EPRI Closed Cooling Water Chemistry Guideline Revision 1 PDF

Closed Cooling Water Chemistry
Guideline, Revision 1
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Closed Cooling Water Chemistry
Guideline, Revision 1
Revision 1 to TR-107396, Closed Cooling Water
Chemistry Guideline
1007820
Final Report, April 2004
EPRI Project Manager

T. Eckert
EPRI 3412 Hillview Avenue, Palo Alto, California 94304 PO Box 10412, Palo Alto, California 94303 USA
800.313.3774 650.855.2121 askepri@epri.com www.epri.com
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This report describes research sponsored by EPRI.
The report is a corporate document that should be cited in the literature in the following manner:
Closed Cooling Water Chemistry Guideline: Revision 1 to TR-107396, Closed Cooling Water
Chemistry Guideline, EPRI, Palo Alto, CA: 2004. 1007820.
iii
PRODUCT DESCRIPTION
This Closed Cooling Water Chemistry Guideline addresses the use of chemicals to mitigate
corrosion, fouling, and microbiological growth in the closed cooling water (CCW) systems of
nuclear power plants. The chemical additives used for these purposes depend on plant design
characteristics, water quality, operating parameters, and the specifications of Nuclear Steam
Supply System (NSSS) suppliers. The list of chemicals is not as extensive as that for service
water systems but can be confusing to utility CCW system engineers and chemists. Both generic
chemicals and proprietary blends are used in CCW systems. Acquiring chemicals with
sufficiently low levels of contaminants (for example, halides and metals) to meet NSSS suppliers
original specifications is an issue in some nuclear plants. This concern relates particularly to many
microbiological control agents.
The use of chemicals in CCW systems will not resolve problems originating from poor design or
maintenance practices that result in excessive system leaks. Excessive leakage makes consistent
chemical control very difficult and offsets the ability of the chemicals to provide adequate
protection.
Results and Findings

The use of operating ranges for the various treatment chemicals discussed in this guideline will
allow a nuclear power plant to limit corrosion, fouling, and microbiological growth in CCW
systems to acceptable levels. The recommended frequencies of analysis for Control and
Diagnostic Parameters document satisfactory chemical control of the systems.
This revision of the Closed Cooling Water Chemistry Guideline provides recommendations for
closed cooling systems of all manufacture and design.
Challenges and Objectives

This guideline will be of value to nuclear power plant chemical personnel, engineering personnel
with closed cooling system responsibility, maintenance personnel, and management personnel.
The guideline provides the technical basis for a reasonable but conservative set of chemical
treatment and monitoring programs. It will assist station management in endorsing a chemistry
program to optimize equipment life, reduce chronic operating problems, and provide assistance
with issues regarding regulatory requirements and plant life extension. Because of the wide range
of operating conditions for closed cooling water systems and the differences in materials of
construction and chemical treatment regimes, each station must develop its own site-specific
chemistry program.
v
EPRI Perspective
This first revision of the Closed Cooling Water Chemistry Guideline has been endorsed by the
utility chemistry community and represents another step in developing a more proactive
chemistry program to limit or control closed cooling system degradation with increased
consideration of corporate resources and plant-specific design and operating concerns. Each
utility should examine its plant-specific situation to determine which recommendations should be
implemented.
Approach
A committee of industry expertsincluding utility specialists, Institute of Nuclear Power
Operations representatives, water treatment service company representatives, consultants, a
primary contractor, and EPRI staffcollaborated in reviewing available data on closed cooling
water system corrosion and microbiological issues. From these data, the committee generated
water chemistry guidelines that should be used at all nuclear plants. Recognizing that each
nuclear plant owner has a unique set of design, operating, and corporate concerns, the Guidelines
Committee developed a methodology for plant-specific optimization.
Keywords
Closed cooling systems
Corrosion
Nitrites
Chromates
Molybdates
Hydrazine
vi
ACKNOWLEDGMENTS
The following individuals were ongoing members of Plant Support Engineerings Closed
Cooling Water Chemistry Guideline Revision 1 Task Group. As such, they have made
significant contributions to the development of this guideline by attending the majority of the
task group meetings, reviewing and commenting on various drafts, and writing portions of the
document.
Ms. Debra J. Bodine, Chairperson Tennessee Valley Authority

Mr. Stephen Preece British Energy Generation, Ltd.
Ms. Jose Chalut Buckman Laboratories, Inc.
Mr. John P. Terry Buckman Laboratories, Inc.
Mr. Jack Bills Constellation Nuclear
Mr. Edward C. Frese Dominion Generation
Mr. Robert A. Martin Duke Energy Corp.
Mr. Richard P. Gerdus Entergy Nuclear Northeast
Mr. William Dunphy Entergy Nuclear Northeast
Ms. Barbara Homyk Entergy Nuclear Northeast
Mr. Daryl Marse Entergy Operations, Inc.
Mr. Timothy Eckert EPRI Charlotte
Mr. S. Chris Baker Exelon Nuclear
Mr. Thomas Britt Exelon Nuclear
Dr. Robert Winters FirstEnergy Nuclear Operating Co.
Ms. Equilla Minga Institute of Nuclear Power Operations
Mr. Edward A. Hinshaw Nuclear Management Co.
Mr. Frank Sperlak Nuclear Management Co.
Mr. Kenneth H. Kingston Omaha Public Power District
Mr. Gregory C. Broxterman Nalco Company
Mr. Peter Ten Eyck Nalco Company
Mr. Trevor Rebel Pacific Gas & Electric Co.
Mr. Daniel W. Miller PPL Susquehanna, LLC
Mr. Michael L. Millinor Progress Energy, Inc.
vii
Mr. Rocky H. Thompson Progress Energy, Inc.
Dr. Richard W. Lutey R. W. Lutey & Associates, Inc.
Dr. Robert Litman Radiochemistry Laboratory Basics
Mr. Stephen E. (Chip) Citzler South Texas Project Nuclear Operating Co.
Mr. Timothy M. Sarette Southern California Edison Co.
Mr. Michael Perry Southern Nuclear Operating Co.
Mr. Dennis D. Rickertsen Southern Nuclear Operating Co.
Mr. Joel R. Robinson Southern Nuclear Operating Co.
Mr. Robert L. Theimer TXU Generation Co., LP
Mr. K. Anthony (Tony) Selby Water Technology Consultants
viii
EPRI Licensed Material
CONTENTS
1 INTRODUCTION ....................................................................................................................1-1
1.1 Background..................................................................................................................1-1
1.2 Terms and Definitions ..................................................................................................1-2
1.2.1 Control Parameters .............................................................................................1-2
1.2.2 Diagnostic Parameters........................................................................................1-2
1.2.3 Investigative Parameters.....................................................................................1-2
1.2.4 System Ranking by Tiers ....................................................................................1-3
Tier 1 System...............................................................................................................1-3
Tier 2 System...............................................................................................................1-3
Intermittent System ......................................................................................................1-3
1.2.5 Remaining Plant Systems ...................................................................................1-3
1.2.6 CCW Action Levels .............................................................................................1-4
CCW Action Level 1.....................................................................................................1-4
CCW Action Level 2.....................................................................................................1-5
1.3 Contaminant Specifications .........................................................................................1-5
1.4 Purpose .......................................................................................................................1-6
1.5 Scope...........................................................................................................................1-6
1.6 Assumptions ................................................................................................................1-7
1.7 Management Responsibility and Program Ownership.................................................1-7
1.7.1 Water Chemistry Management Philosophy.........................................................1-7
1.7.2 Generic Management Considerations.................................................................1-8
1.7.3 Training of CCW Chemistry Control Personnel...................................................1-9
1.8 Roles and Responsibilities of Plant Personnel ..........................................................1-10
1.8.1 Operations.........................................................................................................1-10
1.8.2 System Engineering ..........................................................................................1-10
1.8.3 Chemistry ..........................................................................................................1-10
1.8.4 Maintenance......................................................................................................1-10
ix
2 DESCRIPTIONS OF CLOSED COOLING WATER SYSTEMS .............................................2-1

2.1 Purpose of Closed Cooling Water Systems.................................................................2-1
2.2 Closed Cooling Water System Design.........................................................................2-1
2.3 Variations of Closed Cooling Water System Design....................................................2-2
2.4 System Materials .........................................................................................................2-3
2.5 Classification of Closed Cooling Systems....................................................................2-6
3 PROBLEMS IMPACTING CHEMISTRY IN CLOSED COOLING WATER SYSTEMS..........3-1

3.1 Corrosion .....................................................................................................................3-1
3.1.1 Mechanisms ........................................................................................................3-1
3.1.2 Impact of Corrosion.............................................................................................3-1
3.2 Microbiological Growth.................................................................................................3-2
3.3 Fouling .........................................................................................................................3-2
3.4 Operational and Mechanical Considerations ...............................................................3-3
4 TECHNICAL BASIS OF TREATMENT CHEMICALS USED FOR CORROSION

CONTROL .................................................................................................................................4-1
4.1 Introduction ..................................................................................................................4-1
4.2 Makeup Water Sources ...............................................................................................4-2
4.3 Chemicals Used for Corrosion Control ........................................................................4-3
4.3.1 General ...............................................................................................................4-3
4.3.2 Commonly Used Ferrous Alloy Corrosion Inhibitors ...........................................4-4
Critical Concentration of Nitrite, Molybdate, and Chromate Technical Basis............4-4
Nitrites..........................................................................................................................4-5
Molybdate ....................................................................................................................4-7
Nitrite/Molybdate ........................................................................................................4-10
Chromate ...................................................................................................................4-13
Hydrazine...................................................................................................................4-14
Silicates .....................................................................................................................4-16
4.3.3 Copper Alloy Corrosion Inhibitors .....................................................................4-17
4.4 Closed Cooling Water System Corrosion Control Without Chemicals (Pure
Water Systems)...................................................................................................................4-19
4.5 Blended Glycol Formulations .....................................................................................4-21
x
5 TREATMENT PROGRAM AND MONITORING RECOMMENDATIONS ..............................5-1

5.1 CCW Action Levels ......................................................................................................5-1
5.1.1 CCW Action Level 1 ...........................................................................................5-2
5.1.2 Action Level 2.....................................................................................................5-2
5.2 Nitrite-Based Programs................................................................................................5-2
5.3 Molybdate-Based Programs ........................................................................................5-4
5.4 Nitrite/Molybdate Programs .........................................................................................5-5
5.5 Chromate-Based Programs .........................................................................................5-6
5.6 Hydrazine-Based Programs.........................................................................................5-7
5.7 Silicate-Based Programs .............................................................................................5-8
5.8 Pure Water Systems ....................................................................................................5-9
5.9 Blended Glycol Formulations .....................................................................................5-10
6 TECHNICAL BASIS OF CHEMICALS USED FOR MICROBIOLOGICAL AND

FOULING CONTROL ................................................................................................................6-1
6.1 General ........................................................................................................................6-1
6.2 Non-Oxidizing Biocides................................................................................................6-2
6.2.1 Glutaraldehyde....................................................................................................6-2
6.2.2 Isothiazolone .......................................................................................................6-4
6.2.3 Methylene Bis(Thiocyanate)................................................................................6-5
6.2.4 DBNPA................................................................................................................6-6
6.2.5 THPS...................................................................................................................6-7
6.2.6 Ionine Quaternary Compounds ...........................................................................6-8
6.2.7 Dodecylguanidine Hydrochloride (DGH) ...........................................................6-10
6.2.8 Carbamates.......................................................................................................6-10
6.2.9 Quaternary Ammonium Salts (Quats) ...............................................................6-10
6.2.10 Tris-Nitro ........................................................................................................6-10
6.3 Oxidizing Biocides .....................................................................................................6-10
6.3.1 Hydrogen Peroxide ...........................................................................................6-10
6.3.2 Chlorine Compounds ........................................................................................6-11
6.4 Other Treatments.......................................................................................................6-11
6.5 Methods Used for Fouling Control .............................................................................6-12
6.5.1 General .............................................................................................................6-12
6.5.2 Suspended Solids Deposition ...........................................................................6-12
Water-Borne Foulants from Outside the System ..................................................6-12
xi
Foulants Generated Within the System ................................................................6-13

6.5.3 Chemical Foulant Control Methods...................................................................6-13
Dispersants ................................................................................................................6-13
Surfactants (Biodispersants)......................................................................................6-13
6.5.4 Feed and Bleed.................................................................................................6-14
Disadvantages ...........................................................................................................6-14
6.5.5 Drain and Refill..................................................................................................6-15
6.5.6 Sidestream Filtration and Sidestream Demineralization ...................................6-15
Advantages ................................................................................................................6-15
6.5.7 Other Mechanical Means of Suspended Solids Control....................................6-15
7 TECHNICAL BASIS OF MONITORING PARAMETERS.......................................................7-1

7.1 Introduction ..................................................................................................................7-1
7.2 Testing Parameters......................................................................................................7-2
7.2.1 Corrosion Inhibitors .............................................................................................7-2
7.2.2 pH........................................................................................................................7-2
7.2.3 Percent Glycol.....................................................................................................7-2
7.2.4 Conductivity.........................................................................................................7-3
7.2.5 Cation Conductivity .............................................................................................7-3
7.2.6 Chloride and Fluoride (Halides) ..........................................................................7-3
7.2.7 Nitrate..................................................................................................................7-4
7.2.8 Ammonia .............................................................................................................7-4
7.2.9 Iron and Copper (Corrosion Products) ................................................................7-4
7.2.10 Microbiological Activity.....................................................................................7-5
7.2.11 Radionuclides ..................................................................................................7-5
7.2.12 Specific Microorganisms ..................................................................................7-6
7.2.13 Total Organic Carbon (TOC) ...........................................................................7-6
7.2.14 Dissolved Oxygen ............................................................................................7-6
7.2.15 Sulfate..............................................................................................................7-7
7.2.16 Calcium and Magnesium .................................................................................7-7
7.2.17 Refrigerant Chemicals .....................................................................................7-7
7.2.18 Reserve Alkalinity (RA) ....................................................................................7-7
7.2.19 Visual Evaluation of CCW Fluids .....................................................................7-8
7.3 Monitoring Frequency ..................................................................................................7-8
7.4 Investigative Parameters .............................................................................................7-8
xii
8 ADDITIONAL MONITORING TECHNIQUES .........................................................................8-1

8.1 Corrosion.................................................................................................................8-1
8.1.1 Monitoring Techniques........................................................................................8-2
Corrosion Coupons ......................................................................................................8-2
Electrochemical Means................................................................................................8-3
Electrochemical Noise .................................................................................................8-4
8.2 Fouling .........................................................................................................................8-4
8.3 Microbiological Growth.................................................................................................8-5
8.3.1 Colony Counting Techniques ..............................................................................8-5
Adenosine Triphosphate (ATP)....................................................................................8-6
Dip Slides.....................................................................................................................8-7
Total Aerobic Plate Counts ..........................................................................................8-8
PetriFilm....................................................................................................................8-8
Test Kits .......................................................................................................................8-8
8.3.2 Sessile Bacteria Monitoring Techniques .............................................................8-8
Stainless Steel Corrosion Coupons .............................................................................8-8
Screened Coupons ......................................................................................................8-9
Glass Bead Holders .....................................................................................................8-9
Metal Specimen Holder................................................................................................8-9
Inspections...................................................................................................................8-9
8.3.3 Monitoring for Specific Microbial Species ...........................................................8-9
8.4 Non-Chemistry Monitoring .........................................................................................8-10
8.4.1 Inspections ........................................................................................................8-10
8.4.2 Nondestructive Evaluations (NDEs)..................................................................8-10
Ultrasonic Testing ......................................................................................................8-10
Electromagnetic Automatic Scanning ........................................................................8-11
Eddy Current Testing .................................................................................................8-11
Radiographic Testing .................................................................................................8-11
8.4.3 Leakage ............................................................................................................8-11
8.4.4 Heat Transfer ....................................................................................................8-12
8.5 Trending.....................................................................................................................8-12
8.6 Chemical Analysis......................................................................................................8-12
8.6.1 Ion Chromatography (IC) ..................................................................................8-13
8.6.2 Ion Selective Electrodes (ISE) ..........................................................................8-13
8.6.3 Atomic Absorption (AA) and Inductively Coupled Plasma (ICP) .......................8-14
xiii
8.6.4 Ultraviolet/Visible Spectroscopy (UV/Vis) .........................................................8-14

8.6.5 pH and Conductivity ..........................................................................................8-15
8.6.6 Vendor Test Kits................................................................................................8-15
8.6.7 X-Ray Fluorescence (XRF) of Filtered Material ................................................8-16
9 TROUBLESHOOTING AND CORRECTIVE ACTIONS .........................................................9-1

9.1 Introduction ..................................................................................................................9-1
9.2 Nitrite-Treated Systems ...............................................................................................9-1
9.2.1 System Leakage .................................................................................................9-1
9.2.2 Water In-Leakage................................................................................................9-2
9.2.3 Bacterial Growth..................................................................................................9-2
9.2.4 Nitrate-Forming Bacteria Growth ........................................................................9-3
9.2.5 Ammonia-Forming Bacteria Growth....................................................................9-4
9.2.6 Acid-Forming Bacteria Growth ............................................................................9-4
9.2.7 Increase in System Corrosion Rates...................................................................9-5
9.2.8 Oil In-Leakage.....................................................................................................9-5
9.2.9 Contaminant Ingress ...........................................................................................9-6
9.3 Molybdate-Treated Systems ........................................................................................9-6
9.3.1 System Leakage .................................................................................................9-6
9.3.2 Water In-Leakage................................................................................................9-7
9.3.3 Bacterial Growth..................................................................................................9-7
9.3.4 Increase in System Corrosion Rates...................................................................9-8
9.3.5 Oil In-Leakage.....................................................................................................9-8
9.3.6 Contaminant Ingress ...........................................................................................9-8
9.4 Nitrite/Molybdate-Treated Systems..............................................................................9-9
9.4.1 System Leakage .................................................................................................9-9
9.4.2 Water In-Leakage................................................................................................9-9
9.4.3 Bacterial Growth................................................................................................9-10
9.4.4 Nitrate-Forming Bacteria Growth ......................................................................9-10
9.4.5 Ammonia-Forming Bacteria Growth..................................................................9-11
9.4.6 Acid-Forming Bacteria Growth ..........................................................................9-12
9.4.7 Increase in System Corrosion Rates.................................................................9-12
9.4.8 Oil In-Leakage...................................................................................................9-13
9.4.9 Contaminant Ingress .........................................................................................9-13
xiv
9.5 Chromate-Treated Systems.......................................................................................9-14

9.5.1 System Leakage ...............................................................................................9-14
9.5.2 Water In-Leakage..............................................................................................9-14
9.5.4 Oil In-Leakage...................................................................................................9-15
9.6 Hydrazine-Treated Systems ......................................................................................9-16
9.6.1 Hydrazine Decomposition .................................................................................9-16
9.6.2 System Leakage ...............................................................................................9-16
9.6.3 Water In-Leakage..............................................................................................9-17
9.7 Silicate-Treated Systems ...........................................................................................9-17
9.7.1 System Leakage ...............................................................................................9-17
9.7.2 Water In-Leakage..............................................................................................9-18
9.7.4 Oil In-Leakage...................................................................................................9-19
9.7.6 Bacterial Growth................................................................................................9-19
9.8 Pure Water Systems ..................................................................................................9-20
9.8.1 System Out-Leakage ........................................................................................9-20
9.8.2 Water In-Leakage..............................................................................................9-20
9.8.3 Acidophilic Bacteria Growth ..............................................................................9-21
9.8.4 Ammonia-Forming Bacteria Growth..................................................................9-21
9.8.6 Oil In-Leakage...................................................................................................9-22
9.9 Inhibited Glycol Systems............................................................................................9-23
9.9.1 System Leakage ...............................................................................................9-23
9.9.2 Water In-Leakage..............................................................................................9-23
9.9.3 Glycol Breakdown .............................................................................................9-24
9.9.5 Oil In-Leakage...................................................................................................9-25
9.10 Flow Charts ...........................................................................................................9-25
xv
10 METHODOLOGY FOR PLANT-SPECIFIC TREATMENT OPTIMIZATION ......................10-1

10.1 Introduction ...........................................................................................................10-1
10.2 Determining Chemical Treatment Needs ..............................................................10-1
10.2.1 Metallurgy and Design ...................................................................................10-1
10.2.2 Makeup Water Source ...................................................................................10-2
10.2.3 Operating Conditions .....................................................................................10-3
10.2.4 System Conditions .........................................................................................10-4
10.2.5 Previous Treatment Regime ..........................................................................10-4
10.2.6 Compatibility ..................................................................................................10-5
10.2.7 Impact on Other Plant Systems .....................................................................10-5
10.2.8 Plant Life Extension Experience and Issues..................................................10-6
10.3 Environmental Impact and Health Effects .............................................................10-6
10.4 Nonchemical Treatment Considerations ...............................................................10-6
11 REFERENCES ...................................................................................................................11-1
A POSITION PAPER ON IMPURITY CONCENTRATION LIMITS FOR CLOSED

