumed to yield oil clean enough to be
added to the produced crude without upsetting the
BS&W limits.
Two alternatives are shown for a water stream assumed
to contain very little oil that requires filtration before
subsurface injection. If returning the water to the water
treating system does not negatively affect system opera-
tion, the water stream is combined with the water before

the filters but after the oil/water separation equipment
(e.g., the IGF unit). If it does affect the system, this water
stream must be handled separately, an operation that
includes the use of guard filters (usually cartridge units)
before the stream is injected into wells. These wells
should be separate from those used in the EOR or water-
flood projects for which the bulk water is being treated.
In turn, the solids-laden, spent filter cartridges must be
disposed of properly.
Fig. 4 shows the solids from the waste stream treatment
process being filtered in a dry-cake filter. The filter cake
is disposed of. The water from this filter (the filtrate) is
handled similarly and with the same restrictions as the
water stream described above; i.e., it is recycled to the
water treatment system or filtered and injected sepa-
rately.
The overall goals of this waste stream treatment process
must be to prevent any negative effects of recycling waste
streams back into the water treating system while mini-
mizing the volume and handling requirements of the
separated wastes.
DISPOSAL OF THE SEPARATED WASTES

In the past, regulations concerning the disposal of waste
Recent and proposed streams in an oil field allowed disposal into open pits; as
road paving material; in land farms; into surface waters
regulations limit the
such as rivers, canals, and oceans (within permitted
number of disposal limits); and in disposal wells. Recent and proposed
alternatives. regulations limit the number of disposal alternatives
within a field. Existing open pits must be cleaned up and
removed, and future pits will not be permitted by the
states (e.g., the California Toxic Pits Cleanup Act). IGF
skimmings, tank bottoms, and other sludges can no
longer be used as road paving material. Land-farm
permits will be difficult to secure because states are
reassessing this disposal method in terms of air emis-
sions. Soon, discharge of oilfield waters into open waters
will not be permitted (i.e., “zero discharge”). Injection
into permitted disposal wells may become the only alternative
within a field. At the same time, the process of obtaining
the permits for new disposal wells is becoming increas-
ingly difficult in terms of time, completion design, moni-

toring requirements, number of regulatory agencies
involved, and costs. The relationship between the in-
jected-water quality and well injectivity is becoming even
more critical since it affects the injection life of the well
(see Chapter 4).
Outside the boundaries of the field, disposal alternatives
have been discharge to open waters, disposal wells, local
sanitation districts, landfills, and in some cases evapora-
tion and percolation ponds. Usually, contractors truck
the waste off-site. The regulatory and permitting pro-
cesses for all these alternatives are becoming progres-
sively more difficult. The environmental aspects of the
various waste disposal methods are discussed below.
Waste Disposal and the Environment

As stated, the primary objective of oilfield water treating
is to remove one or more constituents from the water.
Wastes must be generated to achieve this objective. A
second objective is to minimize the number and volume
of the wastes, particularly because they must be disposed of
in an environmentally safe way. However, as we showed
earlier, this second objective must not be accomplished
by arbitrarily recycling the waste streams back into the
system, resulting in waste accumulation and ineffective
operation of the components of the water treating sys-
tem.
Waste can be recycled to minimize the waste volume
through point-source treating to prevent negative im- In the end, at least one
pacts on system operations. Nevertheless, in the end, at
waste stream (in addition
least one waste stream (in addition to the system accumula-
tion) must remain. This waste (or these wastes) will be of to system accumulations)
the following general types: must be disposed of.
1. Water — having a property that makes it unusable for
waterflooding, EOR, or some other field use or for
recycling to the water treating system. Water that
falls into this category may have:
• Extremely high or low pH.
• High unfilterable suspended solids content.
• High concentration of surfactants or other chemi-
cals.

• Excessive hardness.
• Extremely tight oil/water/solids emulsions car-
ried by the water.
2. Oil sludge — tightly emulsified with water and solids
recovered from:
• Pits.
• Separator skimmings.
• Other tank skimmings.
3. Filtered or settled solids — still containing some oil
and water recovered from:
• Pits.
• Tank bottoms.
• Dry-cake and other filters.
These wastes are the separated and concentrated wastes
that must be disposed of economically and in accordance
with environmental regulations. An excellent reference
on the subject of waste management relative to environ-
mental regulations is the API environmental guidance
document, Onshore Solid Waste Management in Exploration
and Production Operations.1 Although written with re-
spect to solid wastes, the document summarizes environ-
mental regulations and discusses liquid wastes.
Environmental Regulations and Regulators

Environmental regulation of waste disposal depends on
California laws and whether the waste is classified as “hazardous.” Federal,
state, and local laws must be complied with when han-
regulations are discussed
dling and disposing of hazardous wastes. The following
here because these are discussion uses California as the example state. Califor-
some of the most nia laws and regulations are some of the most stringent
stringent in the U. S., and in the U. S., although equivalent laws and regulatory
agencies exist in most other states.
generally set the direction
for other states. The environmental laws and regulations relative to
hazardous wastes follow.
Federal
1. Resource Conservation and Recovery Act (RCRA).

2. Comprehensive Environmental Response Compensa-
tion and Liability Act (CERCLA).
3. Superfund Amendments and Reauthorization Act
(SARA).
4. Clean Water Act, including the National Pollution
Discharge Elimination System (NPDES) permitting
process.
5. Implementation regulations relative to the above.
State (California)
1. Health and Safety Code, Division 20, Chapter 6.5,
Hazardous Waste Control, Chapter 6.8, Hazardous
Substance Account.
2. Water Code Division 7, Water Quality.
3. California Environmental Act (CEQA).
4. Toxic Well Control Act (TWCA).
5. Toxic Pits Cleanup Act (TPCA).
6. Implementing regulations relative to the above —
e.g., California Code of Regulations, which imple-
ments CEQA.
Local
1. Various county and city ordinances regarding hazard-
ous wastes.
The federal and state agencies charged with implement-
ing these laws are:
Federal
1. Environmental Protection Agency (EPA).
State (California)
1. State Department of Health Services (DHS) — Toxic
Substances Control Division.
2. State Water Resources Control Board (SWRCB).
3. Regional Water Quality Control Boards (RWQCB).