COOLING WATER SYSTEMS................................................................................................. A-1
A.1 Executive Summary .................................................................................................... A-1
A.2 Introduction ................................................................................................................. A-2
A.2.1 Current Impurity Limits ....................................................................................... A-2
A.2.2 Role of Water Quality in SCC............................................................................. A-3
A.3 Technical Position....................................................................................................... A-3
A.3.1 Factors Affecting SCC of Stainless Steel Materials ........................................... A-3
A.3.2 Failure Modes with Stainless Steel System Materials........................................ A-4
SCC of Stainless Steel Tubing in Heat Exchangers ................................................... A-5
Chloride Ion Concentration in the Crevice .................................................................. A-5
Summary .................................................................................................................... A-6
A.4 Side Effects or Risks................................................................................................... A-6
A.5 Strategy ...................................................................................................................... A-6
A.6 Recommendations ...................................................................................................... A-7
A.7 References ................................................................................................................. A-7
B CHEMISTRY-RELATED PROBLEMS IN CLOSED COOLING WATER SYSTEMS ........... B-1

B.1 Corrosion Mechanisms ............................................................................................... B-1
B.1.1 General Corrosion.............................................................................................. B-1
xvi
B.1.2 Localized Corrosion ........................................................................................... B-1

Pitting Corrosion ......................................................................................................... B-1
Crevice Corrosion ....................................................................................................... B-2
Stress Corrosion Cracking (SCC) ............................................................................... B-2
Galvanic Corrosion ..................................................................................................... B-2
Microbiologically Influenced or Induced Corrosion (MIC) ........................................... B-3
Flow-Accelerated Corrosion (FAC) ............................................................................. B-3
Erosion........................................................................................................................ B-3
B.2 Impact of Corrosion..................................................................................................... B-4
B.2.1 Failures .............................................................................................................. B-4
B.2.2 Fouling ............................................................................................................... B-4
B.3 Microbiological Organisms.......................................................................................... B-5
B.3.1 Nitrogen Biogeochemical Cycle ...................................................................... B-5
Step 1. Fixation of Molecular Nitrogen........................................................................ B-5
Step 2. Ammonification ............................................................................................... B-6
Step 3. Nitrification/Nitrosification ............................................................................... B-6
Step 4. Nitrate Reduction/Denitrification ..................................................................... B-7
Step 5. Recycling and/or Short Cuts........................................................................... B-9
B.3.2 Aerobic Mechanisms.......................................................................................... B-9
Iron and Manganese Bacteria..................................................................................... B-9
Sulfur-Oxidizing Bacteria .......................................................................................... B-10
B.3.3 Anaerobic Mechanisms.................................................................................... B-10
Sulfate-Reducing Bacteria ........................................................................................ B-10
Nitrifying and Denitrifying Bacteria............................................................................ B-10
B.3.4 Microbiologically Influenced/Induced Corrosion (MIC)..................................... B-10
B.3.5 Impact of Microbiological Fouling..................................................................... B-11
B.4 References ............................................................................................................... B-11
B.5 Bibliography ............................................................................................................. B-11
xvii
LIST OF FIGURES
Figure 2-1 Typical Closed Cooling Water System......................................................................2-2

Figure 9-1 Troubleshooting Flow Chart for Sudden Shift in Inhibitor Concentration................9-26
Figure 9-2 Troubleshooting Flow Chart for Contaminant Increase ..........................................9-27
Figure 9-3 Troubleshooting Flow Chart for pH Change ...........................................................9-28
Figure 9-4 Troubleshooting Flow Chart for Change in Conductivity ........................................9-29
Figure 9-5 Troubleshooting Flow Chart for Increase in Corrosion Rate or Corrosion
Product.............................................................................................................................9-30
xix
LIST OF TABLES
Table 2-1 Approximate Percent (%) Composition of Metals Commonly Used in Closed
Cooling Systems ................................................................................................................2-4
Table 2-2 Characteristics of Some Nonmetallic Materials Used in Closed Cooling
Systems .............................................................................................................................2-5
Table 4-1 Typical Corrosion Inhibitors in Closed Cooling Water Systems .................................4-3
Table 5-1 Operating Ranges and Monitoring for Nitrite-Based Programs .................................5-3
Table 5-2 Operating Ranges and Monitoring for Molybdate-Based Programs ..........................5-4
Table 5-3 Operating Ranges and Monitoring for Nitrite/Molybdate Programs ...........................5-5
Table 5-4 Operating Ranges and Monitoring Frequencies for Chromate-Based Programs ......5-6
Table 5-5 Operating Ranges and Monitoring Frequencies for Hydrazine-Based
Programs............................................................................................................................5-7
Table 5-6 Operating Ranges and Monitoring for Silicate-Based Programs ...............................5-8
Table 5-7 Operating Ranges and Monitoring for Pure Water Systems......................................5-9
Table 5-8 Control Ranges and Monitoring for Proprietary Blended Glycol Programs..............5-10
Table 5-9 Control Ranges and Monitoring for Nonproprietary and Plant-Specific Blended
Glycol Programs...............................................................................................................5-11
Table 7-1 Contaminant Concentration Versus Calculated Cation Conductivity .........................7-3
Table 8-1 CCW Corrosion Coupon Rate Guidelines, Mils per Year (mpy) ................................8-3
Table 10-1 Critical Concentration of Chloride and Sulfate, Above Which Pitting of Armco
Iron in Chromate or Nitrite Solutions Occurs (25oC) ........................................................10-2
Table A-1 Recommended CCW Impurity Limits ....................................................................... A-1
Table A-2 Impurity Concentration Levels Allowed by NSSS Vendors ...................................... A-2
Table B-1 Suggested Critical Velocity Limits for Condenser Tube Alloys in Sea Water .......... B-4
xxi
1
INTRODUCTION
1.1 Background
The cooling water needs in electric utility power plants are not limited to steam surface
condensers. Other cooling needs include a variety of applications such as component cooling
systems, emergency diesel generator jackets, enclosure coolers, and lubricating oil coolers.
These cooling needs can be met by closed cooling water (CCW) systems. In nuclear power
plants, the CCW systems provide cooling to both safety-related and non-safety-related heat
exchange equipment. This report provides guidance on chemistry controls in these systems to
minimize corrosion, fouling, and microbiological growth. It is written in a format similar to
several other EPRI guidelines for chemistry control at nuclear power plants. However, this
guideline does not come under the aegis of the NEI 97-06 [1] document that specifies adherence
to guidelines. The purpose of the NEI 97-06 mandate in the other guidelines is to ensure steam
generator long-term reliability at PWRs. This is done by describing control parameter limits that
are to be adhered to without change. The systems described in this guideline are unrelated to the
NEI 97-06 document requirements and, as such, do not fall under those requirements.
Corrosion or fouling of the heat exchange equipment can interfere with its intended function.
This is especially important in safety-related equipment. CCW piping consists of carbon steel in
many (if not most) CCW systems. Carbon steel is subject to corrosion unless protected. In most
cases, carbon steel corrosion control in CCW systems is achieved by adding corrosion inhibitor
chemicals. In nuclear plants, these inhibitors have included chromates, nitrites, molybdates,
hydrazine, and silicates. Inhibited glycol (ethylene glycol or propylene glycol) is also used in
some systems. In addition, some plants achieve satisfactory control of corrosion without
chemicals in pure water systems.
Many plants used chromates initially but have converted to other inhibitors. Chromates are
excellent corrosion inhibitors for carbon steel and have the added advantage of being toxic to
microbiological organisms. Environmental issues led to a decline in the use of chromate
inhibitors in the mid 1980s. This resulted in the replacement of chromates with alternate carbon
steel corrosion inhibitors in many plants. These alternate inhibitors (nitrites, molybdates,
silicates, etc.) can achieve comparable corrosion inhibition, but also introduce more variables
because they do not inhibit the growth of microbiological organisms. EPRI has published a
report that addresses the effectiveness of chromate and chromate replacements [2].
This Closed Cooling Water Chemistry Guideline addresses the use of chemicals to mitigate
corrosion, fouling, and microbiological growth in nuclear CCW systems. The chemical additives
used for these purposes depend on plant design characteristics, water quality, operating
1-1
Introduction
parameters, and specifications of the nuclear steam supply system (NSSS) suppliers. The list of
chemicals is not as extensive as that for service water systems [3], but can be confusing to utility
CCW system engineers and chemists. Both generic chemicals and proprietary blends are used in
CCW systems. Acquiring chemicals with sufficiently low contaminant levels (for example,
microbiological control chemicals) to meet some NSSS suppliers original specifications is an
issue in some nuclear plants (refer to Section 1.3).
The use of chemicals in CCW systems will not resolve problems originating from poor design or
poor maintenance practices that result in excessive system leaks. Excessive leakage makes
consistent chemical control very difficult and offsets the ability of the chemicals to provide
adequate protection.
The guidance provided here is targeted at reducing corrosion, microbiologically influenced

corrosion mechanisms, and system fouling. It also provides examples of troubleshooting based
on changes in chemical parameters and system operation. Deviating from the specifications
outlined in this guideline, with the understanding and approval of plant management, is allowed,
provided that sound technical justification and/or performance monitoring supports the deviation.
1.2 Terms and Definitions
1.2.1 Control Parameters
Control Parameters specify the desired operating chemistry of the system. Control Parameters
are those parameters that have a demonstrated relationship to closed cooling water system
materials degradation. Examples of Control Parameters are pH, corrosion inhibitor
concentration, and corrosive contaminants. There are limits associated with Control Parameters.
Deviation from Control Parameters should be with the understanding and approval of plant
management.
1.2.2 Diagnostic Parameters
Diagnostic Parameters are important to monitor program effectiveness, identify programmatic

problems, and assist in problem diagnosis. These parameters are routinely monitored to ensure
system health or detect adverse trends. Diagnostic Parameters vary depending on the type of
treatment program in use. Depending on the treatment program, Diagnostic Parameters might
include conductivity, ammonia, nitrate, chloride iron, copper, sulfate, and microbiological
activity. There are not limits associated with Diagnostic Parameters.
1.2.3 Investigative Parameters
These nonroutine parameters are part of a toolbox of tests that can be used to respond to a
problem or perceived problem. In certain cases, Investigative Parameters can be used along with
Control and Diagnostic Parameters for system troubleshooting. Examples of Investigative
Parameters include, but are not limited to, individual bacterial species, dissolved oxygen, total
1-2
Introduction
organic carbon (TOC), and calcium and magnesium. Section 9 provides more discussion
regarding the use of these Investigative Parameters in conjunction with the Control and
Diagnostic Parameters.
1.2.4 System Ranking by Tiers
This guideline ranks CCW systems by tiers. The purpose of ranking the systems by tiers is to
provide for more frequent chemical analysis of safety-related systems or systems whose
unavailability will challenge continued plant operations. The tier ranking of a system does not
impact Control or Diagnostic Parameters or impact nominal system concentrations or Action
Levels.
Tier 1 System
This constitutes a cooling or heating system whose unavailability will challenge continued plant
operation. At a minimum, all systems that are safety related, or supporting a safety-related
function, are designated as Tier I systems. Other circuits can be designated as Tier I by the
station at its discretion.
Tier 2 System
This constitutes all remaining systems. Such systems do not usually challenge continued
operation if unavailable.
Intermittent System
An Intermittent (intermittently operated) System can be either Tier 1 or Tier 2, depending on its
intended function. It is operated on an intermittent basis as needed or for routine surveillance.
Assignment as a Tier 1 or Tier 2 system does not impact the control ranges or parameters
monitored but might impact the frequency of monitoring.
1.2.5 Remaining Plant Systems
There can be closed cooling systems associated with a plant that are not normally supervised by
plant technical personnel. Examples of these systems are office building and warehouse cooling
and heating systems. These systems fall outside the scope of this guideline. However, there
might be plant CCW systems that are in Level B storage. It might be necessary to address these
in the site-specific strategic plan. Level B storage refers to ANSI 45.2.2 storage levels for nuclear
components. Level B has the requirements of temperature within the range of 40140F
(460C), no control on humidity, indoors (walls and ceilings intact), and above the floor.
1-3
Introduction
1.2.6 CCW Action Levels
CCW Action Levels have been established for these guidelines so that the importance of out-of-
specification conditions can be effectively communicated to management. The CCW Action
Levels have been written to parallel the actions that are taken in primary and secondary
chemistry systems. However, because closed cooling systems operate at temperatures and
pressures that are significantly lower than the primary or secondary systems of power plants, the
timeframes in which significant effects can be realized are much longer. Revision 0 of this
guideline did not provide guidance on the significance of an out-of-specification condition to
corrosion in that system, or how soon the condition had to be corrected. This made it difficult to
plan appropriate timeframes and work schedules for correcting these conditions. CCW Action
Level 1 conditions are those that can be addressed using the 12-week work schedule concept,
with no discernable increases in corrosion rates or system efficiency. CCW Action Level 2
communicates a more serious condition, requiring action outside the normal 12-week work
schedule.
The CCW Action Levels apply only to Control Parameters, which have defined limits.
Diagnostic Parameters are used as a means to help identify the source of the off-normal
condition, and are generally not a direct function of corrosion inhibition. Diagnostic Parameters
have no CCW Action Levels.
It is important to note that it is expected that these timeframes should be used as not-to-exceed
dates, and that corrective actions will be completed as soon as work schedules permit. The
various Control Parameters can have a negative synergistic effect on system corrosion rates, if
two or more are outside the normal operating range at the same time (see discussion under the
Action Level subsections).
CCW Action Level 1
The normal operating ranges recommended in this guideline represent a conservative

interpretation of closed cooling water chemistry as generally practiced in the nuclear power and
other industries. Action Level 1 denotes a condition where system chemistry Control Parameters
are outside the normal operating levels. The recommended action is to increase monitoring
frequency, as appropriate, and return the parameter to within the prescribed normal operating
range within 90 days. If the parameter has not returned to the normal operating range within 90
days, CCW Action Level 2 is entered.
This timeframe is based on only one Control Parameter being in the Action Level range. If more
than one is beyond established limits, a negative synergistic effect might result. Therefore, if
more than one parameter is in CCW Action Level 1, it is recommended that more aggressive
corrective actions be initiated than if only one parameter is in Action Level 1. Until parameters
are returned to normal, increased sampling frequency should be considered part of those actions.
1-4
Introduction
CCW Action Level 2
Values exceeding the CCW Action Level 2 threshold could initiate short-term system materials
degradation. The recommended action is to return the parameter to within the prescribed control
band within 30 days. If the parameter has not returned to the normal range after 30 days in CCW
Action Level 2, and system operation is to continue, then a risk assessment (engineering
evaluation) shall be performed indicating that the out-of-control parameter will not affect the
long-term reliability of the system. The evaluation should include a sunset date for the out-of-
control condition.
This timeframe is based on only one Control Parameter being in the Action Level 2 range. If
more than one is beyond established limits, a negative synergistic effect might result. Therefore,
if more than one parameter is in CCW Action Level 2, it is recommended that more aggressive
corrective actions be initiated than if one parameter is in the action level. Until parameters are
returned to normal, increased sampling frequency should be considered part of those actions.
1.3 Contaminant Specifications
Nuclear power plants in the United States have been supplied by four Nuclear Steam Supply
System (NSSS) suppliersBabcock & Wilcox, Combustion Engineering, General Electric, and
Westinghouse. Although each of the NSSS suppliers has individual designs, the basic CCW
system and its respective materials are fairly consistent. Each NSSS supplier has issued some
type of guideline covering water quality parameters in CCW systems; however, these guidelines
are inconsistent between suppliers. An example is chloride specification, which ranges from <10
ppm (General Electric) to 150 ppb (Westinghouse).
A goal of the Closed Cooling Water Chemistry Task Group is to establish impurity limits that
will protect system metallurgy but that are reasonable and achievable. With respect to 300 series
stainless steels, impurity limits for chloride and fluoride are recommended to be 10 ppm each.
These are shown in Table A-1 in Appendix A. As reflected in the Diagnostic Parameters for the
various treatment programs, these limits are also considered suitable for the protection of carbon
steel in systems using nitrite, molybdate, and chromate treatment programs. Lower limits are
needed in systems using a hydrazine treatment program or systems using no added chemicals
(pure water systems).
The position paper from which the above limits are derived is located in Appendix A. The
position paper also recommends periodic flushing to avoid sediment buildup in the bottom of
exchangers and that the use of chlorinated solvents for degreasing or other cleaning of closed
cooling water system components be prohibited.
1-5
Introduction
1.4 Purpose
The purpose of the Closed Cooling Water Chemistry Guideline is to provide CCW system
engineers and chemists with guidance for maintaining system chemistry in CCW systems. This
guidance addresses:
Establishing the technical basis for chemical treatment programs
Establishing site-specific programs
Establishing recommended control ranges for the various treatment programs
Establishing Control and Diagnostic Parameters for each type of treatment program
Defining Action Levels to protect the CCW systems
Establishing monitoring frequencies
Establishing appropriate trending programs
Providing guidance for troubleshooting and corrective actions
Determining compatibility with other system materials
Providing industry experience
Providing support for plant life extension
This guideline was developed for nuclear power plants; however, most of the information in the
report is applicable to fossil fueled power plants. They also have CCW systems that are similar
in design and experience many of the same problems.
1.5 Scope
The scope of the Closed Cooling Water Chemistry Guideline is to:

Describe CCW systems
Provide appropriate definitions
Describe water-related problems in CCW systems
Provide a detailed guide to chemical selection
Provide guidance on selecting and monitoring a total water treatment program
Provide guidance on evaluating performance
Although the methods and technologies described in this guideline are extensive, they are not all-
inclusive. There are existing methods that are not described in this guideline, and other methods
continually being developed that could be applicable.
1-6
Introduction
1.6 Assumptions
The systems discussed in this guideline are limited to closed cooling water systems. However,
there are closed low-temperature hot water systems (<82C, 180F) in some plants that are
similar in design and operate in a similar manner to closed cooling systems. The chemical
treatment programs described for closed cooling systems in this guideline are also generally
applicable to closed hot water systems but should be evaluated based on system design.
This guideline does not address steam surface condenser circulating water systems, open or raw
water types of systems, although the treatment programs might be the same or similar. The
guideline does not address Stator Cooling systems because these are addressed in other EPRI
reports [4].
1.7 Management Responsibility and Program Ownership
It is recognized that a specific CCW monitoring program applicable to all plants cannot be
defined due to differences in design, experience, management structure, and operating
philosophy. However, there are standard programs that are used across the industry and most
systems can use one of these standard programs. The overall goal is to minimize corrosion and
maximize the availability and operating life of CCW systems. To meet this goal, an effective
water chemistry control program is essential and should be based upon the following:
Recognition of the long-term benefits of, and need for, proper water chemistry control to
avoid or minimize corrosion degradation of piping, heat exchangers, and other components
Clear management support for operating procedures designed to establish and maintain water
chemistry control (as provided in Sections 4, 5, 6, and 7)
Adequate resources of staff, equipment, funds, and organization
Careful evaluation of site-specific needs and circumstances
Continuing review of plant and industry experience and research
Initiating revisions to the program as appropriate
1.7.1 Water Chemistry Management Philosophy
Management endorsement and support of the CCW strategies is key for successful
implementation. Without it, failure is likely. Management should require predefined methods to
establish and maintain good chemistry for asset preservation.
Nuclear station management is periodically faced with the problem of either keeping a unit
available to produce power and meet short-term power demands, or shutting down to repair
system problems that affect good control of water chemistry, thus helping to ensure the long-
term integrity of system components. The water chemistry philosophy must be effectively
communicated to management so that it is understood that operating with off-normal chemistry
might eventually result in loss of availability of that unit. Limiting the magnitude and duration of
1-7
Introduction
off-normal chemistry can maximize plant availability and system integrity. A program
document, which describes this philosophy, can effectively communicate these concepts to
utility management. This document identifies any deviations that a plant takes from the control
parameters in these guidelines, either permanently or for interim periods when plant conditions
do not allow a prompt return to the control parameter band. Such deviations should be based on
an engineering evaluation, which identifies how the proposed deviations do not have an effect on
system operation. This would be of particular importance for those systems that fall under the
Maintenance Rule.
The information presented in this section is based on the observation that operating and
maintenance philosophies regarding chemistry can significantly affect the integrity and longevity
of CCW systems components. The philosophy and policies discussed reflect the desirability of
operating in a proactive rather than a reactive mode. The costs associated with maintaining CCW
chemistry within these industry recommendations are likely to be less than those associated with
the repair or replacement of heat exchangers and piping, and the outages associated with those
efforts.
Although it is recognized that variety among individual utility organizations exists, there are
basic goals and functions common to all. This section addresses key management considerations
but makes no attempt to specify how they should be integrated into a specific organizational
structure. Additional organizational and administrative guidelines are presented in the INPO
Guidelines for Chemistry at Nuclear Power Stations, Rev. 2 (INPO 88-021, Rev. 2) October
1995. Utility personnel are encouraged to consider both the recommendations in this section and
INPO recommendations when developing or revising their site-specific programs.
1.7.2 Generic Management Considerations
This section lists and discusses the considerations that are common to most utilities, including
the elements of organizations that are needed to carry out a water chemistry program effectively.
Utility-specific implementation policies and procedures should assign responsibilities to specific
positions within the organization. One major element of these guidelines is the need for every
level of management to understand the importance of the site-specific performance goals and
effective chemical treatment presented in Sections 4, 5, 6, and 7. Effective chemical treatment
has great benefits for the utility company by having a positive impact on CCW system integrity.
An important ingredient of a successful management plan for CCW chemistry control is a set of
documents that specify operating guidelines. The documents should:
State the need for the document
State the goal regarding CCW chemistry and station operation
Highlight management support for the document
Assign responsibility for:
Preparation and approval of procedures to implement policy
Implementation of procedures
1-8
Introduction
Assessment of the effectiveness of chemistry control in minimizing component

degradation
Monitoring, analysis, and data evaluation for the chemistry program
Surveillance and review functions
Implementing corrective actions
Utility personnel responsible for plant design in chemistry-related areas should:

Understand CCW systems materials and the operational chemical treatment relationship with
the system materials
Ensure that the system design is reviewed by knowledgeable plant operating personnel,
vendors, and/or consultants as appropriate
Procedures should include:

A plant-specific monitoring program to ensure long-term system integrity
Control limits, sampling frequency, specific corrective action responses, and corrective
action notification and responsibilities
Standardized analytical procedures to ensure accurate laboratory results
Provisions for data review
1.7.3 Training of CCW Chemistry Control Personnel
A program for training all personnel involved with CCW chemistry control should be
established. This program should incorporate the latest information available from EPRI, other
utilities, NSSS suppliers, water treatment vendors, and industry expert consultants. Some
instruction in the basics of the program should be considered for all employees who, by virtue of
their job responsibilities, can affect water chemistry. The training programs should be designed
for the level and qualifications of personnel being trained. The following elements should be
included:
A clear statement of the policy regarding CCW chemistry control, including clarification of
the impact of this policy upon the various responsibility areas.
Identification of the impact of poor chemistry control.
Identification of the chemical treatment control ranges for each program in use in the plant.
Techniques for recognizing unusual conditions and negative trends, particularly for the
station chemists and laboratory technicians. Potential corrective actions and their
consequences should be thoroughly discussed.
The interaction of system operations, engineering, radiation protection, maintenance, and
chemistry departments.
1-9
Introduction
1.8 Roles and Responsibilities of Plant Personnel
1.8.1 Operations
Operators are most familiar with system operational parameters of flow, pressure, and
temperature. These characteristics can be indications of system concerns such as fouling of heat
exchanger surfaces. It is important that changes be effectively communicated to the system
engineer and chemistry personnel so that system chemistry changes can be assessed as part of the
concern. Changes in system alignment (for example, idle pump to operate or alternate train
placed into service) should be reported to the chemistry staff so that system chemistry changes
can be taken into account.
1.8.2 System Engineering

The visual inspection of system component internals is one of the most effective ways of
assessing corrosion mechanisms in a plant system. System engineers are cognizant of ongoing
work for standby trains of equipment and should routinely inspect system internal surfaces for
unusual indications of system wear or corrosion. Their review of system thermal performance
often provides useful information to chemistry personnel in assessing the effectiveness of
chemical treatment. Plant chemistry staff should be notified of system inspections in order to
participate in the evaluation using data from sampling and analysis of debris, deposits, or
corrosion films as available. It is also important to note that if parts substitution arises due to
obsolescence or wear of system components, it is valuable to have chemistry personnel assess
the compatibility of new system materials with the corrosion control agents used in the system.
1.8.3 Chemistry
Maintaining corrosion control agents in a specified concentration band most effectively controls
general corrosion of plant systems. Large swings in concentrations of these control agents can be
detrimental to the protective corrosion film that has been established in the system. Identification
of trends, or changes in trends of these control agents, can provide insight to the system engineer
or operators about potential system problems. Proper assessment of contaminant concentrations
can also provide valuable information regarding system integrity. Thus, routine sampling and
analysis, which is evaluated critically, helps to maintain long-term system integrity.
1.8.4 Maintenance
The repair, replacement, or modification of a plant system can provide opportunities for plant
staff to assess the health of a system. It is also an opportunity for unwanted materials to
inadvertently enter the system. Many new or replacement components are manufactured and
shipped with coatings or materials to preserve their integrity in the dry state. These materials
must be removed prior to installation in the system. Maintenance procedures should address the
types of chemicals that might be used to perform routine work on system components and how
excesses of these materials are to be removed. It should be procedurally required that any
solvents or chemicals that are used in system maintenance must be effectively removed prior to
reassembling the component. Maintenance personnel can also provide valuable insight to
operators, engineers, and chemists about changes in corrosion surfaces of the system.
1-10
2
DESCRIPTIONS OF CLOSED COOLING WATER
SYSTEMS
2.1 Purpose of Closed Cooling Water Systems
There are a number of Closed Cooling Water (CCW) system designs. Some systems cool plant
components that contain radioactive fluids and serve as barriers between radioactive fluids and
the service water system. Other CCW systems are on the evaporator side of a refrigeration chiller
(chiller systems) and some cool the jackets of emergency diesel generators. Some of the CCW
systems cool safety-related components while others cool non-safety-related components. Low-
temperature (<180F, 82C) closed hot water systems (often for building heat) are often included,
based on system design.
A closed system is defined as a heating or refrigerating piping system in which circulating

water or brine is completely enclosed, under pressure above atmospheric, and shut off from the
atmosphere, except that the expansion tank could be open to the atmosphere [5]. A closed
system has also been defined as one in which the water is circulated in a closed loop with
negligible evaporation or exposure to the atmosphere [6].
2.2 Closed Cooling Water System Design
Figure 2-1 illustrates a typical Closed Cooling Water system. The individual heat exchangers are
part of a closed loop. Heat from the closed loop is removed by a heat sink heat exchanger (raw
water heat exchanger or refrigeration chiller). The scope of the Closed Cooling Water Chemistry
Guideline does not, however, include the treatment of the service water side of the heat sink heat
exchanger. This is covered in the Service Water System Chemical Addition Guideline [3].
Low-temperature closed hot water systems are also represented by Figure 2-1. As such, the
principles described in this guideline can also be applied to low-temperature closed hot water
systems.
2-1
Descriptions of Closed Cooling Water Systems
Figure 2-1
Typical Closed Cooling Water System
2.3 Variations of Closed Cooling Water System Design
In addition to water-cooled systems, there are some air cooled CCW systems. There is also at
least one nuclear plant with a hybrid design that operates as a closed loop only during normal
operation. Under emergency or shutdown conditions, the flow is diverted through an open
recirculating cooling tower. This introduces contaminants during those periods of open
recirculation operation. In addition, valve leakage could also introduce contaminants when the
system is operated in the isolated mode.
Although most CCW systems share the same basic design, there are numerous design variations.
These include:
Variations in flow rates
Idle (stagnant) heat exchangers
Low-flow heat exchangers
Variations in thermal load
Makeup water variations
Radiation fluxes
Variations in oxygen content
Shared heat exchangers (cross ties)
2-2
2.4 System Materials
The materials of construction chosen for nuclear CCW systems are a function of engineering
factors, economic factors, and water quality factors. In most plant designs, the piping is typically
unlined carbon steel or stainless steel. The heat exchanger tubesheets, channels, and channel
heads are typically bare or coated carbon steel or stainless steel. Heat exchanger tube materials
are typically a copper alloy (for example, Admiralty brass or copper-nickel) or a stainless steel.
In addition to these materials, emergency diesels might use cast iron, aluminum, and soldered
connections. Other materials that might be included in a CCW system include nonmetallic
materials (gaskets, valve seats, pump seals, packing) and sacrificial anodes.
Table 2-1 is a reference for many different types of metals used in CCW systems. The
approximate concentrations of the composite materials for these alloys are given, as well as the
general Unified Numbering System (UNS) designation. Per ASTM E527, The unified
numbering system (UNS) establishes 18 series of numbers for metals and alloys. Each UNS
number consists of a single letter-prefix followed by five digits. In most cases the letter is
suggestive of the family of metals identified; for example, A for aluminum, P for precious
metals, and S for stainless steels.
Some alloys have trace elements (usually considered <0.01% by weight), which are purposely
included, while, in other alloys, they are present because they are not excluded as part of the
manufacturing process. The more important of these elements are included as notations in Table
2-1.
This table can prove a useful aid to plant personnel who are planning system changes. New or
replacement components for systems should have a UNS number specification. This can help
plant personnel in assessing if the new or replacement part is suitable for the chemical control
currently used in the CCW system. Alternatively, the component might be a significant enough
change of material so that the chemical control agent should be changed to suit the new
component. It might also be useful in assessing if there are other components in the CCW system
that could form galvanic couples with the new material.
2-3
Table 2-1
Approximate Percent (%) Composition of Metals Commonly Used in Closed Cooling Systems
Metal (1)/UNS (3) Fe Cu Ni Cr Zn Mn Al Other (2)

Carbon Steel 98 Carbon = 0.5
C00001-99999
Cast Steelc 98
F11000-12000
Stainless Steel (304) S30400 ~70 810 1820 2 Si=1.00 max
Stainless Steel (400) S40000 80 13 6
Stainless Steel (6%
Molybdenum Austenitic)
S31254 49 0.8 18 20 Mo 6.1
N08367 49 0.1 24.5 20.5 Mo 6.1
N08026 49 3 35 24 Mo 6.1
90/10 Cu/Ni 0.4-1.0 89.0 9.5 0.1 0.10.3 <0.1 Pb trace
C70600 0.7
70/30 Cu/Ni 0.5 68.0 30.0 0.41.0 0.05
C71500w 0.3
Admiralty Brass Sn=1.0, Pb=0.02,
C44300 (Metal B) 0.01 71 28 As=trace
C44500 (Metal D) 71 28 Sn, P trace
Naval Brass (phosphorized) 60 39 Sn+P to 1%
C46700
Phosphobronze 95 Sn=4.3, P=0.3
C60000 90 Sn=10, P=0.1
Muntz Metal 60 39 Pb+As+P+Sb up to 1%
C36000
Copper 99+ Traces of Ag, P, or As,
C10000-14000 depending on grade
Aluminum Bronze
C60800 95 5
C61300 2.5 91 7
C61000 92 8
Monel 400 1.4 31 66 Carbon-0.15
N60000
Aluminum-Nickel-Bronze 85 5 10
C63000
Titanium Up to Up to 8 36 Ti 75-98, Many
R50250-R56322 11 different alloys and
range of percentages.
Also alloys with V and
Mo.
(1) UNS refers to the Unified Numbering System for Metals. This system was developed jointly by ASTM and SAE and is published under ASTM E527/SAE
J1086. Some materials have a range of numbers listed. This signifies that there are several different alloys with similar material composition. The
composition values in this table are the most commonly encountered in CCW systems.
(2) Although these represent minor constituents, they are intentionally added to the metals to provide certain characteristics.
(3) Listings of specific alloy compositions corresponding to specific UNS numbers can be found in Unified Numbering System for Metals and Alloys, ASTM
DS 56H.
w
= wrought, c = cast
Note: Weld materials are not included in the above table.
2-4
Table 2-2 lists names of some nonmetallic components commonly used in CCW systems. It also
shows their generic chemical composition, temperature limits, and some chemical
incompatibilities. The temperature limits are for the materials in pure water. Note that increased
temperature might increase the susceptibility of these materials to degradation with certain
chemicals. This chart should be used as a general guide, and new or replacement components
with nonmetallic parts should be assessed for compatibility with system chemicals during the
work control process. The incompatibilities are based on 48-hour exposure tests, usually at room
temperature. Nonmetallic components can also provide a colonization site and food source for
certain types of bacteria. Any change to the chemical regime or disinfection of a CCW system
due to bacterial contamination should also take these system parts into account.
Table 2-2
Characteristics of Some Nonmetallic Materials Used in Closed Cooling Systems
Temperature
Material
Composition Limit, oF (oC) Use Incompatibilities (3)
Name (1)
(2)
Neoprene Chloro-butadiene 250 (121) Lining for Freon 11, diesel fuel,
polymer piping or heat ammonia, morpholine
exchanger
channel heads
Viton Perfluorinated 350 (177) Gaskets, Ammonia, hydrazine,
hydrocarbon (carbon, O-rings amines
hydrogen, fluorine)
EPDM Hydrocarbon polymer 250 (121) Gaskets,
consisting of ethylene O-rings, tubing,
and propylene chain component
components linings
Teflon Perfluorinated 600 (316) Valve packing,
hydrocarbon (carbon, gaskets,
hydrogen, fluorine) O-rings
Buna N Hydrocarbon polymer 350 (177) Gaskets, Certain Freons
with a nitrile functional O-rings
group
Kalrez Perfluorinated 425600 (218 O-rings, Solutions of some
hydrocarbon (carbon, 316)) gaskets diamines >200oF
hydrogen, fluorine) (93oC) might cause
more rapid deterioration
Polyvinyl Saturated hydrocarbon 390 (199) Piping, valves Sodium hypochlorite at
chloride (PVC) backbone (carbon, 5% (embrittlement with
hydrogen, chlorine) long-term exposure),
ethanolamine
Polypropylene Carbon, hydrogen 250 (121) Hoses Concentrated sulfuric
acid, ethanolamine,
hydrogen peroxide
(1) Information regarding the standard abbreviations for these materials can be found in Standard Practice for Rubber and
Rubber-Lattices-Nomenclature, ASTM D1418.
(2) These are conservative limits for these materials.
(3) A materials incompatibility with specific CCW system chemicals should be verified with the material manufacturer.
2-5
Material composition and chemical reactivity information for Table 2-2 is taken from the
following product literature:
Dupont Dow Elastomers Product Bulletin H-68249, Chemical Resistance and Fluid
Compatibility, Including All Chemicals Under the Clean Air Act.
Montell Polyolefins, Technical Bulletin ID# Tl-010 (1998), Pro-Fax Polypropylene
Chemical Resistance.
DuPont Dow Elastomers, Technical Information Bulletin, VT-500.1, (R3) (1997),
VitonFluid Resistance Guide.
Little Giant Pump Company, Chemical Resistance Chart (also found in Cole-Parmer 2003
2004 Product Catalog).
Compatibility of PWR Gasket and Packing Materials and Ion Exchange Resins with Organic
Amines, EPRI TR-100794, Revision 1, 1994.
2.5 Classification of Closed Cooling Systems
In some nuclear plant designs, there are a limited number of CCW systems. In other designs,
there might be numerous CCW systems (in excess of 20 per unit in some designs). Some of the
CCW systems are far more important to plant safety and reliable operation than others.
This guideline ranks CCW systems by tiers. The purpose of ranking the systems by tiers is to
provide for more frequent chemical analysis of safety-related systems or systems whose
unavailability will challenge continued plant operations. The tier ranking of a system does not
impact Control or Diagnostic Parameters, nominal system concentrations, or Action Levels.
Tier 1 A cooling or heating system whose unavailability will challenge continued plant
operation. At a minimum, all safety-related systems are designated as Tier 1 systems. Other
circuits might be designated as Tier 1 by the station at its discretion. This classification ensures
sampling and testing of key parameters on a more frequent basis.
Tier 2 All remaining plant systems. Such systems usually do not challenge continued operation
if unavailable.
Intermittent An intermittently operated system can be either Tier 1 or Tier 2, depending on its
intended function. It is operated on an intermittent basis as needed or for routine surveillance.
Assignment as a Tier 1 or Tier 2 system does not impact the control ranges or parameters
monitored but might impact the frequency of monitoring.
There might be closed cooling systems associated with a plant that are not normally supervised
by plant technical personnel. Examples of these systems are office building and warehouse
cooling and heating systems. These systems fall outside the scope of this guideline. However,
there can be plant CCW systems that are in Level B storage. It might be necessary to address
these in the site-specific strategic plan. Level B storage refers to ANSI 45.2.2 storage levels for
nuclear components. Level B has the requirements of temperature within the range of 40140F
(460C), no control on humidity, indoors (walls and ceilings intact), and above the floor.
2-6
3
PROBLEMS IMPACTING CHEMISTRY IN CLOSED
COOLING WATER SYSTEMS
Potential problems that could impact chemistry in CCW systems include corrosion,
microbiological growth, and fouling. Scale formation, which is common in open recirculating
systems, is typically not a problem in CCW systems because fresh water is not usually added on
a regular basis.
Mechanical problems can have a significant impact on chemistry in CCW systems. Chief among
these is leakage from the system, which results in the addition of untreated water to the system.
The following provides an overview of the chemistry-related problems in CCW systems. More
detailed discussions are presented in Appendix B.
3.1 Corrosion
3.1.1 Mechanisms
There are a variety of corrosion mechanisms that can occur in CCW systems. These include:
General corrosion
Localized corrosion pitting
Localized corrosion crevice corrosion
Localized corrosion underdeposit
Stress corrosion cracking
Galvanic corrosion (dissimilar metals)
Microbiologically influenced corrosion (MIC)
Flow-assisted corrosion (FAC, also known as erosion-corrosion)
3.1.2 Impact of Corrosion
Excessive corrosion in closed cooling systems will eventually lead to failures, which are most
likely to take the form of through-wall penetration. In extreme cases, a critical piece of
equipment might be lost, which brings about a costly unscheduled outage such as the mid-cycle
shutdown of a nuclear power plant.
3-1
Problems Impacting Chemistry in Closed Cooling Water Systems
Active corrosion within a CCW system can be of significant consequence long before actual
failures occur due to the generation of corrosion products. These corrosion products are not
readily removed by blowdown as in an open cooling water system. Unless a cleanup program is
undertaken, the corrosion products generated within the closed cooling water system do not
leave. When they accumulate on heat transfer surfaces, a loss of efficiency will result. Corrosion
products are much more voluminous than the base metal from which they were produced and can
restrict flow. Accumulations in low-flow or stagnant areas of the system can become breeding
grounds for bacteria. In addition, corrosion can occur beneath the deposits.
3.2 Microbiological Growth
Microbiological organisms will be found in virtually all Closed Cooling Water systems. If not
controlled, these organisms can cause both corrosion and fouling of equipment in the system.
Microorganisms are usually classified according to their ability to grow in the presence or
absence of oxygen. Organisms that require oxygen in their metabolic processes are termed
aerobic, and those that thrive in oxygen-free environments are termed anaerobic.
Microorganisms are also classified according to whether they are free-floating in the bulk water
(planktonic bacteria) or are attached to component surfaces (sessile bacteria).
Growth of sessile organisms can contribute to fouling through the accumulation of slime masses.
These can decrease or block flow in equipment. Slime masses can indirectly contribute to
corrosion because their metabolic waste products accumulate below the slime mass, in contact
with the metal surface. These waste products contain acidic and heteroatom compounds, which
contribute to underdeposit corrosion.
Microbiological growth can also directly impact corrosion by contributing to microbiologically

influenced corrosion (MIC). Certain bacteria, such as acid producing bacteria (APB) and sulfate
reducing bacteria (SRB), create a localized corrosive environment.
Bacteria also create problems in nitrite-treated systems by consuming nitrite. Nitrifying bacteria
consume nitrite and produce nitrate. Denitrifying bacteria can consume nitrite and produce
ammonia or nitrogen. These nitrite conversions can lead to a low or high pH corrosive
environment and loss of capability to inhibit corrosion.
3.3 Fouling
Fouling of CCW systems can be caused by the accumulation of corrosion products,

microbiological growth, or materials introduced from outside the system. Fouling due to
corrosion products and microbiological growth were discussed previously. Another mechanism
for fouling is the introduction of materials from outside the CCW system. Most common is the
use of untreated or raw water for makeup to systems with significant water losses. The impurities
in the makeup water can deposit in the system as mineral scale.
3-2
Problems Impacting Chemistry in Closed Cooling Water Systems
3.4 Operational and Mechanical Considerations
Chemical treatments should not be used to compensate for mechanical problems, operational
problems, errors, or other deficiencies that substantially increase makeup requirements. Systems
described as closed often are not. Water losses usually are usually unnecessary and can be
reduced or eliminated. Some causes of water losses from closed cooling systems are:
Cross connections to other systems operating at lower pressures
Expansion tank discharges
Valve, packing, fitting, piping, seal, and other leakage
Stress corrosion cracking of rolled tubes
The addition of makeup water can dilute the system chemistry below the concentrations at which
the corrosion inhibitors are effective. If the makeup water is demineralized, it is free of dissolved
solids but might contain dissolved oxygen. If the makeup source is service water or potable
water, impurities such as calcium, magnesium, chloride, sulfate, and suspended solids are
introduced. Also, excessive makeup to a closed system, regardless of makeup source, can
introduce microbiological activity due to its presence in the makeup water.
Each system has a corrosion inhibitor decay curve (concentration versus time), the slope of
which is a composite effect of inhibitor decomposition and dilution. Changes to the slope of this
curve can provide early warning of system leakage increases or contaminant ingress.
Other mechanical areas of concern in CCW systems are stagnant or low-flow areas, dissimilar
metals, and temperature fluctuation effects. Stagnant and low flows often do not allow corrosion
inhibitors to maintain adequate contact with metal surfaces. Deposition is also likely to occur in
stagnant and low-flow areas. Dissimilar metals, in contact with each other, can result in galvanic
corrosion. Temperature fluctuations can increase system stresses and impact microbiological
growth.
Many CCW systems have side loops or redundant loops that are operated infrequently. Some
examples of these are cooling loops for radwaste equipment, heating and cooling systems
(sometimes part of one system), and letdown degassifier coolers. These loops can remain
inactive for weeks to months and will be stagnant at their ambient temperature. The
concentration of inhibitor might change (depending on the inhibitor and the length of time
isolated from the main loop), while the concentration of contaminants remains constant. In
addition, the amount of suspended corrosion products might increase. Thus, when the side loop
is put back into service, the concentrations for all these parameters will change slightly. Knowing
when these side loops are put into or taken out of service can provide important information to
the chemist trying to understand changes in inhibitor or contaminant concentrations. For
example, if a side loop will be removed from service for about six months, it might be desirable
to increase the system inhibitor concentration to the high end of the normal range, ensuring that
inhibitor decay does not fall out of the control band for the stagnant loop.
3-3
4
TECHNICAL BASIS OF TREATMENT CHEMICALS
USED FOR CORROSION CONTROL
4.1 Introduction
Chemical treatment in CCW systems is used for the purposes of:

Minimizing corrosion
Controlling microbiological growth
Controlling the deposition of suspended solids
Preventing scale
A variety of water treatment chemicals is available for the control of corrosion, microbiological
growth, and suspended solids deposition in CCW systems. These chemicals can be applied either
as individual products or as blends of two or more products. The selection of these agents is
dependent upon a number of factors. These include, but are not limited to, system design, system
metallurgy, system operating conditions (including temperature and flow velocities),
environmental discharge limitations, radwaste considerations, and makeup water characteristics.
Corrosion inhibitors are materials that react with a metal surface forming a thin film or passive layer
to inhibit the corrosion process. Some inhibitors function at the cathodic areas, while others function
at the anodic areas; thus, they are often referred to as cathodic and anodic corrosion inhibitors.
Some organic inhibitors, such as azoles, form an inhibiting film on the metal surface and could
function in both cathodic and anodic modes.
Microbiological control is a key factor in CCW system operations. Microbiological control

agents include non-oxidizing biocides, oxidizing biocides, and biostatic agents. In nuclear CCW
systems, non-oxidizing biocides are typically used. The selection and application of biocides are
often driven by safety and environmental regulatory concerns. In nuclear power plant CCW
systems, residual contaminants in biocides are also important factors in selection and use.
Deposit inhibitors are low molecular-weight anionic polymers that help keep particulate material
in suspension. They also prevent suspended solids from settling on heat transfer surfaces or in
low-flow areas. These inhibitors are used less in CCW systems than in open recirculating
systems. They do, however, have application in those CCW systems where the accumulation of
suspended solids is a potential problem. Scaling is not usually a problem in CCW systems unless
there is excessive system leakage and raw water is used for makeup. Scale inhibitors are usually
not part of a CCW treatment program.
4-1
Technical Basis of Treatment Chemicals Used for Corrosion Control
In addition to the chemicals discussed, there are other chemicals that are added to the treatment
programs to control pH of the CCW systems. The purpose of pH control is to keep pH in a range
where corrosion is minimized and treatment chemicals are most effective [7]. These might be
chemicals such as sodium (or potassium) hydroxide, sodium bicarbonate, sodium carbonate, sodium
tetraborate (borax), amines, and phosphates (glycol systems).
Water treatment service companies are constantly working to develop new treatment programs
for CCW systems. Although this guideline incorporates the typically used treatment programs
that are commercially available, others might have been developed following the publication of
this guideline. Such new programs could be used, provided a thorough evaluation is performed
prior to introducing them into station systems.
4.2 Makeup Water Sources
Demineralized water is the preferred makeup water source in CCW systems. Industry experience
has shown that other water sources might be acceptable as a makeup water source if all of the
following parameters are considered and periodically analyzed:
Conductivity: High conductivity can be an indication of a corrosive environment.
Alkalinity: Waters with no alkalinity can depress the pH of the system. In almost all cases,
the lowering of pH will increase the potential for general corrosion in the system. The
counterpoint to this is that the addition of makeup water containing alkalinity might decrease
general carbon steel corrosion; however, alkalinity, calcium hardness, and pH should be
evaluated for scaling potential under the actual CCW system chemistry and conditions. This
relates to calcium carbonate scaling.
Calcium Hardness: The system should be evaluated for potential hardness scales (other than
calcium carbonate scales). Such scales include, but are not limited to, calcium phosphate,
calcium phosphonate, calcium molybdate, and calcium fluoride.
Chloride, Fluoride, Sulfate: Chloride, fluoride, and sulfate can contribute to corrosion.
Manganese, Iron, Copper: Manganese, iron, and/or copper can cause corrosion and/or
deposition problems.
Residual Chlorine and Other Oxidants: Makeup water with residual chlorine (or other
oxidants) can be corrosive to system materials and degrade chemical additives.
Ammonia: Ammonia can be aggressive to copper alloys.
Total Organic Carbon (TOC): Total organic carbon can contribute to microbiological
growth.
Suspended Solids: Suspended solids can lead to deposition.
As long as the above items are considered, other water sources, particularly potable water, can be
successfully used in CCW systems.
4-2
4.3 Chemicals Used for Corrosion Control
4.3.1 General
Corrosion control requires knowledge of the metallurgy of the system, an understanding of the
susceptibility of the metals to corrode under the operating conditions encountered, and an
understanding of the limitations of the specific corrosion inhibitors applied. It should also be
noted that corrosion inhibitors require metal surfaces free of deposits in order to be effective.
The purpose of a corrosion inhibitor is to reduce the flow of electrons that are an integral part of
the corrosion process. Cathodic inhibitors act by reducing the flow of electrons at the cathodic
areas. They are typically not applicable to CCW systems, mainly because of system pH levels.
Anodic inhibitors act by reducing the flow of electrons at the anodic areas. Anodic inhibitors are
often considered pitting prone because underfeed of the inhibitor can cause pitting.
Hydrazine concentrations in the range of 550 ppm provide a reducing environment in the closed
cooling water system. Although reaction with oxygen is not rapid at the systems normal
operating temperatures (~75150F [2466C]), maintaining this concentration range will reduce
dissolved oxygen to the 110 ppb range. Additionally, long-term exposure to hydrazine
concentrations of this range will maintain iron oxides in the magnetite form. This helps to
minimize general corrosion rates.
Inhibitors described as film formers create a thin protective layer on the metal surface. Because
the film is created on the entire metal surface, they are considered neither anodic nor cathodic.
The corrosion inhibitors used for protection of copper and copper alloys are film formers.
Typical corrosion inhibitors used in CCW systems are shown in Table 4-1.
Table 4-1
Typical Corrosion Inhibitors in Closed Cooling Water Systems1
Anodic Film Formers Reducing Agents

Nitrite Tolyltriazole Hydrazine
Molybdate Benzotriazole
Chromate Mercaptobenzothiazole
Polysilicate
1
See Section 4.5 for a discussion of inhibitors used in glycol systems.
4-3
4.3.2 Commonly Used Ferrous Alloy Corrosion Inhibitors
The typical corrosion inhibitors for mild carbon steel in power plant CCW systems are:
Nitrites
Molybdates
Chromates
Reducing agents
Silicates
Combinations of these chemicals (nitrite plus molybdate) are also frequently used. By combining
inhibitors, the total inhibitor concentration required is often less than if either inhibitor was used
alone.
The above inhibitors will almost always require the addition of a copper corrosion inhibitor if
there is copper or a copper alloy in the system. They will also usually require the addition of a
pH control agent to adjust pH into a range that will assist the inhibitor with corrosion control.
Critical Concentration of Nitrite, Molybdate, and Chromate Technical Basis
Considerable research in the 1950s and 1960s indicated that the critical concentration of
passivators such as chromate (CrO42-), nitrite (NO2-), and molybdate (MoO42-) lies somewhere in
the range of 10-3 to 10-4 M [8]. The critical concentration is defined as the point below which
passivity is lost in anodic areas and pitting may be initiated. The presence of chloride ions and
elevated temperatures can increase this critical concentration. It should be noted that these
experiments were conducted with demineralized water under laboratory conditions. Actual plant
conditions are different from laboratory conditions and must be taken into account.
It is noted that there is an order of magnitude difference in the range cited by Uhlig. For purposes
of this guideline, the critical concentration of nitrite, molybdate, and chromate is considered to
be the more conservative 10-3 M. This translates to 46 ppm of nitrite as NO2-, 160 ppm of
molybdate as MoO42-, and 116 ppm of chromate as CrO42-. The mechanisms of other inhibitor
systems (silicates, reducing agents, pure water) are different and do not follow the same critical
concentration guidelines.
The working control range for an inhibitor should be technically justified, sufficiently
conservative, but not overly narrow. This guideline will recommend a normal operating range
based on applicable research and industry experience. The discussion of each inhibitor will
indicate exceptions that might justify establishing a lower or higher control band if technically
justified and documented.
The characteristics, advantages, and disadvantages of various corrosion inhibitors are identified
in the following paragraphs.
4-4
Nitrites
Mechanism
Nitrite forms a passivating iron oxide film at the anode. Nitrite complexes with iron surfaces to
form an extremely thin and highly tenacious corrosion product layer in a manner similar to
chromate.
Applicable Metallurgy
Ferrous alloys [9].
Normal Operating Range
For the purposes of this guideline, the normal operating range for nuclear power plants is 500
1500 ppm as NO2-.
Applicable Concentration Low: The lower concentration of 500 ppm as NO2 is based on
general industry experience and offers a conservative inventory of inhibitor to compensate for
potential losses due to leaks, microbiological activity, or oxidation. In other industries, operation
at levels down to 300 ppm as NO2- is not unusual, particularly in chilled water systems that
typically operate in the range of 4550oF (710oC).
Applicable Concentration High: The upper concentration of 1500 ppm as NO2- is based on
general industry experience; however, this is not a level that could be considered harmful for the
system components. Nitrite concentrations up to 4000 ppm as NO2- were tested in one study and
did not appear to damage carbon pump seals [10]. Operation in excess of 1500 ppm as NO2-
should take into consideration such factors as:
Interference with analytical tests for impurities (particularly chlorides and fluorides [see the
discussion on analytical methods in Section 8])
Impact on radwaste
Providing potential for increased biological activity
Associated Additives and Conditions
Nitrite is usually combined with a pH control agent (sodium hydroxide or a buffering compound
such as sodium tetraborate [borax]) and a copper corrosion inhibitor such as an azole. Borax
often cannot be used in BWR plants because of the potential for it to pass through the radwaste
treatment facility and be added to the reactor feedwater. In this case, other pH control agents or
buffers are used.
A pH range of 8.5 to 11.0 is applicable to nitrite-treated systems where an azole is maintained at

recommended concentrations or no copper alloys are present in the system [11]. This pH range
4-5
represents a change over the pH range recommended in Rev. 0 of the Guideline (Sections 8.5
through 10.5). This change has been made based on operating experience at South Texas Project,
input from technical experts in the Task Group, and the beneficial biostatic aspects of increased pH.
An azole is needed for copper corrosion inhibition. Applicable control ranges for copper
corrosion inhibitors are discussed in Section 4.3.3. As noted in Section 4.3.3, an increased azole
concentration (>25 ppm) is recommended when operating at a pH above 10.5.
Nitrates are sometimes added to nitrite formulations to make the inhibitor package applicable to
systems containing aluminum. Nitrates are also produced by the oxidation of nitrites, primarily
by microbiological activity.
Advantages
Nitrite is the most widely used inhibitor component. These treatments are effective inhibitors
that do not require oxygen to form the inhibitor film. The success of nitrite-based inhibitors is
well documented in the industry.
Nitrite is more resistant to the effects of chloride than is chromate, but is somewhat less
resistant to the effects of sulfate [12] (see Section 9, Table 9-1 for more detail). Neither
chloride nor sulfate should be present at significant concentrations in plants where
demineralized water is used as makeup.
Nitrite can be used at higher levels (up to 4,000 ppm) than chromate because it has less of a
tendency to abrade carbon pump seals [10].
Nitrite has lower aquatic toxicity than chromate; however, it might also be subject to
discharge restrictions.
Disadvantages
Nitrite does not inhibit microbiological growth and, in fact, is a nutrient for certain types of
bacteria.
Because nitrite is used at high concentrations, it adds to the difficulty of processing radwaste.
The high concentration reduces the run length of radwaste ion exchange beds.
Under certain conditions, concentrations of nitrate (a byproduct of nitrite-treated systems) in
the range of 10,000 ppm (1%) have been associated with stress corrosion cracking of carbon
steel [13,14]. Concentration mechanisms underneath deposits might serve to achieve these
levels even if nitrate concentration in the bulk water is lower.
The ammonia that might be produced in nitrite-treated systems can attack copper alloys
under oxidizing conditions. Admiralty brass and other brasses might exhibit stress corrosion
cracking in the presence of ammonia and oxygen.
Water drained from systems treated with nitrite should not be reused in the system unless
steps are taken to eliminate biological effects. Nitrite serves as an excellent food source for
biological activity. Reusing water that has been drained from the system increases the
potential for biological contamination.
4-6
Radwaste Considerations
Nitrite-containing wastewater will compete with anionic radioisotopes for ion exchange sites,
resulting in reduced removal capacity for other ions such as iodine. Consumption of cation resin
results from the presence of the nitrite counter-ion (sodium or potassium). In addition to the
exhaustion of resin sites, the introduction of CCW water will shift the inlet pH to the
demineralizers. Nitrite-containing CCW water can:
Act as a regenerant solution for the anion and cation resin, causing the sloughing or bleed-off
of radionuclides.
Precipitate some metal ions (notably iron) by shifting inlet demineralizer pH from pH of 45
to 78. This will foul resin bead surfaces, choking off resin capacity, and might lead to
increased p on beds causing premature changeout.
Change the chemical form of 58/60Co2+ and 125SbO+1 and +3 to hydroxy-colloids, which are
neither exchangeable nor filterable.
Nitrite is added as sodium salts because of solubility characteristics. This can present a challenge
to those plants that recycle water back to the primary system because the sodium ion will bleed
through ion exchangers in the radioactive waste processing systems and can add to 24Na
formation in the primary coolant system.
Waste from closed cooling loops is often processed through the radioactive waste processing
systems. If significant changes are made to the corrosion control agents used (either
concentrations or types), the plant Updated Final Safety Analysis Report (UFSAR) should be
consulted regarding changes to chemical processes and the Radwaste Process Control Program.
The presence of tetraborate in many commercial nitrite formulations is also of concern at BWR
plants because reuse of water containing boron might cause reactivity changes and tritium
production when used for makeup in reactor cooling water systems. Borates can also affect the
analysis of contaminants like fluorides and chlorides if the water is recycled.
High concentrations of nitrates can react with organic material to create an exothermic reaction.
Nitric acid is known to react with ion exchange materials and create a potentially explosive
situation.
Molybdate
Mechanism
Molybdate operates by a similar passivation mechanism as chromate and nitrite. It forms a

passivating film at the anode, consisting of ferric, ferrous, and molybdenum oxides.
Molybdenum is in Group VI A in the periodic table, along with chromium. It shows inhibitive
effects on the general and localized corrosion of ferrous and nonferrous metals.
4-7
It is generally accepted that the corrosion inhibition of iron is achieved by adsorption of

molybdate onto the porous oxide surface. The mechanism is thought to be a process of ion
exchange, followed by the formation of an insoluble film reported to be ferric molybdate
(FeMoO4). The adsorption produces a layer that resists the corrosive effects to other anions,
particularly chlorides and sulfates.
Role of Dissolved Oxygen
It is commonly believed that formation of the passive film requires the presence of dissolved
oxygen or another oxidizing agent, but it is not clear how much oxygen might be required. There
are conflicting references on this subject. Vukasovich provided a literature review on the subject
[15]. One of the most commonly cited references is Pryor and Cohen [16]. This study states that
oxygen is the primary passivator with adsorbed molybdate acting in film repair to maintain a
passive oxide film. This study concluded that molybdate is ineffective in deaerated solutions. It
has been pointed out by May [17], however, that the Pryor and Cohen study compared an
oxygen-saturated solution versus an oxygen-free solution. The molybdate grew a film of
interference in deaerated water but the solution became colored with iron. The measured
corrosion rate in the deaerated water was 0.09 mils per year. Uhlig and King also indicate that
both oxygen and molybdate adsorb on the corroding iron surface [18].
Other studies have indicated that oxygen does not play a central role in the molybdate corrosion
mechanism. Robertson indicated adsorption of molybdate is at the metal-solution interface and
formation of a molybdate complex with iron having protective properties [19]. Cartledge
identified the precipitation of ferrous-ferric molybdates, which block corroding anodic sites [20].
Meziane indicated that the inhibiting effect of molybdates in the range of 10-4 to 10-3 M was
increased by the presence of dissolved oxygen. However, passivity was also obtained in
deaerated conditions [21].
The bulk of the literature indicates that oxygen does play some role in the molybdate corrosion
inhibition mechanism. What is not clear are the amount of oxygen that might be needed and the
impact of molybdate concentration and pH level on inhibitor effectiveness.
Most closed cooling systems are not completely oxygen free. There are several points in a typical
system for oxygen ingress. These include the air-water interface in expansion tanks, oxygen
saturated makeup water, and pump seals. Some oxygen can be beneficial but there is no available
information that establishes a critical oxygen concentration. Based on available empirical
evidence, adequate molybdate concentrations and pH ranges will provide satisfactory corrosion
protection.
Molybdate is applicable to ferrous alloys and aluminum.
4-8
1000 ppm as MoO42-.
Applicable Concentration Low: The lower concentration of 200 ppm as MoO42- is based on
industry experience and offers an inventory of inhibitor to compensate for system leaks. Because
molybdate is not subject to loss by microbiological activity or oxidation, less of an inventory is
needed than for nitrite. Initial (passivation) dosages should be in the upper part of the typical
operating range (6001000 ppm as MoO42-).
Applicable Concentration High: There has not been an upper acceptable dosage established for
molybdate, based on pump seal degradation, as there has been for chromate. However, the
impact of high dosages on overall system condition has not been investigated and it is prudent to
stay within the recommended operating range. Operating in excess of 1000 ppm as MoO42-
Interference with analytical tests for impurities (particularly chlorides and fluorides [see
discussion of analytical methods in Section 8])
Impact on radwaste
Molybdate is often used with sodium hydroxide, sodium carbonate, sodium bicarbonate, an
amine, or a borate to control pH. A pH range of 9.011.0 is applicable for molybdate-treated
systems where an azole is maintained at recommended concentration or no copper alloys are
present in the system.
Molybdate is added as the sodium molybdate salt. This ionizes in water to form MoO42-
(molybdate) ions. Molybdate ion is the conjugate base of the weak acid H2MoO4. The molybdate
ion is the species that participates in the passivation process. If the pH of the solution is lowered,
two effects occur. First, the molybdate ion becomes protonated, forming the H2MoO4 species
(which does not participate in the passivation process). Secondly, the molybdate ion forms
polyhydroxy complexes below pH 7.0 and polymeric molybdate species at approximately pH
6.0. This transformation to species other than the MoO42- species below pH 7.0 reduces the
efficacy of the added molybdate [22].
corrosion inhibitors are discussed in Section 4.3.3.
Advantages
Molybdate does not exhibit the toxicity of chromate.
Molybdate does not act as a nutrient for microbiological growth.
Concentration of molybdate in the system is only reduced via system demand and leakage.
Once formed, the protective film is tenacious and provides good protection against the effects
of chlorides and sulfates [23].
4-9
Disadvantages
Molybdate does not inhibit microbiological growth as does chromate.
Incomplete understanding of the role of dissolved oxygen on film formation.
Molybdate is more costly than nitrite but this might be offset by not being lost through
microbiological activity.
Molybdate might have some environmental restrictions.
Molybdate can be activated to 99Mo, which decays to 99Tc. This might, however, be less
significant than the activation of sodium to 24Na (molybdate is present as the sodium salt so
both radionuclides have the potential to be formed).
Molybdate-containing wastewater will compete with anionic radioisotopes for ion-exchange