Wastes are regulated by federal and state agencies. Be-
cause California regulations are generally more stringent
than federal regulations, we use them in the following
discussion. California regulations are good examples of
the regulations other states already follow or will follow
soon. California generally sets the direction other states
follow.
Classification and Relative Disposal of

Wastes
It is the responsibility of the waste generator to charac-
terize a waste to determine whether or not it is to be
classified as “hazardous”.
Four general criteria, outlined in the California Code of
Regulations (CCR), Title 22, Article 11, must be tested in
making this determination:
1. Toxicity.
Four general criteria to
2. Ignitability.
test whether a waste is
3. Corrosivity.
hazardous is toxicity,
flammability, corrosivity, 4. Reactivity.
or reactivity. These tests must be conducted by a Certified Hazardous
Waste Testing Laboratory following the procedures
specified in the CCR.
In addition, if the waste contains at least 1 of 791 chemi-
cals listed in CCR, Title 22, Article 9, it is assumed to be
hazardous. Each of these 791 chemicals, including both
organic and inorganic compounds, is considered toxic,
ignitable, corrosive, and/or reactive. Article 9 lists vari-
ous wastes by their “common names” that come under
the provisions of this section of the code if they contain a
hazardous material. Of note, relative to oilfield water
treating, are:
• Acid and water.
• Corrosion inhibitors.
• Oil and water.
• Tank bottom sediments.
• Tank cleaning sludges.

• Waste chemicals.
A copy of CCR, Title 22, Articles 9 and 11, is included in
the Appendix.
When any potential for groundwater contamination
exists, the RWQCB becomes involved, and additional
tests may be required even if the waste is not classified as
hazardous. The California Water Code gives the RWQCB
authority in governing discharges to land, including the
classification and regulation of waste disposal. These
boards have a separate classification of wastes that dic-
tates the type of facility where the waste can be disposed
of on land:
1. Hazardous Wastes — Wastes that are hazardous
according to the DHS definitions described above
(CCR, Title 22, Articles 9 and 11). These can only be
disposed of in a Class I facility.
2. Designated Wastes — Wastes that are:
A. Nonhazardous but consist of or contain pollutants
that could be released at levels exceeding appli-
cable water quality objectives or that could cause
degradation of the waters of the state.
B. Hazardous wastes that have been granted a vari-
ance by the DHS. These can be disposed of only in
a Class I or Class II facility.
3. Nonhazardous Solid Wastes — Wastes that are de-
gradable and nondegradable solids, semisolids, and
liquids (garbage, paper, trash, and demolition and
construction wastes) and similar wastes that do not
contain Designated Wastes. These can be disposed of
in permitted landfills.
4. Inert Wastes — Wastes that do not contain any of the
above or any significant amount of degradable waste,
including clean earth, concrete, inert plastics, tires,
and similar materials. These may be disposed of in
unclassified landfills.
Local governments (cities and counties) may become
involved and require additional tests or handling prac-
tices.

Restricted Wastes are a special waste classification. These
cannot be disposed of to land. Examples are liquid wastes
containing PCB’s at concentrations of 50 ppb and higher
and those containing high concentrations of heavy met-
als, cyanides, etc. In addition, the disposal of untreated
hazardous wastes of various types is restricted. For
example, the California DHS is considering treatment
standards for petroleum hazardous wastes, including a
prohibition on land disposal of untreated wastes contain-
ing an organic concentration of 1% or higher.
Water quality programs and requirements regulated by
federal, state, and local agencies are concerned with
waste-water disposal. These programs cover discharges
to navigable waters or land (as described above), injec-
tion wells, surface impoundments (pits, ponds, etc.),
drinking water protection, spill protection, sanitation
districts, and similar programs.
At the federal level, the EPA is primarily responsible for
implementing the Clean Water Act, including the NPDES
permitting system. Within California, the SWRCB and
RWQCB, which adopt and implement regulations regard-
ing water quality within the state, have received author-
ity from the EPA to administer the NPDES permits.
The regulated methods for the discharge of wastewater
are the following:
1. Discharge to water or land — Waste water may be
discharged to water or land under a permit from the
RWQCB (NPDES and California Waste Discharge Re-
quirements as described above). Permits are applicable
to navigable waters, other waters, and land if the
waste water may potentially reach groundwater.
Both federal and state Permits include monitoring and reporting require-
ments. Note that state and federal laws prohibit
agencies get involved in discharge of oil in “harmful quantities” into navigable
regulating underground water or all waters of the state. Harmful quantities
disposal of waste water are defined as “causing a sheen.”
by injection wells. 2. Discharge to sanitation or sewer districts — Waste
water may be discharged to publicly owned treatment
works. Permit and monitoring requirements are