sites, resulting in reduced removal capacity for other ions such as iodine. The counter-ion
(sodium or potassium) will increase consumption of cation resin. Large volumes of resin are,
therefore, required to process wastewater from molybdate-treated systems. If tetraborate is used
as a pH buffer, the reactivity management concerns discussed previously will also be of concern
to BWR plants. Borates can also affect the analysis of contaminants such as fluorides and
chlorides if the water is recycled.
Molybdate is added as sodium salt because of solubility characteristics. This can present a
challenge to those plants that recycle water back to the primary system because the sodium ion
will bleed through ion exchangers in the radioactive waste processing systems. This can add to
24
Na formation in the primary coolant system.
concentrations or types), the plant UFSAR should be consulted regarding changes to chemical
processes and the Radwaste Process Control Program.
Nitrite/Molybdate
Mechanism
A nitrite/molybdate combination inhibitor operates by the same mechanisms described for the
individual components. Sodium nitrite is an oxidizing salt that can accelerate the rate at which
the ferric-molybdate film is formed on the metal surface. The combination of nitrite and
molybdate is synergistic in that nitrite maintains the surface oxide film and molybdate protects
the surface oxide from sulfate and chloride attack [23].
4-10
Nitrite/molybdate is applicable to ferrous alloys and aluminum.
Wide ranges of nitrite-to-molybdate ratios are provided by various suppliers. For the purposes of
this guideline, the normal operating range for nuclear power plant CCW systems is 501500 ppm
NO2- and 1601000 ppm MoO42-.
Applicable Concentration Low: The lower concentrations of 50 ppm NO2- and 160 ppm
MoO42- are based on general industry experience and offer a conservative inventory of inhibitor
to compensate for potential losses due to leaks, microbiological activity, or oxidation.
Applicable Concentration High: The upper concentrations of 1500 ppm NO2- 1000 ppm
MoO42- are based on the upper concentrations for the individual nitrite and molybdate programs.
Operating in excess of these levels should take into consideration such factors as:
Interference with analytical tests for impurities (particularly chlorides and fluorides [see
Impact on radwaste
Providing potential for increased biological activity
Sodium tetraborate (borax), sodium hydroxide, sodium carbonate, or sodium bicarbonate can be
added for pH control in order to achieve a pH range of 8.511.0. Borax often cannot be used in
BWR plants because some might pass through the radwaste treatment facility and be added to
the reactor feedwater. A pH range of 8.511.0 is applicable to nitrite/molybdate-treated systems.
This is the same pH range as for nitrite-treated systems.
corrosion inhibitors are discussed in Section 4.3.3.
Nitrates are sometimes added to nitrite/molybdate formulations to make the inhibitor package
applicable to systems containing aluminum. Nitrates are also produced by the oxidation of
nitrites, primarily by microbiological activity.
Advantages
Nitrite and molybdate exhibit low aquatic toxicity.
The total dissolved solids content of the closed cooling water might be lower than if either is
used alone when using the low-concentration end.
4-11
The nitrite/molybdate combination is less prone to system upsets. If nitrite is lost through
microbiological action, the molybdate remains and provides protection.
Nitrite and molybdate are synergistic and can be operated near the bottom of the ranges
applicable to nitrite or molybdate.
Disadvantages
The nitrite might be a nutrient for microorganisms.
Both nitrite and molybdate might have some environmental restrictions.
Water drained from systems treated with nitrite should not be reused in the system unless
steps are taken to eliminate biological effects. Nitrite serves as an excellent food source for
biological activity. Reusing water that has been drained from the system increases the
potential for biological contamination.
As previously discussed, both nitrite and molybdate will compete with anionic radioisotopes.
Anion resin has a high relative selectivity for nitrite and molybdate in comparison to anionic
radioisotopes such as iodine. Sodium or potassium used as counter-ions to nitrite and molybdate
will consume cation resin and inhibit removal of cationic radioisotopes. Large volumes of resin
are therefore required to process wastewater from molybdate-treated systems. If tetraborate is
used as a pH buffer, the reactivity management concerns discussed previously, will also be of
concern to BWR plants that might reuse borated water. Borates can also affect the analysis of
contaminants such as fluorides and chlorides if the water is recycled.
Molybdate can be activated to 99Mo, which decays to 99Tc (a very long-lived radionuclide).
Molybdate and nitrite are both added as sodium salts because of their solubility characteristics.
This can present a challenge to those plants that recycle water back to the primary system
because the sodium ion will bleed through ion exchangers in the radioactive waste processing
systems. This can add to 24Na formation in the primary coolant system.
High concentrations of nitrates can react with organic material to create an exothermic reaction.
Nitric acid is known to react with ion exchange materials and create a potentially explosive
situation.
4-12
Chromate
Chromate is a strong oxidizing agent that accelerates the oxidation of ferrous ions to ferric ions
so that a thin adherent iron oxide quickly forms at the anodic surface. Metal oxides caused by
this reaction become passive and are relatively inert to further oxidation or corrosion. Chromate-
based inhibitors provide excellent corrosion protection for CCW systems but offer challenges
because of toxicity concerns. At the levels recommended for corrosion control, chromate is also
an effective microbiological control agent.
Mechanism
Chromate forms a passive surface layer of ferric and chromic oxides.
Chromate is applicable to ferrous alloys, copper alloys, zinc, aluminum and soft solder.
300 ppm as CrO42-or as specified by NSSS Supplier.
Applicable Concentration Low: The lower concentration of 150 ppm as CrO42- is based on
industry experience and offers an inventory of inhibitor to compensate for system leaks. Because
chromate is not subject to loss by microbiological activity or oxidation, less of an inventory is
needed than for nitrite.
Applicable Concentration High: The 300 ppm maximum is due to the degradation of carbon
pump seals caused by high chromate levels (above 500 ppm) [10]. One NSSS vendor
recommends 1000 ppm CrO42- on the initial fill. Operating in excess of 1000 ppm as CrO42-
Interference with analytical tests for impurities (particularly chlorides and fluorides [see the
Impact on radwaste
Although chromate-based inhibitors are effective over a broad pH range, sodium or potassium
hydroxide is often added to adjust the pH into a range of 8.0 to 11.0. Potassium dichromate or
disodium phosphate can be used for pH reduction. Because chromate is a good copper alloy
corrosion inhibitor, the addition of an azole is not required. Chromate, however, is compatible
with the azoles.
4-13
Advantages
High level of effectiveness as a corrosion inhibitor
Action as a biocide or biostat
Disadvantages
Due to the aquatic and mammalian toxicity of chromate, care must be given to maintaining a
leak-free system. Leaks (for example, pump or valve packing leaks) will flow to a waste
collection system and require processing. In the event that part (or all) of the system must be
drained, the chromate-containing water must be routed to an appropriate wastewater
treatment facility or be collected and reused if at all possible. However, chromate is easier to
reuse because the inhibitor is less likely to become microbiologically contaminated.
Above approximately 500 ppm as CrO4=, chromate can degrade carbon pump seals [10]. No
information is available on its impact on metallic or ceramic pump seals, based on the fact
that one NSSS supplier recommends 1000 ppm CrO42- on initial fill.
Because chromate will compete with anionic radioisotopes, large volumes of resin might be
required to process wastewater from chromate-treated systems. The relative selectivity of anion
resin for chromate is high in comparison to anionic radioisotopes such as iodine. Similar effects
are seen on cation resin from the counter-ion used with chromate (typically potassium or
sodium). Additionally, the resin generated by radwaste processing of chromate waste might also
be considered a mixed waste, depending on the extent of its loading on the resin. Determination
of the mixed waste implications of spent chromated resin should be made on a case-by-case
basis. Handling of chromated wastewater could also be a concern from a personnel safety
standpoint.
Hydrazine
Mechanism
Hydrazine reacts with iron oxide and copper oxide to form protective oxide (passive) films [24].
The corrosion inhibiting effect of hydrazine is based essentially on the activation and
acceleration of the oxidation of Fe0 to Fe(II) and subsequent formation of a protective layer of
magnetite on the surface of the steel.
4-14
Hydrazine has been successfully used in all-ferrous and mixed metallurgy systems. For mixed
metallurgy systems, the hydrazine and pH operating ranges require site-specific optimization to
minimize the total corrosion product concentration in the coolant.
For the purposes of this guideline, the normal operating range is 550 ppm. Levels up to 200
ppm are used in some all-ferrous alloy systems.
Applicable Concentration Low: The lower concentration of 5 ppm is based on plant

experience.
Applicable Concentration High: The upper concentration of 50 ppm is based on plant

experience in plants with mixed metallurgy. The upper concentration of 200 ppm in plants with
all-ferrous metallurgy is also based on plant experience.
Hydrazine is either used without additives or with the addition of an amine for pH control. The
applicable pH ranges are 8.59.6 when copper alloys are present, or 8.510.5 when in all-ferrous
alloy systems.
Advantages
Hydrazine does not add any dissolved solids to the water being treated.
Impact on radwaste ion exchange is minimal.
Plants using hydrazine have not experienced microbiological problems.
Disadvantages
Hydrazine decomposes to ammonia, which can attack copper alloys under high-oxygen
conditions.
Discharges to the environment are regulated due to hydrazine toxicity.
Oxygen ingress can result in localized corrosion.
The passive or protective oxide film formed by hydrazine is loosely bound.
Hydrazine-treated systems typically have a lower specific conductivity than chromate-, nitrite-,
and/or molybdate-treated systems. Radwaste processing of hydrazine-containing wastewater is
generally not as difficult as with other treatment methods.
4-15
Large volumes of hydrazine-treated water can change the chemical form of 58/60Co2+ and
125
SbO+1 and +3 (due to pH change) to hydroxy-colloids, which are neither exchangeable nor
filterable.
Silicates
Mechanism
The most frequently used silicate inhibitors are the glassy amorphous polymeric silicates.
Silicates react with dissolved metal ions at the anode. One likely mechanism for their corrosion
protection is the fact that they hydrolyze in water to form a negatively charged colloidal particle
that migrates to the anodic area [25]. Uhlig indicates that silicates facilitate passivation by
making conditions more favorable for adsorption of oxygen [26]. In alkaline waters, a silicate
with a formula of Na2O 3.3SiO2 is often used, although other silicates, such as solid glassy
silicates, have been used. The gel formed at anodic sites is highly tenacious and the inhibiting
properties of silicates increase with increasing temperature and pH. Silicates have surface-active
properties that allow them to penetrate deposits of corrosion products and inhibit active
corrosion.
Silicates protect copper, aluminum, and ferrous alloys. Some diesel engine manufacturers
prohibit silicates. Silicates have been used in nuclear plants but less frequently than the other
inhibitors.
The normal operating range is 2060 ppm as SiO2 above the inorganic silica content of the
water. However, dosages up to 200 ppm are not uncommon.
Applicable Concentration Low: The lower concentration of 20 ppm above background is based
on general and plant experience.
Applicable Concentration High: The upper concentration of 60 ppm above background (and
sometimes up to 200 ppm) is based on general and plant experience.
Silicates do not perform well at pH levels below 7.0, but are satisfactory in low dissolved solids
water above pH 7.5 and as high as 11.0. Polysilicates are in an alkaline medium and increase the
pH of CCW water. Sodium hydroxide can be used to provide additional pH control. Azoles are
usually not required but can be added for additional copper alloy corrosion protection.
4-16
Advantage
The toxicity of silicates is low.
Disadvantages
Film formation is slow (days or weeks versus hours).
Polysilicates form a fragile film (easily destroyed).
Silicates appear to be primarily anodic inhibitors, but have not been reported to contribute to
pitting.
Limited shelf life of the polysilicate product.
Polysilicates are non-ionic and will act as inert species when processed with ion exchange. Few
radwaste processing considerations apply to polysilicate-containing wastewater at PWR plants.
At BWR plants, however, polysilicates are of concern because they will break down to
orthosilicates when used for reactor coolant makeup.
4.3.3 Copper Alloy Corrosion Inhibitors
Chemicals used for copper corrosion control are nitrogen containing organic compounds
(azoles). Three chemicals of this type are used: tolyltriazole (TTA), benzotriazole (BZT), and
mercaptobenzothiazole (MBT).
After the first quarter of 2004, there might be no U.S. domestic manufacturers of MBT. MBT is
still available in the U.S. via the European market.
There is also a halogen-resistant azole available. This is a modification of the TTA molecule that
has been chlorinated, improving resistance to degradation by oxidizing biocides. Because this
molecule contains chlorine, its use will add chloride to the CCW water.
Mechanism: Azoles react with copper ion to form a thin film that reinforces the oxide film on the
copper layer [27]. MBT is the fastest film former of its type. Azoles are general film formers
the film is formed at both the anode and the cathode [28].
Although TTA and BZT form a protective film more slowly than MBT, they are more stable
under conditions of high temperature. BZT and TTA are used in both open recirculating and
CCW systems. Some suppliers blend TTA or BZT with MBT to incorporate both rapid film-
forming properties and stability into a single formulation.
The azoles also react with copper present in the bulk water. The copper-azole complex is a fine
particulate that can be removed with a 0.45- filter [29].
4-17
All three azoles are effective for copper alloys. MBT has been identified as the most effective for
soft solder connections in emergency diesel generators [30].
For the purposes of this guideline, the nominal system concentration for CCW systems in nuclear
power plants is 5100 ppm azole.
Applicable Concentration Low: The lower concentration of 5 ppm is based on general industry
experience and offers a conservative inventory of inhibitor to compensate for potential losses due
to leaks and system demand. One study confirmed the applicability of a 10-ppm azole dosage
[31]. This study did not test TTA concentrations below 10 ppm. The 5-ppm azole lower limit
recognizes that a protective film exists on the metal and a maintenance dosage is required.
TTA/BZT will protect the zinc in brasses although the information available involves a
laboratory study using city water [32]. The study tested brass with a higher zinc content (37%)
than Admiralty (27%) and suggested a range of 2050 ppm azole.
Applicable Dosage Range High: There has not been an upper dosage established from the
standpoint of ineffectiveness or risk to system components. The recommended maximum of 100-
ppm azole is based on economics and TOC considerations. Concentrations in excess of this
would offer little benefit.
At 10100 ppm, the azoles are effective in the pH range of 8.511.0. TTA dosage should provide
a residual concentration of 25 ppm azole or greater for an operating pH of 10.511.0 [11].
The azoles are typically used as additives to ferrous alloy inhibitors.
Advantages
The presence of an azole reduces deposition of copper ion on steel.
Azoles are low in toxicity compared to chromate.
Disadvantages
MBT produces disulfide and sulfate upon degradation.
Decreasing commercial availability of MBT.
4-18
At typical use concentrations (5100 ppm azole), radwaste processing of filming inhibitors such
as TTA, BZT, or MBT is not of great concern. Because the inhibitors are sparingly soluble in
water, high concentrations can lead to fouling of ion exchange resins. Because MBT degrades to
sulfate, slightly higher sulfate concentrations could result in water treated with MBT. Continuous
input of these chemicals to radwaste will increase the amount of organic loading on anion resins.
4.4 Closed Cooling Water System Corrosion Control Without Chemicals

(Pure Water Systems)
Corrosion control of CCW systems without chemicals has been successful. These systems
typically have low operating temperatures (<100oF) and use demineralized water for makeup.
Boiling water reactors have used demineralized water in CCW systems to prevent system
chemicals from leaking into floor drains and entering the radioactive waste treatment and water
recycle systems. A disadvantage is the lack of chemical buffering, which requires that system
purity and integrity be maintained. The primary impurities of concern are anions that can
accelerate a variety of corrosion mechanisms (general and pitting corrosion, as well as stress
corrosion cracking of stainless steels).
Oxygen control in these systems is a very important parameter as well. Most CCW systems
contain copper or copper alloys. The mechanism of formation for copper corrosion films can
take place in two separate oxygen control ranges. One of these regimes controls oxygen
concentration to <100 ppb. For this range the cuprous oxide film is formed on the surface of the
copper alloy. The other regime maintains the system in an oxygenated state at >2000 ppb. Here
the cupric oxide film forms the protective barrier for the metal. Both of these oxygen control
regimes can be used successfully, but they must be used separately.
The rate of copper corrosion significantly increases when the system is allowed to operate in the
oxygen concentration range between 1002000 ppb. The corrosion film is in a state of flux
between cuprous and cupric oxide and easily sloughs off the metal surface, causing additional
corrosion. This will have the effect of reducing flow, increasing solids and copper content, and
reducing heat transfer efficiency.
Although stator cooling systems are not included in this guideline, most experiences with
significant corrosion problems due to poor oxygen control are related to stator coolant systems
[4]. In one case, the vent line outside a building became blocked with avian debris, prohibiting
exchange of outside air with the system. The oxygen concentration slowly depleted, the copper
corrosion rate increased, and system flow decreased [33]. In a separate case, oxygen intrusion
into a low-oxygen system occurred in a time period of a few minutes, causing a 35% flow
reduction and significant increase in copper corrosion products2.
2
Seabrook Station, February 1996.
4-19
Mechanism and Effectiveness
Low ionic impurities and dissolved oxygen in the cooling water allows the formation of a stable
oxide film with acceptably low corrosion rates. Impurity control can be achieved with sidestream
filters for particulates and demineralizers for ionic contaminants. Feed and bleed is also used
for impurity control but this can change dissolved oxygen levels, potentially affecting the
corrosion film. It is important to ensure that the makeup water to the system has approximately
the same oxygen content as the system.
Corrosion control without chemicals (pure water systems) is applicable to ferrous and copper
alloys.
Control Range
System corrosion will increase with impurity concentrations. The impact of the individual
impurities is additive. If more than one parameter is greater than the recommended range, effort
should be expended to correct that condition. The recommended control values are:
Conductivity 2 S/cm
Chloride 50 ppb
Fluoride 50 ppb (for systems with stainless steel and temperature >150F [66C])
Sulfate 50 ppb
Dissolved oxygen <200 ppb (100 ppb or >2000 ppb based on stator cooling guidelines for
systems with copper)
Chemical additives are not used for demineralized water CCW systems. In the event of
microbiological activity, a biocide that does not increase system impurities should be used.
Advantages
No chemical additive costs
System leakage has minimal impact on other plant systems
Low probability of biological activity due to pure water
Disadvantages
Lack of a corrosion inhibitor
Low buffering capacity
Little room for error
4-20
4.5 Blended Glycol Formulations
Blended glycol formulations are used in closed cooling systems that require protection against
freezing. Glycol formulations are typically not used in systems that do not require freeze
protection because heat transfer characteristics are not as good as water. In systems requiring
freeze protection, the heat transfer characteristics have been considered in the original design. If
converting from an aqueous coolant to a glycol-based coolant, the reduction in heat transfer
characteristics should be evaluated.
Corrosion inhibitors are added to glycol formulations to minimize corrosion rates. In most cases,
glycol antifreeze solutions are generally supplied containing an appropriate proprietary inhibitor
package. There are at least two plants that are purchasing glycol without inhibitors and adding
inhibitors.
If the intent is to purchase an inhibited glycol, care should be taken to specify an inhibited
ethylene glycol solution and not simply ethylene glycol. Commercial glycol antifreeze solutions
also commonly contain a minor percentage of di-ethylene glycol in addition to ethylene glycol.
The corrosion inhibitor objectives for glycol coolants are similar to those of pure water corrosion
inhibitors. Different approaches exist, but they are all equally appropriate in water or glycol
solutions.
One of the contributors to corrosion problems in glycol-water cooling systems is the slow
breakdown of glycol into organic acids at elevated temperature, resulting in a loss of buffering
capacity and a drop in pH. The inhibitor blend should retard glycol breakdown by buffering the
solution to counter the effect of the organic acid breakdown products.
Buffering capacity is usually provided by a high concentration of trisodium phosphate,

sometimes fortified with sodium tetraborate and caustic soda to provide a system pH of 10.0
10.5 (when the concentrate is diluted to 50% in the system). Typical phosphate concentrations
range up to 20,000 mg/L as PO4 in the concentrate. Potassium phosphate salts are also used as
buffers due to the greater solubility of the potassium salt at high pH. At these concentrations, the
phosphate also serves as a corrosion inhibitor for steel.
Tolyltriazole is generally added to the concentrate at concentrations of 5003000 mg/L active,

which is 100-fold higher than typical for non-glycol systems. The tolyltriazole serves several
purposes. It inhibits copper alloy corrosion and controls solder corrosion by shutting down the
cathodic reaction on the copper/solder galvanic couple. In a closed cooling system, a buildup of
corrosion products can deplete tolyltriazole concentrations between extended maintenance
intervals. Because the cost of the tolyltriazole is small compared to the glycol cost, a high initial
concentration provides inexpensive insurance against premature tolyltriazole depletion.
Tolyltriazole depletion (caused by corrosion products) is sometimes used as an indicator that the
corrosion inhibitor is failing or at the end of useful life.
The principal corrosion inhibitor for aluminum and cast iron in antifreeze solutions is silicate.
Silicate can also be effective in inhibiting the copper/solder galvanic couple, should the
tolyltriazole become depleted. Silicate is added to the glycol concentrate at 5001100 mg/L as
4-21
SiO2. Some engine manufacturers require low silicate coolant to prevent silicate dropout
(gelation), which creates deposits that plug radiators and heat exchange equipment. Sodium
nitrate (NaNO3), at a concentration of 5001500 mg/L (as NO3), can be used in addition to
silicate to control aluminum pitting corrosion; however, it is more for use with ferrous metals.
An antifoam, such as silicone or ethylene oxide/propylene oxide copolymer, is generally added