issued and regulated by local sanitation districts and
must comply with the EPA-regulated pretreatment require-
ments.
3. Discharge to injection wells — Both federal and state
agencies get involved in regulating the disposal of waste
water into underground injection wells. The Califor-
nia DHS has strict regulations regarding disposal of
hazardous wastewater. The EPA regulates disposal
into injection wells according to five classes of wells:
Class I — Hazardous waste disposal wells and indus-
trial and municipal disposal wells meeting certain
criteria. These wells are subject to the most stringent
conditions for injection of wastes classified as hazard-
ous under RCRA:
A. The well must be located far enough away from
another Class I well to prevent wastes from escap-
ing from one well to the other.
B. The well must be cased, cemented, and completed
with a packer.
C. Injection must be below the lowest underground
source of drinking water.
D. Mechanical integrity must be demonstrated by
construction logs and repeated mechanical integ-
rity testing (at least every 5 years).
E. Injected wastes must be sampled and analyzed
periodically.
F. Injection rates of injected fluids and pressures in
tubing and annulus must be continuously re-
corded.
G. Monitoring wells must be installed near sources of
drinking water.
H. All pressures (injection, tubing, annulus) are
regulated.
Class II — Wells for injection of produced fluids, for Class II wells are
EOR, and for storage of hydrocarbons that are liquid designated for injection
at standard temperature and pressure. Regulations
for these wells and Class III wells are tailored to the of produced water.
industries to which they apply.

Class III — Wells used for injection in the extraction of
minerals (solution mining of salts or potash, Frasch
mining of sulfur, in-situ production of uranium and
other metals, etc.).
Class IV — Wells for disposal of hazardous and radioac-
tive wastes that meet certain criteria. Class IV wells
are being banned as the RCRA regulations for the
disposal of hazardous wastes, as so defined, are being
applied more broadly under the conditions of Class I
wells.
Class V — Injection wells that do not fall into any of the
above classes.
While retaining oversight responsibility, the EPA has
authorized the California Division of Oil and Gas (DOG)
to regulate Class II wells. Class II wells are not covered
under the California Toxic Injection Well Control Act.
These wells must be used only for injection of the speci-
fied fluids; they must not be used for the injection of
nonspecified fluids, such as hazardous wastes.
As noted, pits are being regulated out of existence. Like
Pits are being regulated many other states, California has passed a Toxic Pits
Cleanup Act (TPCA) to regulate surface impoundments
out of existence.
(which contain liquid hazardous wastes or hazardous
wastes containing free liquids). These impounds must
meet certain standards or be closed. (Tanks are ex-
cluded.) Surface impoundments include natural depres-
sions, diked areas, and artificial excavations that are
formed of earthen materials but may be lined with artifi-
cial materials. The requirements of the act affect closure,
restriction of wastes placed in the impoundment, design
standards, monitoring, and notification requirements.
The act is regulated locally by the RWQCB.
REFERENCE
1. Onshore Solid Waste Management in Exploration and
Production Operations, Order No. 811-10850, Publica-
tions and Distribution Section, API, 1220 L St. NW,
Washington, DC 20005 (202/682-8375).

GLOSSARY
anionic surfactants — soaps that inherently have a
negative charge.
BS&W — bottom sediment and water.
cationic surfactants — soaps containing a positive
charges.
Class I wells — hazardous waste disposal wells. Subject
to the most stringent conditions.
Class II wells — designated for the injection of produced
water.
Class III wells — designated for waters used for extrac-
tion of minerals.
Class IV — wells for disposal of hazardous and radioac-
tive wastes.
Class V — injection wells not covered by any other
category.
dry-cake filter — filter device that captures solids to
form a moist cake.
EOR — enhanced oil recovery.
filteraid — solid materials added to stream to enhance
capture of suspended materials in filter.
heavy metals — larger, multicharged cations. Some like
arsenic and mercury have a low permissible limit in
discharged water.
IGF skimmings — Induced gas flotation skimmings; oil-
rich reject stream from a device that removes residual
dispersed oil from water.
landfarms — locations where dispose of solid wastes by
mixing and burying with clean soil.
PCBs — polychlorinated biphenyls. Hazardous com-
pounds containing chlorine and two benzene rings.
perlite — solid material used as a filter aid.
point source treating — treating a waste stream at the
point it is generated.
water softeners — devices that remove calcium and
magnesium from a water.

workovers fluids — liquids used in well remediations
such as acidizing or fracturing.
zero discharge — discharge of oilfield waters into open
waters is not allowed.

APPENDIX

Index
Symbols
4,6-diamino-2-phenylindole (DAPI) 7-29
A
acetate utilizer 7-12, 7-24
acetic acid 5-33
acid producing bacteria (APB) 7-6, 7-17
acid wastes 10-10
acid-insoluble suspended solids 2-65
acid-soluble suspended solids 2-65
acids 9-7
organic 7-6, 7-8, 7-17
volatile fatty 7-17
acridine orange (AO) 7-29
acrolein 7-40
acrylate coagulants 8-18
acrylate polymers 8-18
acute toxicity 7-53
adenosine-5'-phosphosulfate (APS) reductase enzyme 7-29
adenosine-5'-triphosphate (ATP) 7-28
aerobic 7-10, 7-12
agar deep method 7-27
aldehydes 1-17, 7-40, 8-24
aliphatic acids 2-10, 2-11
alkalinity 2-3
alkyl aryl sulfonate surfactants 8-18
aluminum 6-7, 6-20, 6-21, 8-8
amine 6-9
amine-type biocides 8-24
amines 6-18, 6-23
ammonium bisulfite 6-23
anaerobic 7-10, 7-12
analytical methods 2-20
scale inhibitors 5-17
anhydrite 5-7
anionic 8-14
anionic surfactant 8-18
anionic surfactants 10-10
anionic-cationic interaction 8-23
anions 8-4
anodic 6-4, 6-5, 6-6, 6-11
antifoamer solubility 8-9
antifoamers 1-17, 8-9, 8-14
API Environmental Guidance Document 10-16
API separators 3-9
aquatic toxicity test 7-54
Index I-1
arbitrary recycling 10-9
assimilation 7-8
atomic weight 2-25
ATP assay 7-28
autotrophic bacteria 7-9, 7-17
B
backwash 10-9
backwashing 3-31
bacteria 6-3, 6-9, 6-10, 6-12, 6-23, 8-10, 8-24
acid producing 7-6, 7-17
autotrophic 7-9, 7-17
heterotrophic 7-8, 7-12
iron 7-17
lithotrophic 7-8
mesophilic 7-27
planktonic 7-18, 7-19, 7-21, 7-22, 7-25, 7-38, 7-41, 7-42,
7-45, 7-47, 7-49, 7-55
sampling methods 7-21
sessile 7-19, 7-21, 7-22, 7-25, 7-38, 7-41, 7-42, 7-45,
7-46, 7-47, 7-49, 7-56
slime forming 7-16
sulfate reducing 7-5, 7-6, 7-8, 7-11, 7-13, 7-15, 7-17, 7-19,
7-22, 7-24, 7-25, 7-30, 7-32, 7-33, 7-49
sulfide producing 7-13, 7-30, 7-32
sulfite reducing 7-27
sulfur oxidizing 7-17, 7-18
thermophilic 7-27
bacteria detection
culturing methods 7-23
direct methods 7-23, 7-28
bacterial activity 10-9
barium 2-7
barium sulfate 5-7, 5-11, 5-32, 8-15
batch frequency 7-46
batch treatment 7-53, 10-11
bench scale flotation units 3-24
best available practical technology 3-6
bicarbonate 5-4
bioassay 7-54
biocide effectiveness 7-44
biocide resistance 7-42
biocide selection 7-41
biocide solubility 8-7
biocide testing 7-49
biocide treatment procedures 7-53
Biocides 1-12
biocides 1-11, 1-12, 1-13, 1-17, 6-3, 6-10, 7-38, 8-5, 8-7,
8-10, 8-13, 8-14, 8-24, 10-7
inorganic 7-40
organic 7-41
oxidizing 7-38, 7-40
I-2 Water Treatment Handbook

biofilm 7-4, 7-8, 7-19, 7-22, 7-34, 7-38, 7-41, 7-42, 7-46,
7-47, 7-49, 7-56
biomass 2-12
bisulfide 2-11
black water 2-8, 5-9, 7-8
bottle reduction 7-46
bottle reductions 7-44
broth bottles 7-25
BS&W 10-12
bug bottles 7-25
C
calcium 2-7
calcium carbonate 5-4, 5-10, 5-30, 6-9, 6-12, 6-19, 6-23, 8-15
calcium sulfate 5-4, 5-31, 9-8
calcium sulfate (anhydrite) 8-15
calcium sulfate (gypsum) 8-15
calcium sulfate converters 5-32
calcium sulfite 8-18
California regulations 10-17, 10-19
carbon adsorption 1-13, 1-18
carbon dioxide 2-10, 5-4, 6-8, 6-18, 6-21, 6-22, 6-23, 6-24, 7-7
carbonate 2-5, 5-4
carboxylates 8-18
cathodic 6-4, 6-5, 6-8, 6-12
cathodic protection 6-9, 6-16, 6-21, 6-24
cation-anion interactions 8-15
cationic 8-14
cationic polyelectrolytes 3-24
cationic surfactants 8-18, 10-10
cations 2-7, 8-4
celestite 5-8, 5-11
cell surface antibody methods 7-29
chelating agents 6-11
chelation 5-14, 5-30, 5-31, 5-33
chemical additives 1-5, 10-7, 10-10, 10-11
chemical analysis 7-31
chemical cleaning 7-36
chemical compounds 8-5
chemical concentration units 2-41
chemical consumption 7-7
chemical incompatibilities 10-12
chemical interactions 5-18, 8-14
chemical solubility 8-5
chemicals 8-11, 10-12
residual 8-6
chloride 2-5
chlorine 7-37, 7-39, 7-53, 8-24
chlorine dioxide 1-17, 6-3, 6-8, 6-10, 6-24, 7-37, 7-53, 8-24
chlorinity 2-9
chlorinity, ‰ 2-9
chromium 6-4, 6-7, 6-19
Index I-3
chronic toxicity 7-54
citric acid 5-33
Class I wells 10-21
Class II wells 10-21
Class III wells 10-22
Class IV wells 10-22
Class V wells 10-22
classification of wastes 10-18
clay stabilizers 9-13, 9-14
clays 1-5, 9-3, 9-8
expanding type 9-4
cleaning 8-9
coagulant solubility 8-8
coagulants 1-18, 3-33, 8-14, 8-20
coagulants and flocculants 8-8
coagulation/coalescence 8-21
coalescence 1-14, 1-15, 3-9, 3-16, 3-32
coalescers 8-20
coalescing agents 3-24
color 2-16
combined wastes 10-11
complete oxidizers 7-12, 7-15, 7-25
compounds
polymers 1-12, 1-18
conductivity 2-16
consortium 7-15, 7-19
continuous treatment 7-53, 10-11
copper 6-4, 6-10, 6-20, 6-21
copper-nickel 6-17
core samples 9-13
coreflood procedures 3-4
corrosion 1-5, 1-7, 1-13, 10-9
microbiologically influenced 7-5, 7-11, 7-32, 7-50
pitting 7-5, 7-16
corrosion inhibitor solubility 8-7
corrosion inhibitors 1-11, 1-12, 1-17, 8-5, 8-6, 8-13, 8-14, 10-7
corrosivity 10-18
coupons 6-12, 6-13, 6-17
cracking 6-5, 6-8, 6-9, 6-13, 6-19, 6-20, 6-21
crevice corrosion 6-6, 6-19, 6-21
crude dehydration 3-10
crude oil dehydration 3-32, 3-34
cupronickel 6-10
cyanides 10-20
D
de-oilers 8-20
deflocculation 9-3, 9-5, 9-9
dehydration 3-33
demulsifier 3-34
bottle testing 8-21
chemistry 8-19