to the glycol concentrate to inhibit foaming that might produce air pockets within the cooling
system, cause false level indications, or result in foam overflowing the surge tank. A red, yellow,
or green dye is generally included in the concentrate to provide a visual indication of the
presence or condition of the glycol solution. For example, 30 mg/L of Alizarine Cyanone Green
G-Extra plus 20 mg/L of Uranine C yellow will produce the characteristic yellow-green hue of
most consumer and industrial glycol antifreeze solutions.
Inexpensive soft solder (containing greater than approximately 92% lead) is very susceptible to
corrosion when galvanically coupled to copper alloys. Nitrite at levels above 4000 mg/L as NO2
can greatly accelerate the solder corrosion rate, causing corrosion product (lead phosphate)
blooms, which can restrict cooling flow in radiator tubes or cause the solder joint to fail. Sodium
nitrite up to a concentration of 3,000 mg/L as nitrite (NO2), however, is often an additional
component of heavy-duty diesel glycol coolant applications and is used to inhibit cavitation-
induced pitting of the cast iron piston sleeve liners. The vibration of the pistons can induce
cavitation bubble formation on the outside of the sleeve liners, often resulting in intense pitting
of the liner. Nitrites are particularly effective at inhibiting this cavitation-induced pitting.
Silicates and additional tolyltriazole can effectively counteract the impact of nitrite on solder
corrosion.
Heavy-duty diesel glycol formulations could also be formulated with polymeric dispersants, such
as polyacrylate and sequestrants (for example, phosphonates), to complex the calcium in the
water, which is used to dilute the glycol concentrate. These dispersants and sequestrants are also
useful in complexing and dispersing ferrous corrosion products, but coolant filters are far more
effective. Calcium phosphate deposits are prone to form in both the extreme hot and cold zones
of the cooling system. Deposits in hot areas on the engine can cause hot spots to form near the
firing areas, which can change engine timing. Deposits in cold areas, such as the heater core, can
reduce heat transfer and plug the core in extreme cases. It is important to realize that the amount
of calcium deposit is limited to the calcium introduced in the dilution water, which is small for
most glycol containing closed cooling systems. For example, the total amount of calcium
phosphate that could theoretically form from the calcium contained in 120 gallons of raw water
with 100 mg/L of calcium hardness (as CaCO3) is only 0.3 lbs (0.14 kg).
Solutions of ethylene and propylene glycol as low as 20% [34] to 25% [35] have been shown to
be effective at controlling most types of microbiological growth. Because not all microorganisms
are represented by these studies, it is possible for some growth to occur in this concentration
range. Concentrations above 30% are readily recognized as maintaining biostatic conditions.
Seabrook Station has used ethylene glycol systems at concentrations of 2530%, with no
measurable microbiological activity for over 15 years.
Testing parameters and frequencies for inhibited glycol solutions are described in Section 5.9.
4-22
5
TREATMENT PROGRAM AND MONITORING
RECOMMENDATIONS
When properly applied, there are several chemical treatment programs that have a documented
history of success in nuclear power plant closed cooling systems. The technical basis of the
various corrosion inhibitors is discussed in Section 4. This section will summarize these
treatment programs, establish common control ranges, and identify where exceptions might exist.
Deviating from the specifications outlined in this guideline, with the understanding and approval
of plant management, is allowed provided that sound technical justification and/or performance
monitoring supports the deviation.
5.1 CCW Action Levels
CCW Action Levels have been established for these guidelines so that the importance of out-of-
specification conditions can be effectively communicated to management. The CCW Action
Levels have been written to parallel the actions that are taken in primary and secondary
chemistry systems. However, because closed cooling systems operate at temperatures and
pressures that are significantly lower than the primary or secondary systems of power plants, the
timeframes for significant adverse effects on system materials are much longer. Revision 0 of
these guidelines did not provide guidance on the significance of an out-of-specification
condition, or how soon the condition had to be corrected. This made it difficult to plan
appropriate timeframes and work schedules for correcting these conditions. CCW Action Level 1
conditions are those that can be addressed using the 12-week work schedule concept, with no
discernable increases in corrosion rates or system efficiency. CCW Action Level 2
communicates a more serious condition, requiring action outside the normal 12-week work
schedule.
The CCW Action Levels apply only to Control Parameters, which have defined limits.
Diagnostic Parameters are used as a means to help identify the source of the off-normal
condition, and are generally not a direct function of corrosion inhibition. Diagnostic Parameters
have no CCW Action Levels.
It is important to note that it is expected that these timeframes should be used as not-to-exceed
dates, and that corrective actions will be completed as soon as work schedules permit.
The various Control Parameters can have a negative synergistic effect on system corrosion rates
if two or more are outside the normal operating range at the same time. For these circumstances,
consideration should be given to elevating to CCW Action Level 2 if two or more parameters are
in CCW Action Level 1 conditions.
5-1
Treatment Program and Monitoring Recommendations
5.1.1 CCW Action Level 1
The normal operating ranges recommended in this guideline represent a conservative

interpretation of closed cooling water chemistry as generally practiced in the nuclear power and
other industries. Action Level 1 denotes a condition where system chemistry Control Parameters
are outside the normal operating levels. The recommended action is to increase monitoring
frequency, as appropriate, and return the parameter to within the prescribed normal operating
range within 90 days. If the parameter has not returned to the normal operating range within 90
days, CCW Action Level 2 is entered.
corrective actions be initiated than if only one parameter is in the Action Level. Increased
sampling frequency, until parameters are returned to normal, should be considered as part of
those actions.
5.1.2 CCW Action Level 2
Values exceeding the CCW Action Level 2 threshold could initiate short-term system materials
degradation. The recommended action is to return the parameter to within the prescribed control
band within 30 days. If after 30 days in CCW Action Level 2, the parameter has not returned to
the normal range and system operation is to continue, then a risk assessment (engineering
evaluation) shall be performed indicating that the out-of-control parameter will not impact the
long-term reliability of the system. The evaluation should include a sunset date for the out-of-
control condition.
corrective actions be initiated than if one parameter is in the Action Level. Increased sampling
frequency, until parameters are returned to normal, should be considered as part of those actions.
5.2 Nitrite-Based Programs
Nitrite-based corrosion control programs use sodium nitrite as a carbon steel corrosion inhibitor
in addition to a pH control agent. The pH control agent can either be sodium hydroxide or a
sodium tetraborate buffer. A nitrite-based program will also contain a copper corrosion inhibitor
(tolyltriazole or benzotriazole) if copper alloys are present in the system. Tables 5-1 and 5-2 list
operating ranges and monitoring frequencies for nitrite- and molybdate-based programs.
5-2
Table 5-1
Operating Ranges and Monitoring for Nitrite-Based Programs
Parameter Normal Action Levels Monitoring Frequency

Operating
Range (AL 1 90 days Tier 1 Tier 2 Intermittent
Systems (1) Systems Systems
AL 2 30 days)
Control Parameters
Nitrite 5001500 ppm AL 1: <500 ppm Weekly Monthly Monthly or as
as NO2- operated
AL 2: <300 or >4000
ppm
pH 8.511.0 AL 1: <8.5 or >11.0 Weekly Monthly Monthly or as
operated
AL 2: <8.0 or >11.5
Azole (2) 5100 ppm AL 1: <5 ppm Monthly Monthly Monthly or as
azole (3) operated
AL 2: <3 ppm
Chloride and 10 ppm Cl AL 2: >10 ppm Monthly Monthly Monthly or as
Fluoride (4) operated
10 ppm F
Diagnostic Parameters
Conductivity Consistent with Weekly Monthly Monthly or as
nitrite level and operated
Evaluate trend
Nitrate (5) Evaluate trend Quarterly Quarterly Quarterly or as
operated
Ammonia (2) Evaluate trend Quarterly Quarterly Quarterly
Chloride and Evaluate trend Monthly Monthly Monthly or as
Sulfate (6) operated
Total Iron, Total Evaluate trend Monthly Monthly Monthly or as
Copper (7) operated
Microbiological Evaluate trend Monthly Monthly Monthly or as
operated
Radioactivity (8) Evaluate trend Quarterly Quarterly Quarterly or as
operated
(1) The weekly frequency for Tier 1 parameters can be reduced to up to once per month if steady-state chemical control has
been maintained (all control parameters are maintained within the normal operating range) for at least one quarter and
microbiological activity is under control.
(2) Not required if it can be documented that there are no copper alloys in the system.
(3) Azole to be in excess of 25 ppm if pH is in the range of 10.511.0.
o o
(4) Applies to systems that contain stainless steel where the temperature is >150 F (66 C). Strategic plan should consider
that NSSS vendor specification might be more restrictive.
(5) Some blended products might contain nitrate. This reduces the value of nitrate analysis and trending.
(6) If not applicable as a Control Parameter, chloride should be a Diagnostic Parameter due to general corrosion concerns.
(7) Iron and copper monitoring can be quarterly if corrosion rate monitoring is being performed.
(8) Applicable to those systems with the potential to become contaminated.
5-3
5.3 Molybdate-Based Programs
Molybdate-based corrosion control programs use sodium molybdate as a carbon steel corrosion
inhibitor in addition to a pH control agent. The pH control agent can be either sodium hydroxide
or a sodium tetraborate buffer. In some cases, carbonate, bicarbonate, or an amine are used to
avoid the use of borate. A molybdate-based program will also contain a copper corrosion
inhibitor (tolyltriazole or benzotriazole) if copper alloys are present in the system.
Table 5-2
Operating Ranges and Monitoring for Molybdate-Based Programs
Normal Action Levels Monitoring Frequency

Parameter Operating (AL 1 90 days Tier 1 Tier 2 Intermittent
Range AL 2 30 days) Systems (1) Systems Systems
Control Parameters
2001000 ppm AL 1: <200 ppm Monthly or as
Molybdate = Weekly Monthly
as MoO4 AL 2: <160 ppm operated
AL 1: <9.0 or >11.0 Monthly or as
pH 9.011.0 Weekly Monthly
AL 2: <8.5 or >11.5 operated
5 to 100 ppm AL 1: <5 ppm Monthly or as

Azole (2) Monthly Monthly
as azole (3) AL 2: <3 ppm operated
Chloride and Fluoride 10 ppm Cl Monthly or as

AL 2: >10 ppm Monthly Monthly
(4) 10 ppm F operated
Monthly or as
Conductivity Evaluate trend Weekly Monthly
operated
Monthly or as
Chloride and Sulfate (5) Evaluate trend Monthly Monthly
operated
Monthly or as
Iron and Copper (6) Evaluate trend Monthly Monthly
operated
Quarterly or as
Microbiological Evaluate trend Quarterly Quarterly
operated
Quarterly or as
Radioactivity (7) Evaluate trend Quarterly Quarterly
operated
(1) The weekly frequency for Tier 1 parameters can be reduced to up to once per month if steady-state chemical control has been
maintained (all control parameters are maintained within the normal operating range) for at least one quarter.
o o
(4) Applies to systems that contain stainless steel where the temperature is >150 F (66 C). Strategic plan should consider that
NSSS vendor specification might be more restrictive.
5-4
5.4 Nitrite/Molybdate Programs
Nitrite/molybdate corrosion control programs use the combination of sodium nitrite and sodium
molybdate as a carbon steel corrosion inhibitor in addition to a pH control agent. The pH control
agent can be either sodium hydroxide or a sodium tetraborate buffer. In some cases, carbonate,
bicarbonate, or an amine is used to avoid the use of borate. A nitrite/molybdate program will also
contain a copper corrosion inhibitor (tolyltriazole or benzotriazole) if copper alloys are present in
the system. Table 5-3 lists operating ranges and monitoring frequencies for nitrite/molybdate
programs.
Table 5-3
Operating Ranges and Monitoring for Nitrite/Molybdate Programs

Operating (AL 1 90 days
Range AL 2 30 days) Tier 1 Tier 2 Intermittent
Control Parameters
Nitrite 501500 ppm AL1: <50 ppm Weekly Monthly Monthly or
NO2- AL2: <25 ppm or>4000 ppm as operated
Molybdate 1601000 ppm AL1: <160 ppm Weekly Monthly Monthly or
MoO42- AL2: <80 ppm as operated
pH 8.511.0 AL 1: <8.5 or >11.0 Weekly Monthly Monthly or
AL 2: <8.0 or >11.5 as operated
Azole (2) 5100 ppm as AL 1: <5 ppm Monthly Monthly Monthly or
azole (3) AL 2: <3 ppm as operated
Chloride and Fluoride 10 ppm Cl AL 2: >10 ppm Monthly Monthly Monthly or
(4) 10 ppm F as operated
Conductivity Evaluate trend Weekly Monthly Monthly or
as operated
Nitrate Evaluate trend Monthly Monthly Monthly or
as operated
Ammonia (2) Evaluate trend Monthly Monthly Monthly or
as operated
Chloride and Sulfate Evaluate trend Monthly Monthly Monthly or
(5) as operated
Iron and Copper (6) Evaluate trend Monthly Monthly Monthly or
as operated
Microbiological Evaluate trend Monthly Monthly Monthly or
as operated
Radioactivity (7) Evaluate trend Quarterly Quarterly Quarterly or
as operated
maintained (all control parameters are maintained within the normal operating range) for at least one quarter and microbiological
activity is under control.
o o
5-5
5.5 Chromate-Based Programs
Chromate-based corrosion control programs use a chromate salt as a carbon steel corrosion
inhibitor in addition to a pH control agent. Potassium dichromate or disodium phosphate can be
used for pH reduction. Because chromate is a good copper alloy corrosion inhibitor, the addition
of an azole is not required. Chromate is compatible, however, with the azoles. Table 5-4 lists
operating ranges and monitoring frequencies for chromate-based programs.
Table 5-4
Operating Ranges and Monitoring Frequencies for Chromate-Based Programs

Operating (AL 1 90 days
Range AL 2 30 days) Tier 1 Tier 2 Intermittent
Control Parameters
Chromate 150300 ppm AL 1: <150 or >300 Weekly Monthly Monthly or as
as CrO42- (1) ppm operated
AL 2: <115 or >500
ppm
pH 8.011.0 AL 1: <8.0 or >11.0 Weekly Monthly Monthly or as

operated
AL 2: <7.5 or >11.5
Chloride and Fluoride 10 ppm Cl AL 2: >10 ppm Monthly Monthly Monthly or as

(3) operated
10 ppm F
Conductivity Evaluate trend Weekly Monthly Monthly or as
operated
Chloride and Sulfate (4) Evaluate trend Monthly Monthly Monthly or as
operated
Iron and Copper (5) Evaluate trend Monthly Monthly Monthly or as
operated
Radioactivity (6) Evaluate trend Quarterly Quarterly Quarterly or as
operated
=
(1) Some NSSS suppliers request an initial chromate concentration of 1000 ppm CrO4 . This indicates that no system components
will be damaged by the high chromate level. This requirement constitutes a legitimate exception to the normal control range and
should be accommodated.
o o
5-6
5.6 Hydrazine-Based Programs
Hydrazine-based programs have been successfully used in all-ferrous and mixed metallurgy
systems. The two types of systems require different hydrazine levels and operating pH ranges.
Table 5-5 lists operating ranges and monitoring frequencies for hydrazine-based programs.
Table 5-5
Operating Ranges and Monitoring Frequencies for Hydrazine-Based Programs

Control Parameters
Hydrazine, mixed 550 ppm as AL 1: <5 ppm Monthly or as
Weekly Monthly
metallurgy N2H4 AL 2: <1 ppm operated
Hydrazine, all-ferrous 5200 ppm as AL 1: <5 ppm Monthly or as

Weekly Monthly
metallurgy N2H4 AL 2: <1 ppm operated
Monthly or as
pH, mixed metallurgy 8.59.6 AL 2: <8.0 or >10.0 Weekly Monthly
operated
pH, all-ferrous Monthly or as
8.510.5 AL 2: <8.0 or >10.5 Weekly Monthly
metallurgy operated
Chloride, Fluoride, 150 ppb as AL 1: >150 ppb Monthly or as
Sulfate (2) Monthly Monthly operated
ion (each) AL 2: >1000 ppb
Dissolved Oxygen AL 1: >100 ppb Monthly or as
100 ppb Monthly Monthly operated
AL 2: >1000 ppb
Monthly or as
Cation conductivity (3) Evaluate trend Weekly Monthly
operated
Monthly or as
Ammonia Evaluate trend Monthly Monthly
operated
Monthly or as
Iron and Copper Evaluate trend Monthly Monthly
operated
Quarterly or as
operated
(1) The weekly frequency for Tier 1 parameters can be reduced to once per two weeks if steady-state chemical control has been
(2) Weekly cation conductivity can be substituted for Cl, F, and SO4 if organic anions are not present. If cation conductivity is <1
S/cm, Cl, F, and SO4 are considered to be within specification.
(3) See section 7.2.5 for specific effects of some contaminants on cation conductivity.
5-7
5.7 Silicate-Based Programs
Silicates are attractive from an environmental standpoint but do not offer the same level of
corrosion protection as nitrites, molybdates, chromates, and hydrazine. They should be used in
applications where corrosion rate monitoring capability is installed. Table 5-6 lists operating
ranges and monitoring frequencies for silicate-based programs.
Table 5-6
Operating Ranges and Monitoring for Silicate-Based Programs

Control Parameters
2060 ppm as AL 1: <20 or >200 ppm
- Monthly or as
Silicate SiO2 above Weekly Monthly
AL 2: <15 ppm operated
background
AL 2: <7.5 operated
5 100 ppm as AL 1: <5 ppm Monthly or as

Azole (2) Monthly Monthly
azole (3) AL 2: <3 ppm operated
Chloride and Fluoride 10 ppm as Cl Monthly or as

AL 2: >10 ppm Monthly Monthly
(4) 10 ppm as F operated
Monthly or as
Conductivity Evaluate trend Weekly Monthly
operated
Monthly or as
Chloride and Sulfate (5) Evaluate trend Monthly Monthly
operated
Monthly or as
Iron and Copper (6) Evaluate trend Monthly Monthly
operated
Monthly or as
Microbiological Evaluate trend Monthly Monthly
operated
Quarterly or as
operated
(3) TTA to be in excess of 25 ppm if pH is in the range of 10.511.0.

o o
5-8
5.8 Pure Water Systems
Pure water systems have been used successfully in several plants. Success relies on maintaining
water purity and low or high dissolved oxygen levels. Table 5-7 lists operating ranges and
monitoring frequencies for pure water systems.
Table 5-7
Operating Ranges and Monitoring for Pure Water Systems
Action Levels Monitoring Frequency

Parameter Control Range (AL 1 90 days Tier 1 Tier 2 Intermittent
AL 2 30 days) Systems Systems Systems
Control Parameters
AL 2: <5.0 or >8.5 operated
AL 1: >2 S/cm Monthly or as

Conductivity <2 S/cm Weekly Monthly
AL 2: >5 S/cm operated
AL 1: >50 ppb Monthly or as

Chloride (1) 50 ppb Monthly Monthly
AL 2: >100 ppb operated

Fluoride (2) 50 ppb Monthly Monthly

Sulfate (1) 50 ppb Monthly Monthly

Dissolved Oxygen (3) 200 ppb Weekly Monthly
Monthly or as
Iron and Copper Evaluate trend Monthly Monthly
operated
Monthly Monthly or as
Microbiological (4) Evaluate trend Monthly (4)
(4) operated (4)
Quarterly or as
operated
(1) See discussion in Section 10.2.2 for systems containing no stainless steel.
o o
(2) Applies to systems that contain stainless steel where temperature is >150 F (66 C). Strategic plan should consider that NSSS
vendor specifications might be more restrictive.
(3) This represents the control range for ferrous systems or ferrous systems with copper alloys. Systems that have copper
components should follow the Stator Cooling Water Guidelines for oxygen control. The Action Levels in this instance would be
>100 ppb or <2000 ppb for AL 1, and >300 ppb or <1000 ppb for AL 2.
(4) Pure water has a low nutrient value. Frequency of microbiological monitoring can be decreased with documented history of low
microbiological activity.
5-9
5.9 Blended Glycol Formulations
Blended glycol formulations are not monitored as frequently as other systems because of the
stability of the glycol and the presence of relatively high concentrations of inhibitors. In addition,
vendors of proprietary formulations typically will not provide details on correcting adverse
conditions or trends outside of the scope of their service agreement. It is generally necessary to
accept the sampling schedule they provide and follow their specific recommendations for
adjusting the inhibitor package. However, analysis and trending of certain key parameters by the
site can provide an early warning of incipient problems for which corrective actions can be taken
either at the site or by notifying the vendor of the condition. Tables 5-8 and 5-9 list control
ranges and monitoring frequencies for blended glycol programs.
Table 5-8
Control Ranges and Monitoring for Proprietary Blended Glycol Programs
Action Levels Monitoring Frequency