field evaluation 8-21
interactions 8-19
selection 8-21
treatment problems and interactions 8-20
demulsifier chemistry 3-33
demulsifier/reverse demulsifier interactions 8-19
demulsifiers 5-22, 8-19, 8-23
overdosing and underdosing 8-20
density 2-9
deposits 6-6, 6-13, 6-14, 6-21, 6-25
designated wastes 10-19
diatomaceous earth 10-12
differential dissolution 9-6
discharge 1-12
dispersants 8-23
dispersed oil 2-55, 2-57
dispersibility 8-9
dispersion 3-9
disposal 10-3
Disposal well classification 10-21
disposal wells 1-9
dissimilation 7-8
Dissolution 9-3
dissolved gas flotation 3-17
full flow pressurization 3-17
partial flow pressurization 3-17
dissolved gases 1-5, 2-22, 8-4
dissolved inorganic 10-3, 10-7
dissolved oil 2-55
dissolved organic 10-3, 10-7
dissolved oxygen 1-6, 8-10
dissolved salts 8-15
doubling time 7-46
downflow sand/multimedia filters 3-31
drilling new wells 1-9
drinking water 1-13
dry-cake filter 10-14
dry-cake filters 10-12
Dynaclean 3-26, 3-29
E
EDTA 5-14, 5-30, 5-33
eductor IGF 3-20
effect of deposits 6-12
effective concentration, median (50%) (EC50) 7-54
effective oil field water treatment 10-3, 10-9
electrochemical methods 2-25
electron acceptor 7-9, 7-10
electron donor 7-9
emission spectroscopy 2-26
emulsifying agent 3-33
emulsion 3-10, 3-33, 10-12
Index I-5
emulsion breaker solubility 8-8
emulsion breakers 8-7, 8-14
emulsions 3-24, 3-31, 10-12
endpoint 2-25
enhanced oil recovery 10-3
environment 10-15
environmental 1-7, 1-12
environmental problems 7-6
environmental regulations 10-3, 10-16
EOR 10-14
EPA 3-6, 10-20
epifluorescence methods 7-29
equivalence point 2-26
equivalent 2-5
equivalent weight 2-31
erosion-corrosion 6-10
extinction dilution 7-26
extracellular polymeric substance (EPS) 7-3, 7-4, 7-10, 7-16, 7-19
F
federal regulations 10-16
fermentation 7-9, 7-16
fibrous coalescers 3-14
filter backwash 1-4, 1-8, 10-7, 10-10, 10-12
filter backwash chemicals 8-5
filter media cleaning 10-10
filter vessels 10-9
filteraid 10-12
filters 10-7
filtrate 10-12
filtration 1-7, 1-9, 1-16, 10-11, 10-12
fines
injection 9-6
Fines; injection 9-4
firefly luciferase 7-28
fixed media coalescers 3-13
flame photometry 2-26
flocculant solubility 8-8
flocculants 8-14, 8-20
flocculation 3-32
flotation 1-14, 1-16, 3-16, 3-32, 8-21, 10-7
dissolved 3-17
dissolved gas 3-17
eductor induced 3-17
retention time 3-20
rotor induced 3-17
skimmings 3-19
flotation aids 3-24, 3-33
flotation cell 3-34, 8-22
flotation cell skimmings 10-7
fluorescein diacetate (FDA) 7-29
fluorescence spectroscopy 2-26

foaming agent 8-21
formaldehyde 7-40
formation damage 7-8, 9-3, 9-6
formation rock 9-9
formation rock analyses 9-13
formulation 8-8
free oil 1-5, 1-10, 1-14, 2-21, 2-55
G
galvanic 6-3, 6-6, 6-8, 6-12, 6-15, 6-17, 6-21, 6-22
gas concentration 3-22
gas dehydration chemicals 8-11, 8-14
gas flotation units 8-9
gas flotation vessels 10-9
gas production 8-11
gas stripping 1-17
gas/liquid contact time 3-21
gas/water ratio 3-21
genus 7-11
geochemical thermometer 2-12
glutaraldehyde 7-40
glycol 8-11
grains per gallon (gpg) 2-38
gravimetric analysis 2-22
gravimetric factor 2-31
gravity separation 3-32
Gulf of Mexico 7-55
gypsum 5-7, 5-11, 5-31
H
hardness 2-3
Hastelloy 6-20
hazardous wastes 10-19
heat 10-12
heavy metals 10-20
heterotrophic bacteria 7-8, 7-12
hydrate inhibitor solubility 8-11
hydrate inhibitors 8-11, 8-14
hydraulic eductor units 3-20
hydrazine 6-23
hydrocarbon-soluble suspended solids 2-65
hydrocyclone 3-33
operating pressure 3-27
hydrocyclones 3-24
hydrogen 6-4, 6-16
hydrogen peroxide 6-8, 7-37
hydrogen sulfide 1-5, 1-6, 2-10, 5-8, 6-8, 6-9, 6-10, 6-13,
6-18, 6-21, 6-22, 6-23, 6-24, 7-5, 7-6, 7-7, 7-11, 7-15,
7-16, 7-17, 7-33, 8-10
(TLV) 7-6
Hydropack 3-25, 3-29
Index I-7
Hydroswirl 3-25
hydroxyaluminum 9-14
hypochlorite 7-37, 7-39, 7-53, 8-24
I
IGF selection 3-20
IGF skimmings 3-33, 10-10, 10-12, 10-14
ignitability 10-18
in-line probes 7-52
incompatible waters 1-6, 1-11, 5-3, 5-12
incomplete oxidizers 7-12, 7-13, 7-15
indirect recycling 10-10
induced gas flotation 1-8, 3-18
infrared light scattering 3-37
inhibitor 6-6, 6-25
inhibitors 6-3, 6-18
injected water 10-15
injection water 1-9, 9-3, 9-13
injection well
plugging 1-11, 9-3, 9-6, 9-7, 9-9
injection well disposal 10-3
injectivity impairment 3-4
injectivity loss 3-3
inlet oil concentration 3-23
inorganic biocides 7-40
inorganic metal salts 8-8
inspection 6-13, 6-17, 6-24
integrated treatment systems 3-32
inter wastes 10-19
interface pad 3-33
ion chromatography 2-29
ion exchange 3-7, 10-11
ion selective electrode 2-27
ionic character 8-14
ionic properties 8-14
IR absorption 3-37
iron 2-7, 8-8
iron and calcium silicates 8-18
iron bacteria 7-17
iron carbonate 5-12, 6-6, 6-9, 8-15
iron counts 6-14
iron deposits 5-8, 5-12, 5-29, 5-33
iron oxide 2-8
iron oxides 6-3, 6-4, 6-8
iron sulfide 1-5, 2-8, 5-8, 7-6, 7-8, 8-15
iron sulfides 6-3, 6-4, 6-8, 6-13
isotope 7-32
J
Jackson Turbidity Units (JTU) 2-42

K
Kuparak Field 7-5
L
laboratory methods 3-40
landfarms 10-14
lethal concentration, median (50%) (LC50) 7-54
linear polarization 6-15
linings 6-24
liquid-liquid hydrocyclone 8-22
lithotrophic bacteria 7-8
log reduction 7-44, 7-46
loose media coalescers 3-12
luciferin-luciferase firefly reaction 7-28
M
magnesium 2-7
magnesium hydroxide 8-18
maximum droplet size 3-9
mean gas bubble size 3-22
mechanical design 7-35
media
fibrous cartridge 3-13
sponge type 3-13
media filtration 3-32, 8-9
melt agar tube method 7-27
mesophilic bacteria 7-27
methanogens 7-32
mica alteration 9-5, 9-13
microbial profile modification (MPM) 7-3
microbial reservoir souring 7-4
microbially enhanced oil recovery (MEOR) 7-3
microbiologically influenced corrosion (MIC) 7-5, 7-11, 7-32, 7-50
Microtox 7-55
migration 9-3, 9-5, 9-9
mild steel 6-5, 6-7, 6-8, 6-15
milliequivalents per liter (meq/L) 2-38
milligrams per liter (mg/L) 2-37
milligrams per liter (or parts per million) 2-39
milligrams per liter as calcium carbonate 2-39
Minas Field 7-31
mixing incompatible waters 8-15
molality (m) 2-41
molarity (M) 2-40
mole 2-39, 2-40
molecular weight 2-22
monel 6-20
monitoring 6-17
mudballing 3-31
Index I-9
N
naphthenic acids 2-10
National Association of Corrosion Engineers Standard 2-65
neutral components 8-4
nickel 6-4, 6-10, 6-19, 6-20, 6-23
Ninian Field 7-5
no-observed-effect concentration (NOEC) 7-54
nonhazardous solid wastes 10-19
nonionic 8-14
normality 2-40
normality (N) 2-40
NTA 5-33
nutshell filters 3-31
O
obligative anaerobe 7-12
offshore discharge 3-6
oil droplet coagulation 8-22
oil droplet size 3-9, 3-22, 3-33, 8-21
oil field chemicals, types 8-5
oil field waters
natural components 1-5, 8-4
oil soluble 8-7
oil/water separation 8-5, 8-20
oil/water separation equipment 10-12
on-line monitors 3-37
onshore systems 3-12
organic acids 2-10, 7-6, 7-8, 7-17
organic biocides 7-40, 7-41
organic polyelectrolytes 8-8
organic polyquaternary amine 9-14
overdosing 3-33, 3-34
oxidation-reduction 7-9
oxidizers
complete 7-12, 7-15
incomplete 7-12, 7-13, 7-15
oxidizing agent 7-9
oxidizing biocides 7-38, 7-40
oxygen 1-5, 1-6, 1-11, 2-4, 6-3, 6-4, 6-6, 6-7, 6-8, 6-9, 6-10,
6-11, 6-13, 6-14, 6-17, 6-18, 6-21, 6-22, 6-23, 9-8
oxygen scavenger solubility 8-10
oxygen scavengers 8-7, 8-10, 8-13, 8-14, 8-24
oxygen scavenging 1-17
ozone 7-37
P
PAIR 6-15
paraffin deposits 8-9
paraffin dissolvers 8-10
paraffin treating 8-9

paraffin treating chemicals 8-14
paraffins 8-23
parts per million (ppm) 2-8, 2-37
parts per thousand (ppt, ‰) 2-9, 2-38
passive 6-5, 6-7, 6-9, 6-19, 6-21
PCBs 10-20
percent kill 7-44
perlite 10-12
permeability damage 9-3, 9-5, 9-8
permeability decline 3-4
permits 10-14
pH 2-7
phenolphthalein 2-10
phosphate esters 5-15, 5-24
phosphates 1-18, 8-18
phospholipid signature 7-30
phosphonates 1-18, 5-15, 5-24, 8-18
physical cleaning 7-35
pig 6-17
pigging 5-34, 6-25, 7-36
pit sludges 10-7
pits 1-5, 1-15
pitting 6-5, 6-7, 6-8, 6-9, 6-10, 6-12, 6-13, 6-14, 6-15, 6-19,
6-20, 6-21, 6-24
pitting corrosion 7-5, 7-16
planktonic bacteria 7-18, 7-19, 7-21, 7-22, 7-25, 7-38, 7-41,
7-42, 7-45, 7-47, 7-49, 7-55
plant upset 8-15
plastic 6-25
plastics 6-17, 6-21
plate pack separation 8-21
plate pack separator 8-22
point source treating 10-10
polyphosphates 5-15
potassium 2-5
potassium extraction 9-6
potentiometric 2-27
pour plate method 7-27
pourbaix diagrams 6-11
precipitates 10-10
precipitation 9-3, 9-8, 9-9
primary crude dehydration 8-19
processing 10-5
produced water 8-11, 10-7
profile control 1-9
Prudhoe Bay Field 7-5
Q
qualitative identification 2-66
quality control 2-37
quaternary amines 1-17
quaternary ammonium salts 8-18
Index I-11
R
radium 2-7
RapidChek 7-29
reactivity 10-18
recirculation loop 7-50
recycle streams 3-33
recycling 10-7
red water 2-8, 5-9
reducing agent 5-33, 7-9, 7-11
Regulations 1-12
regulations 1-7, 1-9, 3-3, 10-14
reject ratio 3-28
reject stream 3-27
remedial treatments 9-8
requirements for discharge 3-6
requirements for enhanced oil recovery (EOR) 3-6
requirements for injection 3-3
reservoir souring 7-4
residence time 3-10, 10-12
resistance 6-14, 6-17
resistivity 2-21
restricted wastes 10-20
retrofitting 3-36
reverse breakers 8-8, 8-14, 8-20
reverse demulsifiers 8-19, 8-21
reverse osmosis 3-7
rock analyses 9-9
S
salinity 2-3
salinity, ‰ 2-9
salinity of produced water 3-22
sample identification 2-17
sampling 2-3
sampling methods
bacteria 7-21
sampling procedures 2-16
sand filters 10-9
saturation index 5-9, 5-10
scale 10-7
scale formation 1-13, 8-15
scale identification 5-28
scale inhibitor
application 5-18, 5-20
batch treatments 5-20
continuous recirculation 5-21
evaluation 5-18
selection 5-17
squeeze 5-22, 5-24
squeeze model 5-25
scale inhibitor solubility 8-6

scale inhibitors 1-11, 1-12, 1-17, 1-18, 6-11, 8-5, 8-6, 8-14,
8-23, 10-7
phosphate esters 5-15, 5-24
phosphonates 5-15, 5-24
polymers 5-15, 5-24
polyphosphates 5-15
scale mixtures 8-15
scale precipitation 8-15
scaling 10-9
scaling tendency 5-9, 5-10, 5-11, 5-12
scanning electron microscopy 2-67
scraping 7-36
seawater 6-8, 6-10, 6-12, 6-17, 6-20, 6-21, 8-10
separated gases 10-5
separated oil 10-5
separated solids 10-5
separated water 10-5
separation equipment 8-21
separators 10-7
serial dilution 7-26
sessile bacteria 7-19, 7-21, 7-22, 7-25, 7-38, 7-41, 7-42,
7-45, 7-46, 7-47, 7-49, 7-56
settling time 3-8
sewer system 1-7
side stream loop 7-50
silica 2-21
skimmings 1-5, 1-15
slime forming bacteria 7-16
sludge 10-7, 10-12
sludges 10-14
slug treatment 7-53
sodium 2-5
sodium chloride 8-15
sodium sulfite 6-10, 6-23
softening 3-7
solid culture media 7-26
solids 1-10
solids generation 10-9
solids stabilized emulsions 8-23
solubility 5-3, 8-9
solubility calculations 2-47, 5-9, 5-11
solubility of surfactants 8-19
soluble iron(II) 2-13
solvents 8-5
sour water 8-10
souring 7-4
SP-Pack 3-16
species 7-11
specific gravity 2-9
specific resistivity 2-21
spools 6-13
spread plate method 7-27
Index I-13
stainless steels 6-5, 6-7, 6-8, 6-9, 6-19
steam generation 3-7, 10-3
steam injection 9-7, 9-8
steam quality 3-7
stimulation 1-8, 1-9
acids 8-11
diverters 8-13
flushes 8-12
frac fluids 8-12
stimulation acids 8-5, 8-14
stimulation fluid additives 8-14
stimulation job 8-11
stimulation liquids 10-10
Stokes law 3-8
Stokes’ Law 3-26
strong oxidizers 8-24
strontium 2-7
strontium sulfate 5-8, 5-11, 8-15
subsurface disposal 3-5
sulfate 2-5, 6-10, 6-23, 9-8, 9-9
sulfate reducing bacteria (SRB) 7-5, 7-6, 7-8, 7-11, 7-13, 7-15,
7-17, 7-19, 7-22, 7-24, 7-25, 7-30, 7-32, 7-33, 7-49
sulfates 6-9, 8-18
sulfide producing bacteria (SPB) 7-13, 7-30, 7-32
sulfide scavenger solubility 8-10
sulfide scavengers 8-10, 8-14
sulfite reducing bacteria 7-27
sulfonates 8-18
sulfur dioxide 6-10, 6-23
sulfur isotope differentiation method 7-32
sulfur oxidizing bacteria 7-17, 7-18
supersaturation ratio 5-10
surface disposal 1-7
surfactant 8-8, 8-14, 8-23
solubility 8-19
surfactant cleaners 8-14
surfactant interactions 8-18, 8-23
surfactant solubility 8-9
surfactants 1-10, 1-12, 1-15, 1-17, 3-24, 3-31, 5-22, 8-5, 8-9,
8-23, 10-7
suspended solids 1-5, 1-7, 1-16, 2-4
system accumulation 10-7
system chemistry 8-23
system design 10-10
system upsets 10-10
T
tank bottoms 1-5, 1-15, 8-23, 10-7, 10-10, 10-12, 10-14
tanks 10-9
TDS 2-5
temperature 2-9, 6-11, 6-17, 6-24
thermophilic bacteria 7-27

Threshold Limit Value (TLV) 7-6
time-kill procedure 7-44
titrimetric analysis 2-25
total suspended solids 2-65
total cell counts 7-16, 7-29
total dissolved solids 2-5
total system approach 1-9, 8-25
toxicity 1-12, 7-6, 10-18
acute 7-53
chronic 7-54
treated water quality 10-7
treatment design 10-11
treatment plateau 8-21
treatment volume 10-11
turbidimetric analysis 2-26
turbidity 2-13
turbulence 6-6, 6-10, 6-13, 6-17
U
U.S. Environmental Protection Agency 2-69
ultrasonic 3-37, 6-16
ultraviolet radiation 7-38
unwanted wastes 10-9
UV absorption 3-37
V
velocity 6-17, 6-21
vertical tube coalescer 3-16
vessel internals 3-11, 3-36
viable cell counts 7-29
viscosifiers 8-13
volatile acids 2-20
volatile fatty acids 7-17
voltammetric analyses 2-28
Vortoil 3-25, 3-28
W
waste stream 3-31
waste streams 8-22, 8-23
waster disposal 10-15
water analysis
reasons for 2-3
water characteristics
handling and treatment 1-5
open waters 1-6
produced waters 1-5
source wells 1-6
water chemistry 7-7, 8-3, 10-11
water dispersible 8-7
water phase residence time 3-34
water quality 1-10, 1-13, 10-7
Index I-15
water sensitivity 3-4
water softeners 10-9
water sources
open water 1-4, 1-6
produced waters 1-4, 1-5
source wells 1-4, 1-6
water treating
challenges 1-3
enhanced oil recovery 1-3, 1-4, 1-12, 1-14
new waterfloods 1-4
old waterfloods 1-3
systems 1-3, 1-8
water treatment
general objectives 1-10, 1-13
injection requirements 1-9, 1-10
methods - chemical 1-10, 1-15, 1-17
methods and equipment 1-10, 1-15
requirements 1-10, 1-13
special objectives 1-7
surface disposal requirements 1-10, 1-12
water treatment chemicals 3-33
water treatment plan design 10-7
waterflood 10-14
waterflooding 10-3
waxes 8-23
weight percent (% or wt %) 2-37
weighted brines 8-13
well backflowed 8-13
well completion 10-21
well injectivity 10-15
well squeeze 8-6
well stimulation chemicals 8-11
well workovers 10-7
wetting agent 1-12
wetting agents 8-23
Wilmington Field 7-5
workover fluids 8-13, 8-23, 10-10
X
x-ray diffraction (XRD) 2-66
x-ray fluorescence (XRF) 2-66
Z
zero discharge 10-14
zinc chlorides 8-8

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Water Treatment Handbook

CHAPTER 1: INTRODUCTION ............................ 1-1

Water Treatment Handbook i

ii Water Treatment Handbook

Water Treatment Handbook iii

iv Water Treatment Handbook

Water Treatment Handbook v

vi Water Treatment Handbook

Water Treatment Handbook vii

viii Water Treatment Handbook

Water Treatment Handbook ix

x Water Treatment Handbook

Chapter 1: Introduction 1-1

Existing Systems Designed for Old

Chapter 1: Introduction 1-3

A New System To Be Installed for a New

OILFIELD WATER REQUIRING TREATMENT

1-4 Water Treatment Handbook

Characteristics of Waters That Affect Their

Chapter 1: Introduction 1-5

Source Well Waters:

1-6 Water Treatment Handbook

WATER TREATMENT OBJECTIVES

Chapter 1: Introduction 1-7

POSSIBLE TREATMENTS REQUIRED TO

1-8 Water Treatment Handbook

Treatment Objective — Injection

Chapter 1: Introduction 1-9

Removal of Free Oil from Water

1-10 Water Treatment Handbook

Effective Corrosion, Scale, and Biological

Separate Treatment of Waters

Chapter 1: Introduction 1-11

EOR Treatment Considerations in Addition to

Treatment Objective — Surface Disposal

1-12 Water Treatment Handbook

Additional Water Treatment Objectives

Corrosion, Scale, and Biological Control

Chapter 1: Introduction 1-13

Recovery of Free Oil in Water and Lost

Special Treatment for EOR Requirements

1-14 Water Treatment Handbook

Nonroutine Treatments of “Special” Oilfield

OILFIELD TREATMENT METHODS AND

Chapter 1: Introduction 1-15

1-16 Water Treatment Handbook

1. Various sulfides ( SO 2 , HSO −32 , SO −3 2 )

Chapter 1: Introduction 1-17

1-18 Water Treatment Handbook

Chapter 1: Introduction 1-19

Analytical and Test Methods

Chapter 2: Analytical and Test Methods 2-1

Reasons for Water Analysis

Chapter 2: Analytical and Test Methods 2-3

Constituents Determined and Properties

2-4 Water Treatment Handbook

Significance of Components or Properties

Chapter 2: Analytical and Test Methods 2-5

Properties pH (field and lab)

2-6 Water Treatment Handbook

Chapter 2: Analytical and Test Methods 2-7

2-8 Water Treatment Handbook