Normal
Parameter Operating (AL 1 90 days Tier 1 Tier 2
Range Systems Systems
AL 2 30 days)
Control Parameters
Glycol, % Volume AL 1: <30 or >60
30-60 (2) Quarterly Annually
(Freeze Point) (1) AL 2: <25 or >65
AL 1: <7.5 or >11.0
pH 7.5-11.0 [36] Quarterly Annually
AL 2: <6.5
Appearance Evaluate trend Quarterly Annually
Conductivity Evaluate trend Quarterly Annually
Contaminants, Corrosives, or
(3) Annually Annually
Scale Formers
Corrosion Inhibitors (3) Annually Annually
Glycol Properties and Breakdown
(3) Annually Annually
Products (organic acids)
Corrosion Products Evaluate Trend Annually Annually
Reserve Alkalinity (3) Annually Annually
(1) Freeze point can be used in conjunction with, or in lieu of, %v glycol. Both are typically determined by index of refraction
or specific gravity.
(2) To be consistent with specific freeze protection requirements.
(3) Formulation or engine manufacturers might provide recommendations for particular parameters to monitor based on
makeup water source and other factors. Maintain in the recommended range.
5-10
Table 5-9
Control Ranges and Monitoring for Nonproprietary and Plant-Specific Blended Glycol
Programs

Parameter Operating (AL 1 90 days Tier 1 Tier 2
Range AL 2 30 days) Systems Systems
Control Parameters
Glycol, % Volume AL 1: <30 or >60

3060 (2) Quarterly Annually
(Freeze Point) (1) AL 2: <25 or >65
AL 1: <7.5 or >11.0
pH 7.511.0 [37] Quarterly Annually
AL 2: <6.5
Corrosion Inhibitors (3) Quarterly Annually
Appearance Evaluate trend Quarterly Annually
Conductivity Evaluate trend Quarterly Annually
Reserve Alkalinity (3) Quarterly Annually
Contaminants,
Corrosives and Scale (3) Annually Annually
Formers
Corrosion Products Evaluate trend Annually Annually
Glycol Properties and
Breakdown Products (3) Annually Annually
(organic acids)
(1) Freeze point can be used in conjunction with or in lieu of, %v glycol. Both are typically determined by index of
refraction or specific gravity.
(2) To be consistent with specific freeze protection requirements.
(3) Added inhibitors might be from a manufacturer other than the glycol manufacturer. Maintain inhibitors in range
recommended by inhibitor manufacturer.
5-11
6
TECHNICAL BASIS OF CHEMICALS USED FOR
MICROBIOLOGICAL AND FOULING CONTROL
6.1 General
An effective closed cooling water biocide should:

Be effective against sessile as well as planktonic microorganisms and particularly effective
against the strains of bacteria that contribute to fouling or MIC mechanisms in CCW systems
Be compatible with corrosion inhibitors, dispersants, and other chemicals used in the system
Be effective at the pH of the cooling water
Be able to penetrate and disperse biomass
Be persistent, maintaining its toxic properties while in the system. Ideally, it should degrade
to compounds that do not interfere with CCW system operation
Be susceptible to a degradation or deactivation mechanism to facilitate discharge
Provide ease of handling to the greatest extent possible
Biocides used to control microbiological growth fall into two broad categoriesnon-oxidizing
and oxidizing.
Oxidizing biocides are chemicals whose effectiveness depends upon their ability to oxidize and,
thus, destroy organic material. Oxidizing biocides are not frequently used in CCW systems and
cannot be used with nitrite-based programs.
A chemical that is not an oxidizing agent but is toxic to one or more classes of microorganisms
(and in some cases macroorganisms) is classified as a non-oxidizing biocide. There are many
different types used, each with certain limitations. Non-oxidizing biocides are chemicals that kill
organisms via a metabolic mechanism, cell transpiration or ingestion/digestion disruption,
reproductive disruption, suffocation, starvation, poisoning, or trauma.
In many cases, it is necessary to use more than one non-oxidizing biocide in a CCW system. In a
microbiologically active system, more than one species of bacteria is usually growing. A
particular biocide is more effective against some types of organisms than others. The more
resistant organisms might continue to grow in spite of an application of a specific biocide. The
use of a second biocide on an alternating basis helps prevent the establishment of resistant
6-1
Technical Basis of Chemicals Used for Microbiological and Fouling Control
microflora. This does not mean, however, that a plant cannot achieve satisfactory
microbiological control through the use of a single specific biocide.
Selection and application of a biocide must be made with careful consideration. Some biocides
contain constituents (for example, chloride) that are incompatible with some CCW system
components.
After a biocide is added, the active portion eventually degrades and loses effectiveness. Organic
material remains that can then become a nutrient for bacteria or can add to TOC loading of the
CCW system.
Some of the non-oxidizing biocides available are outlined in the following subsections. There are
other biocides that are also available but less commonly used. There is ongoing research into
new non-oxidizing biocides.
Non-oxidizing biocides provide an additional benefit. Subsequent to addition for biocidal

purposes, the biocide remains a biostat for certain periods of time. The persistence is referred to
as the half-life of the compound and depends on system pH and temperature. In many cases the
degradation products have biostatic properties. A biostat is a compound that does not kill
organisms but has a significant impact on the organisms capability to reproduce.
There are conditions in the CCW system that can have a biostatic effect. An example is pH. At
the higher levels of the CCW system pH operating ranges (for example, >10), microbiological
growth rates are reduced.
6.2 Non-Oxidizing Biocides
There are numerous non-oxidizing biocides available for potential use in closed cooling water
systems. A few have been commonly used in nuclear power plants. Others have the potential for
use as long as their limitations are understood. For example, many of the non-oxidizing biocides
are chloride contributors. This might be a limiting factor in CCW systems containing stainless
steel but might be less important if stainless steel is not present.
The following is a discussion of many of the non-oxidizing biocides available. It is not an all-
inclusive list. In addition, new biocides are frequently introduced. Several of the biocides are
discussed in detail. Others are discussed in less detail but should be given consideration based on
their merits as long as their limitations are evaluated.
6.2.1 Glutaraldehyde
Glutaraldehyde is a linear, 5 carbon dialdehyde (1,5-pentanedial).
6-2
Glutaraldehyde disrupts the organism by cross-linking cell protein [38]. It is effective against
bacteria, yeasts, and molds and is most effective over a pH range of approximately 69. Above a
pH of 9, it starts to degrade but can achieve a rapid kill before degradation. The increasing pH
does not impact its effectiveness, only the rate of degradation. San Onofre has reported good
control when using glutaraldehyde in CCW systems operating in the 9.09.5 pH range3.
Glutaraldehyde is effective against both aerobic and anaerobic microorganisms. It is effective

against both planktonic and sessile organisms and against sulfate-reducing bacteria. This is one
of the most common biocides used in the nuclear industry.
Glutaraldehyde is noncorrosive to metals at recommended use levels.
Dosage Range
Typical dosages are 25100 ppm active, but the manufacturers label might allow a broader
range. The rate of degradation due to pH can be taken into account when selecting the initial
concentration or considering the use of a biodispersant.
Residual Contaminants
Glutaraldehyde contains only carbon, hydrogen, and oxygen and does not contain significant
levels of residual contaminants.
Deactivation and Degradation
Glutaraldehyde is deactivated by reacting with an amine (for example, ammonium hydroxide) at

a neutral or elevated pH. Glutaraldehyde undergoes a reaction at pH >9.0 to form higher
molecular weight aldehydes, which are not biocidal. Ultimately, these products are
biodegradable to carbon dioxide at the elevated pH.
Advantages
Glutaraldehyde is compatible with common corrosion inhibitors.
Active concentrations can be measured with a field test kit. This kit is available from the
biocide manufacturer (Dow Chemical), water treatment service companies, and some
suppliers of chemical test kits. The user should confirm that nitrites will not interfere with the
test. It should also be noted that the test kits are not glutaraldehyde-specific. Test kits will
3
Data provided to Task Group by Tim Sarette, Southern California Edison Co.
6-3
respond to other aldehydes as well. The intermediate step in glutaraldehyde decomposition at

pH >9 is polymerization to other aldehydes (which are not biocidal). Thus, a false positive
indication of biocidal concentration can be inferred when high system pH values exist.
Disadvantages
Glutaraldehyde ultimately decomposes to carbon dioxide and possibly to glutaric acid. This
can result in pH depression in the CCW system.
Incomplete decomposition creates organics that might be nutrients for certain organisms.
Glutaraldehyde increases TOC in the CCW system and can cause foaming.
Glutaraldehyde is deactivated by ammonia or amine (1:1 molar basis required).
6.2.2 Isothiazolone
This biocide is a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-

3-one. It is usually supplied as a 1.5% solution (nonionic).
Isothiazolone inhibits macromolecular synthesis (for example, protein, RNA, and cell wall). It is
effective against planktonic and sessile bacteria. It is also effective against anaerobes, including
sulfate-reducing bacteria (SRB). It is typically used in a pH range of 6.09.0, with 8.0 being
optimum. Above a pH of 9.0, the rate of hydrolysis increases. The increasing pH does not impact
its effectiveness, only the rate of degradation.
Isothiazolone is noncorrosive to metals at recommended use levels.
Dosage Range
Typical dosages are 15 ppm active, but the manufacturers label might allow a broader range.
The rate of degradation due to pH can be taken into account when selecting the initial
concentration or considering the use of a biodispersant.
This biocide contains magnesium chloride and nitrate as a stabilizer. The stabilizer will contribute
chloride to the water. The biocide might also contain a significant concentration of copper
(0.050.25 ppm copper at normal biocide dosage). There is a formulation of the biocide currently
available that does not contain copper. The addition of 1.5 ppm active biocide will contribute 0.3
ppm chloride from the chloride that is part of the 5-chloro-2-methyl-4-isothiazolin-3-one molecule.
6-4
The magnesium chloride present as a stabilizer will contribute additional chloride. The supplier
should be asked to quantify this chloride contribution prior to use. The compound also contains
sulfur and can be a sulfate contributor. The addition of 1.5 ppm active biocide will contribute
approximately 1 ppm of sulfate to the water.
The rate of hydrolysis of isothiazolone increases with increasing pH. The increasing pH does not
impact its effectiveness, only the rate of degradation.
Advantages
Low dosages are required.
It is a water-based material and does not contain residual organics.
Isothiazolone acts very rapidly.
It is very effective against nitrifying and denitrifying bacteria.
Disadvantages
Sulfate and chloride contribution.
Possible copper contribution (depending on formulation).
No field test kit.
6.2.3 Methylene Bis(Thiocyanate)
Methylene bis(thiocyanate) is the methylene ester of thiocyanic acid with a chemical formula of
CNS-CH2-CNS. Note: methylene bis(thiocyanate) is commonly referred to by the acronym MBT.
This is not to be confused with mercaptobenzothiazole (copper corrosion inhibitor), also called
MBT.
The thiocyanate fragment of the molecule blocks the transfer of electrons in the respiratory
system of microorganisms [39]. It is very effective against bacteria and fungi. At pH levels
above 7.5, the compound hydrolyzes but can be effective up to a pH of 8.5. At a pH of 8.5, the
half-life of the biocide is approximately 4 hours [40]. At pH 9.5 it must be slug-fed to be
effective.
Methylene bis(thiocyanate) is noncorrosive to metals at recommended use levels.
6-5
Dosage Range
Typical dosages are 18 ppm active.
1 ppm of the biocide will contribute 0.75 ppm of sulfate to the water.
Methylene bis(thiocyanate) hydrolyzes to less toxic compounds.
Advantages
Effective at low dosages
A broad-spectrum biocide
Readily deactivated and hydrolyzed
Biofilm penetrator and not affected by the presence of other organics
Disadvantages
Repeated applications can increase TOC content of CCW system
Not a water-based product
Contributes sulfate to the water
Solvent might contain chloride
No practical field test kit
6.2.4 DBNPA
DBNPA is 2,2-dibromo-3-nitrilopropionamide.
DBNPA interacts with enzymes and interferes with cell respiration and metabolism. It is very
effective against bacteria and achieves a significant kill in 13 hours. It is effective against both
aerobic and anaerobic bacteria. At pH levels above 7.5, the compound hydrolyzes but can be
effective up to a pH of 8.3 or higher. As pH increases, the rate of hydrolysis increases. For
example, at 37oC, the half-life at pH 7.32 is 7.5 hours, but, at a pH of 8.3, it is only 25 minutes.
The rate of degradation due to pH can be taken into account when selecting the initial
6-6
concentration or considering the use of a biodispersant. In spite of the rapid rate of hydrolysis at
elevated pH, it has been used successfully in nuclear CCW systems4.
DBNPA is noncorrosive to metals at recommended use levels.
Dosage Range
Typical dosages are 0.510 ppm active. As noted, the rate of degradation due to pH can be taken
into account when selecting the initial concentration or considering the use of a biodispersant.
1 ppm of DBNPA will contribute 0.7 ppm of bromide to the water. DBNPA is contained in a glycol
solvent (47 to 60% polyethylene glycol) that might provide a nutrient source for bacteria.
DBNPA degrades to carbon dioxide, bromide ion, and ammonia. Strong reducing agents, such as
sulfites, deactivate DBNPA via debromination. Mercaptobenzothiazole (copper corrosion inhibitor)
also deactivates DBNPA.
Advantages
DBNPA acts very rapidly.
Low dosages are required.
A field test kit is available.
Disadvantages
The glycol solvent adds considerable TOC to the CCW system.
Degradation produces ammonia.
Bromide is added to water.
6.2.5 THPS
THPS is tetrakis(hydroxymethyl) phosphonium sulfate. It is a non-foaming, water-soluble
quaternary phosphonium compound with broad-spectrum biocidal efficacy.
4
Oconee and Catawba experience.
6-7

THPS disrupts cell wall integrity by denaturing protein. THPS is effective over a pH range of
310. THPS exposure results in rapid inhibition of lactate dehydrogenase activity in the
metabolism of SRB.
THPS is noncorrosive to metals at recommended use levels.
Dosage Range
Typical dosages are 20100 ppm active.
A 50 ppm dose of THPS (active) will contribute 12 ppm of sulfate and 34 ppm of phosphate.

THPS is absorbed by activated carbon. It can be deactivated with ammonium bisulfite (and
probably sodium bisulfite). Its effectiveness is reduced in systems with high turbidity or
suspended solids because of adsorption to solids in bulk water.
Advantages
THPS exhibits low toxicity to mammals, fish, and Daphnia magna.
Halide free.
Field test kit available (minimum detection level 10 ppm active).
Disadvantages
High dosages required
Sulfate contribution
Limited data on effectiveness in closed cooling systems
6.2.6 Ionine Quaternary Compounds
These are low molecular weight polymeric, ionine quaternary nitrogen biocide/biostats. Their
chemical description is poly (oxyethylene iminio-ethyleneiminio-ethylene dichloride);
approximate nominal molecular weight is 5,00010,000.
The ionine quaternary biocides are algaecidal, bactericidal, and actively biostatic in closed
cooling water environments. They are also effective against mollusks, hydroids, and other
macrofouling organisms. They are non-foaming and not affected by pH. Some of these
6-8
compounds have National Sanitation Foundation (NSF) allowances as potable water biocide.
They are also effective as a biodispersant, especially in preventing biofilm deposits.
The mode of action is in disruption of cell membranes. The molecule penetrates the membrane,
thereby interrupting ion and electron transport, and other transport mechanisms. Disruption of
the cell membrane can also cause leakage of intracellular materials, thus causing death.
Application Metallurgy
Ionine quaternary biocides are noncorrosive to metals and other materials of construction at
recommended use levels.
Dosage Range
Ionine quaternary biocides are typically used at 525 ppm active in closed cooling water
systems.
A 25-ppm (active) dose of an ionine quaternary biocide will contribute approximately 4 ppm of
chloride.
Activated carbon, corrosion products, and high levels of turbidity or suspended solids in bulk
water absorb the ionine quaternary biocide.
Advantages
Ionine quaternary biocides persist under most situations in closed loop cooling systems,
thereby providing significant biostatic activity in treated systems.
Field test kit available minimum detection level approximately 0.6 ppm active.
Ionine quaternary biocides are compatible with most inhibitors used to control corrosion.
Disadvantages
Contributes approximately 16% chloride w/w per addition level of active ingredient.
Shock dosage of an ionine quaternary biocide at maximum levels might limit the
effectiveness of anionic compounds used for scale and deposit control at minimal dosage
levels.
6-9
6.2.7 Dodecylguanidine Hydrochloride (DGH)
This product contains chloride and is incompatible with many nuclear CCW systems because of
chloride limitation. At typical use rates (2550 ppm active), it would contribute 37 ppm of
chloride to the CCW system.
6.2.8 Carbamates
Carbamates can attack copper alloys and precipitate iron. They are more applicable to open
recirculating systems.
6.2.9 Quaternary Ammonium Salts (Quats)
These products contain chloride and are incompatible with many CCW systems because of
chloride limitation. Because there are many different quat formulations on the market, the
chloride contribution can vary. Quats can cause foam that could cavitate pumps.
6.2.10 Tris-Nitro
Tris-nitro (2-nitro-2hydroxymethyl-1,3-propanediol) is unstable at a pH greater than 8.5 and

releases formaldehyde and ammonia.
6.3 Oxidizing Biocides
Oxidizing biocides are rarely used in closed cooling systems. They are not compatible with
nitrite-treated systems because the biocide will oxidize the nitrite to nitrate. Of the oxidizing
biocides, only hydrogen peroxide is compatible with nuclear CCW systems.
6.3.1 Hydrogen Peroxide
Hydrogen peroxide (H2O2) is an aqueous oxidizing agent.
Hydrogen peroxide (H2O2) is a strong oxidizing agent and acts by destroying the protein groups
in microbiological substances. Hydrogen peroxide is not compatible with nitrite-treated systems.
It oxidizes the nitrite to nitrate. It can be used in chromate- or molybdate-treated or pure water
systems, but, because it is an oxidizing agent, it might increase corrosion rates.
It is compatible with all metallurgy, but oxidizing action could increase corrosion rates of ferrous
and copper alloys.
6-10
Dosage Range
Applicable dosage ranges for H2O2 in CCW systems have not been well established. Dosages in
the range of 10100 ppm have been effective in open recirculating and spray pond systems.
None. Hydrogen peroxide degrades to water and oxygen, thus making it attractive from the
standpoint of residual contaminants.
Advantage
Hydrogen peroxide does not add any residual contaminants to the system.
Disadvantages
Hydrogen peroxide might cause foaming if it reacts with any significant amounts of
biological material.
At Surry, the addition of approximately 1500 ppm as hydrogen peroxide to a bearing cooling
water system generated sufficient gas to create oscillations in pump amperes and discharge
pressure [41].
6.3.2 Chlorine Compounds
The use of chlorine compounds will add significant levels of chloride to the CCW water. Like
other oxidants, chlorine compounds are not compatible with nitrite.
6.4 Other Treatments
Most vegetative cells are killed when exposed to temperatures exceeding 62C (145F).
However, specific bacteria (for example, Bacillus sp. and anaerobic Clostridium sp.) have the
capability of forming endospores when exposed to adverse conditions such as an increase in
temperature. Endospore-forms of these types of bacteria are resistant to thermal effects of
temperatures exceeding 100C (212F). When the temperature is reduced to 62C (145F), the
endospores germinate into reproducing vegetative cells and the population regenerates. Thermal
treatment is not typically used in CCW systems as a remedial measure, but there are potential
applications. Many emergency diesel generator jacket water systems achieve an operating
temperature sufficient to kill many bacteria during the monthly surveillance operation.
6-11
6.5 Methods Used for Fouling Control
6.5.1 General
Fouling in closed cooling systems results from the settling of suspended solids, usually corrosion
products, in piping or on heat exchange surfaces. Such deposits shield a localized area of metal
from the bulk cooling water flow, creating two different chemical environments or a differential
concentration cell. The effect of localized corrosion or pitting attack can be severe on thin-walled
heat exchanger tubes.
Suspended material tends to drop out in low-flow areas of a cooling system or onto biologically
active sites. The amount of suspended solids that chemical treatment can keep dispersed
depends upon characteristics of the cooling system. When there are low cooling water velocities
(<2 feet/second or <0.6 meters/second), and certainly when shell-side cooling is present,
suspended solids levels above approximately 50 ppm in the cooling water, might drop out even if
chemical treatment is used. In systems with consistently high-flow velocities (>2 feet/second or
>0.6 meters/second), chemical treatments can effectively control suspended solids of several
hundred ppm.
6.5.2 Suspended Solids Deposition
Suspended solids are a cause of fouling in CCW systems. These solids settle on the cooling
system surfaces, often being glued by microbiological slimes.
Foulants originate from two sources:

Water-borne foulants from outside the system
Foulants generated within the system
Water-Borne Foulants from Outside the System
Potential foulants are transferred to the closed cooling systems by some type of in-leakage. Both
chemical and mechanical methods are used for control. In the case of closed cooling systems,
known foulants must be removed from the makeup water. There is the potential for formation of
mineral scale if raw water is used for makeup and if there is significant makeup. Such foulants
cannot be handled effectively in the recirculating water with chemical treatment. The application
of chemicals such as dispersants, sludge fluidizers, and surfactants will not deliver acceptable
results unless employed with side-stream filtration, full-flow filtration, feed and bleed, or drain
and refill.
Oils and other contaminants can be introduced to CCW systems through leaks. In auxiliary
cooling systems containing lubricating oils, leakage is typically from the higher pressure oil side
to the lower pressure cooling water system. Leaks in service water system heat exchangers will
also introduce foulants into the CCW system.
6-12
Foulants Generated Within the System
Corrosion of system materials, particularly carbon steel components, can result in the
introduction of significant quantities of suspended material to the system. Although copper and
copper alloy corrosion might not produce significant levels of suspended solids, the corrosion
products can cause pitting of carbon steel.
6.5.3 Chemical Foulant Control Methods
There are two types of chemicals that are used for suspended solids control in CCW systems
dispersants and surfactants. In many CCW systems, one of these could be part of the water-
treatment program. Supplementary doses of dispersants or surfactants are usually applied only in
response to an identified or perceived problem. There is often more than one technique that can
be used. It is important that the foulant first be identified before a dispersant or surfactant is
selected.
Dispersants
Low molecular weight acrylate-based polymers (carboxyl active groups) are typically used as
dispersants in cooling water systems. Polyacrylic acid and sodium polyacrylate (sodium salt of
polyacrylic acid) are the forms of polyacrylates used. In addition to straight polyacrylates,
polyacrylamides and acrylamide/acrylate copolymers are also applicable. The low molecular
weight dispersants (10002000 MW) are typically used, although up to 10,000 MW polymers have
been successfully used. Several copolymers and terpolymers are also used.
When dispersants are used in CCW systems, it is important that the suspended material be
removed from the system. This can be done by feed and bleed or by filtering.
Dispersants are manufactured by several producers of basic and specialty chemicals. In addition,
some of the larger water treatment service companies manufacture their own polymeric
dispersants.
Treatment levels will vary depending upon the needs of the cooling system and water
characteristics. The factors that influence dispersant dosage are suspended solids composition
and concentration. Dispersant dosages of 23 ppm (as 100% active polymer) might be adequate
for general duty if suspended solids loading is minimal (<20 ppm). At higher suspended solids
loading (>20 ppm), 510 ppm might be needed.
Surfactants (Biodispersants)
The effectiveness of a biocide program can be enhanced or improved with the addition of a
surfactant. These are nonionic chemicals applied in conjunction with a biocide for removing and
dispersing microbiological slime deposits. A surfactant can help prevent attachment of
microorganisms on surfaces by reducing the surface tension of the water. Surfactants also improve
the effectiveness of biocide penetration into the biofilm or biomass when control is lost. This helps
6-13
to dislodge the microorganisms into the bulk water where they are more easily controlled with
biocides. A surfactant must be compatible with the primary biocide and be approved for use in the
specific system.
Surfactants are used when oil or slime deposits are found in the cooling water system. These
surfactants are wetting agents similar to low-foaming detergents. They act by emulsifying and
dispersing the slimy or oily foulants. Even though the surfactants are of the low-foaming variety,
they must be used carefully. Once the biomass in the system is released by the surfactant, the
total concentration of organic material could result in foaming.
When the biomass of sessile organisms is thus disturbed, the effectiveness of microbiocide
applications is enhanced. Non-ionic surfactants are typically used because charged (anionic or
cationic) structures might not be compatible with other components in the water treatment
program.
These surfactants are also called biodispersants by many manufacturers. They are very different
from polymeric dispersants in that they are not highly charged and, therefore, do not act in the
same way.
Surfactants are manufactured by basic and specialty chemical suppliers. For water treatment,
they are typically marketed through water treatment service companies. Because surfactants have
many uses other than water treatment, they are also available through other sources.
Dosages of 1020 ppm or more are added as needed to clean up the cooling water equipment.
Low dosages (less than 5 ppm) have been used as biopenetrants. Surfactants should only be used
to address a specific problem rather than as a general addition to a water-treatment program.
When used, they should be added at an adequate dosage to have a measurable effect. Care should
be exercised, however, to prevent excessive foaming, which could impair pumping and heat
transfer efficiencies.
6.5.4 Feed and Bleed
Feed and bleed is commonly used in nuclear plants to reduce the concentration of a contaminant.
This consists of bleeding some of the CCW system water to drain and replacing it with fresh
water. Inhibitor is added before, during, or after the bleed to maintain the inhibitor concentration
range.
Disadvantages
Significant quantities of water must often be removed and replaced in a CCW system to
effect the desired reduction in suspended solids.
Water bled from the system can have a negative impact on radwaste.
The replacement water might destabilize the protective film and increase corrosion rates.
6-14
6.5.5 Drain and Refill
This consists of completely draining fluid from the CCW system and replacing it with fresh
water and inhibitor.
6.5.6 Sidestream Filtration and Sidestream Demineralization
Sidestream filtration is often a more effective means of removing suspended material from CCW
systems than feed and bleed.
Advantages
Only particulate matter is removed.
Specific particle size ranges can be targeted (depending on filter design).
No additional load on radwaste is created.
Sidestream filtration will not remove dissolved impurities; however, sidestream demineralization
can be used to remove dissolved impurities. This can be accomplished by either a deep bed
demineralizer or a precoat powdered ion exchange resin filter demineralizer. There are numerous
factors that must be evaluated in considering the addition of sidestream filtration or sidestream
demineralization to a CCW system. In a nuclear plant, this is not a simple and straightforward
choice. The modification process is complex and expensive. Therefore, this guideline document
cannot make any recommendation regarding the installation of sidestream filtration or sidestream
demineralization beyond pointing out the potential advantages of the technology.
6.5.7 Other Mechanical Means of Suspended Solids Control
In addition to chemical methods, there are mechanical means of mitigating suspended solids
fouling. These include mechanical cleaning and flow reversal or backwashing. A detailed
discussion of these methods is beyond the scope of this guideline.
6-15
7
TECHNICAL BASIS OF MONITORING PARAMETERS
7.1 Introduction
This section provides the technical basis for parameters monitored in closed cooling water
systems. It provides the technical basis for parameters with limits and where Investigative
Parameters may apply to specific treatment regimens.
Corrosion, biological growth, and fouling in CCW equipment can interfere with its intended
design function. Control of these processes is important in both closed and open recirculating
cooling systems. The importance is greater, however, in closed systems because the foulants
(corrosion products, slime masses, etc.) are retained in the system rather than being lost through
systematic blowdown (bleed).
The overall goal for a CCW system chemistry program is to control those conditions that might
impact the intended function(s) of the CCW system or unacceptably shorten component life.
Because CCW systems in nuclear plants vary in design, it is important to maintain flexibility in
addressing specific performance targets and view those targets in the context of the total
program.
The purpose of monitoring CCW systems is to:

Confirm that specified chemical parameters in the CCW system are being maintained
Confirm that performance goals are being met
Identify adverse trends
An appropriate monitoring program for a particular CCW system will be dependent on several
factors. These include but are not limited to:
System metallurgy
System design
System integrity (leaks)
Chemical treatment program
Site-specific history
7-1
Technical Basis of Monitoring Parameters
There are certain measurement tools that can be used to help determine the effectiveness of the
treatment program. These tools may include:
Chemical treatment and impurity measurements
Corrosion control measurements
Microbiological measurements
Non-chemistry monitoring
There is no single monitoring program that is appropriate for all CCW systems. Most programs
will use chemical testing, but the frequency and range of parameters will vary. Microbiological
measurements are helpful but do not provide information on deposits in the CCW system.
Corrosion rate monitoring (coupons or electrochemical probes) might provide valuable
information in some systems, but might not be meaningful in other systems.
The necessity of performing specific measurements is a function of system design, operating

conditions, and system history. Regardless of the specific measurements used, the trending of
data is an important part of the overall CCW performance monitoring program.
7.2 Testing Parameters
7.2.1 Corrosion Inhibitors
This test is a direct measurement of the corrosion control components in the treatment program.
It is measured to ensure that there is an adequate level of protection for system metallurgy. Refer
to Section 4 for the technical basis for corrosion inhibitors.
7.2.2 pH
Refer to Section 4. CCW system pH is monitored because:

pH has a direct impact on corrosion rate
pH might be an important indicator of microbiological activity in the system
pH can be an indicator of system in-leakage
In inhibited glycol systems, pH is monitored because the conversion of glycol to organic acids
can cause a pH decrease and accelerate corrosion.
7.2.3 Percent Glycol
In systems containing an inhibited glycol formulation, the percent glycol or freeze point
(typically determined by index of refraction or specific gravity) is tested to determine that it is in
the proper range. A glycol percentage that is too high or too low will not provide the required
freeze protection. A glycol percentage that is below 30% can potentially act as a microbiological
nutrient and glycol can be degraded.
7-2
7.2.4 Conductivity
Conductivity is tested because it is an indirect measurement of the concentration of chemical

treatment in the CCW system. Conductivity might also be a rapid indicator of system leaks or
contaminant ingress.
7.2.5 Cation Conductivity
Cation conductivity is a diagnostic parameter for Hydrazine-treated closed cooling water system
chemistry programs and can also be used in pure water systems. Cation conductivity is an on-line
continuous measurement and can be used as a quick and simple means of monitoring and
controlling anionic contaminants without having to analyze for each anion. The values shown in
Table 7-1 were calculated using the EPRI ChemWORKs Plant Chemistry Simulator 4.0. The
table shows that controlling a closed cooling water system on hydrazine-based chemistry to a
cation conductivity of 1.3 S/cm or less would ensure that the limit of 150 ppb (see Table 5-5)
would not be exceeded for sulfate, chloride, or fluoride. Similarly, for a pure water chemistry,
controlling cation conductivity to 0.45 S/cm would ensure that neither chloride nor sulfate
would exceed the 50 ppb limit (see Table 5-7).
Table 7-1
Contaminant Concentration Versus Calculated Cation Conductivity
Contaminant, ppb Calculated Cation Conductivity, S/cm

-
150 ppb F 3.17 S/cm
-
50 ppb Cl 0.60 S/cm
-
150 ppb Cl 1.80 S/cm
50 ppb SO42- 0.45 S/cm
150 ppb SO42- 1.34 S/cm
The presence of organic acids or other anions that are not specified in Section 5 will result in
higher cation conductivities, which will make cation conductivity less useful for controlling
sulfate, chloride, or fluoride. When cation conductivities are routinely above 1.3 S/cm for
hydrazine-based chemistry or 0.45 S/cm for pure water-based chemistry, then the concentration
of each anionic control parameter must be determined by chemical analysis.
7.2.6 Chloride and Fluoride (Halides)
Chloride can contribute to carbon steel corrosion and chlorides and fluorides can be related to
stress corrosion cracking of 300 series austenitic stainless steels.
The chloride and fluoride limit for Hydrazine-treated systems is based on the Westinghouse limit
of 150 ppb. The 50 ppb limit for pure water systems is based on consensus of the Closed Cooling
Water Chemistry Guideline Task Group. For pure water systems without stainless steel, fluoride
would be a diagnostic parameter. For chemistries other than hydrazine and pure water, refer to
Appendix A (stainless steel) and Section 10.2.2 (carbon steel).
7-3
7.2.7 Nitrate
This applies to the measurement of nitrate in nitrite or nitrite/molybdate-treated systems only.

Nitrite can be converted to nitrate in one of two ways:
Nitrate is produced by the conversion of nitrite to nitrate by nitrifying bacteria.
Although nitrate can be produced by the direct oxidation of nitrite by dissolved oxygen, the
kinetics are very slow and high temperatures are required.
An increase in nitrate concentration is primarily an indicator of the presence of nitrifying

bacteria. A nitrate increase can be used to diagnose this condition.
Some CCW treatment formulations contain added nitrate. When this is the case, the nitrate test
might have less meaning as a nitrifying bacteria indicator because of the statistical significance
in measuring small changes to a large background concentration.
Nitrates are generally not harmful in closed cooling water systems but have been reported to
contribute to stress corrosion cracking of carbon steel at high concentrations. Under certain
conditions, concentrations of nitrate in the range of 10,000 ppm (1%) have been associated with
stress corrosion cracking of carbon steel [13,14]. Concentration mechanisms underneath deposits
might serve to achieve these levels, even if nitrate concentration in the bulk water is lower.
7.2.8 Ammonia
Ammonia can be a corrodent to copper and copper alloys under oxidizing conditions, and can
impact pH. Ammonia can be produced by denitrifying bacteria in nitrite and nitrite/molybdate-
treated systems. Microbiological testing is a confirming diagnostic tool. Ammonia can also be
produced by hydrazine and amine decomposition in hydrazine- and amine-treated systems. In
addition, ammonia can be present in potable water used for makeup (rarely used in nuclear
plants).
Ammonia is measured as a possible indicator of denitrifying bacteria. There is no need to

measure ammonia in molybdate-, chromate- or silicate-treated systems.
7.2.9 Iron and Copper (Corrosion Products)
The accumulation of corrosion products (iron, copper, and other metal oxides) in the CCW
system is an indirect indication of corrosion. In nitrite-, molybdate-, nitrite/molybdate-, and
hydrazine-treated systems, the pH generally favors insoluble iron oxide. However, the pH can
vary over a wide range and, thus, the percentage of insoluble iron will vary. In pure water
systems, both soluble and insoluble iron might exist.
Each system establishes a normal concentration of these corrosion products based on the
corrosion inhibitor(s) used, the materials of construction of the system, and their respective
surface areas. Consequently, a specific number cannot really be assigned as a not-to-exceed
value. It should also be noted that conditions in a system that might lead to pitting corrosion
7-4
would not be observable in these trends of metals because the overall increase in concentration
from this effect would be very small. Additionally, it is very difficult to sample for dissolved
versus insoluble species unless specifically engineered sample points (isokinetic sampling) are
available. This means that the most reliable method of analysis to be used in trending will be
total metal.
The trends of the total concentration of these metals will provide general information about
upsets to the system. Metal concentrations, which trend higher in bulk coolant, might be
significant because they can foul heat exchanger tube surfaces, pump seals, and flow-measuring
devices. This can result in loss of flow, increased P, loss in efficiency, and increased
maintenance for components.
The values chosen for acceptable ranges or limits for iron and copper should be developed on a
plant-specific basis. Factors to be considered in establishing the limits are:
Components with thinnest nominal wall thickness yielding a maximum mm/yr corrosion rate.
Makeup water rate to the system.
Are maintenance crews identifying component repairs or failures due to the presence of
solids?
Does the system have filtration or demineralization capabilities?
Is there an historical correlation between iron or copper levels and system parameters such as
flow, pressure, or temperature?
Are component specifications being used as part of plant life extension justification?
7.2.10 Microbiological Activity
An increase in microbiological activity, particularly in nitrite-treated systems, can lead to

corrosion and fouling. In molybdate-treated systems, microbiological activity can reduce system
pH. Microbiological activity is typically not a problem in chromate- or hydrazine-treated
systems.
7.2.11 Radionuclides
The presence of certain radionuclides in systems cooling a primary system component, can be an
indication of leakage into the CCW system or neutron activation of corrosion inhibitors. Refer to
NRC Information and Enforcement Bulletin 80-10. This bulletin directs operators of nuclear
power plants in the United States to have a 10CFR50.59 screening performed for continued
operation of a system, which does not normally contain radioactive materials, when it becomes
radioactively contaminated.
7-5
7.2.12 Specific Microorganisms5
Detecting specific microorganisms or groups of microorganisms is an important Investigative

Parameter. The need arises to isolate and characterize microorganisms found during a visual or
microscopic deposit examination when determining the root cause for non-conformance. Several
of the microorganisms associated with MIC and other microbiological problems have unique
shapes and sizes and can be characterized by the use of the microscope alone. In other cases,
they can be isolated or detected from a deposit at the site of the non-conformance by using
selective culturing procedures.
By culturing samples on selective culturing media, it is possible to determine the presence of

slime-forming bacteria, sulfate-reducing bacteria, metal-oxidizing bacteria, and nitrite- or nitrate-
metabolizing bacteria. Fungi and algae (blue-green algae) can also be characterized by selective
culturing techniques. The microorganisms most commonly looked for include:
Sulfate-reducing bacteria (for example, Desulfovibrio sp.)
Metal-oxidizing bacteria (for example, Gallionella sp., Leptothrix sp.)
Acid-producing bacteria (for example, Clostridium sp., Vibrio sp.)
Slime-forming bacteria (for example, Siderocapsa sp., Pseudomonas sp., Bacillus sp.)
Nitrite- or nitrate-oxidizing bacteria and ammonia producing bacteria (for example,
Nitrosomonas sp., Nitrobacter sp., Nitrococcus sp.)
7.2.13 Total Organic Carbon (TOC)
Total organic carbon in CCW systems is produced by various sources, primarily azoles and
biocides. TOC can provide food for bacteria and make microbiological control more difficult.
There is no evidence that increased TOC can lead to increased system corrosion. Elevated TOC
could be related to foaming but this would be more a function of the type of organic compound
in the systems than TOC itself. The Entergy Waterford 3 plant experienced evidence of foaming
when sampling a CCW system that had been aggressively treated with glutaraldehyde. No pump
cavitation was observed, but the plant used TOC analysis as a troubleshooting tool. The analysis
revealed that TOC in the system was in the range of 100300 ppm above what would be
expected because of the presence of TTA. TOC is considered an investigative parameter.
7.2.14 Dissolved Oxygen
Dissolved oxygen plays a part in the corrosion process. In inhibited CCW systems (nitrite,
molybdate, nitrite/molybdate, chromate, silicate), a passive film is established and the presence
of dissolved oxygen does not appear to have a significant impact on corrosion rates. In fact, it is
commonly believed that some dissolved oxygen is helpful in molybdate-treated systems (see
Section 4.3.2). Unless there is significant makeup or the system is designed so that oxygen
5
Abstracted from the EPRI Microbiologically Influenced Corrosion Training Course, Ed.2002.
7-6
ingress is normal, dissolved oxygen is rapidly depleted and CCW systems will be relatively free
of dissolved oxygen. In inhibited systems, dissolved oxygen is an Investigative Parameter. There
is little value in routine measurement.
In pure water and hydrazine systems, dissolved oxygen is a Control Parameter. In these systems,
oxygen can play a significant role in copper and copper alloy corrosion because most systems do
not employ a copper corrosion inhibitor. The limits for hydrazine-treated and pure water systems
are based on the Stator Cooling Guidelines [4].
7.2.15 Sulfate
The sulfate ion can contribute to IGSCC in 300 series stainless steels. Sulfate can compete with
the corrosion inhibitor in carbon steel. Sulfate contamination can come from poor quality
makeup water, service water in-leakage, or biocide additions. Sulfate is a routine Control
Parameter in pure water and Hydrazine systems and an Investigative Parameter in other inhibited
systems.
7.2.16 Calcium and Magnesium
In systems with raw water makeup, hardness ions (calcium and magnesium) can lead to the
formation of mineral scales if there is excessive makeup. Calcium and magnesium can also be
introduced by service water in-leakage. The presence of magnesium can be observed due to the
use of isothiazolone, which has magnesium chloride added as a stabilizing agent. Calcium and
magnesium are Investigative Parameters and are not measured unless raw water ingress is
suspected.
7.2.17 Refrigerant Chemicals
Refrigerant chemicals (for example, Freon) were listed in Table 5-1 in Revision 0 of the
Closed Cooling Water Chemistry Guideline. In reality, the evaporator section of a chiller
operates under a vacuum. Therefore, the refrigerant gas cannot make its way into the chilled
water during system operation. Analyzing for refrigerant chemicals in chilled water would have
little value, even as an Investigative Parameter.
7.2.18 Reserve Alkalinity (RA)
Reserve Alkalinity is a term applied to inhibited glycol engine coolants to give an approximate
indication of the amount of remaining alkaline inhibitors. The alkaline inhibitors provide
buffering action and neutralize acids that are introduced into the coolant or created by the
oxidation of ethylene or propylene glycol. Some inhibitors that contribute little or no RA can
give excellent corrosion protection to certain metals but have little capacity to combat acid
contamination. Therefore, caution should be used when monitoring RA. Reserve Alkalinity is
not the sole dependable measure of the coolants ability to prevent corrosion, nor can it
satisfactorily indicate the additional life of the coolant [42].
7-7
7.2.19 Visual Evaluation of CCW Fluids
The condition of the system fluid can be qualitatively assessed from visual examination of a
sample. This is particularly true in glycol systems, but can be applied to other systems as well.
The attributes that should be qualitatively evaluated on a fresh sample of coolant are:
Color Glycol formulations (as well as other inhibitor packages) will have a proper color
and intensity for the concentration of inhibitor present. A visual comparison with an inhibitor
concentration of the approximate concentration should be made to assess these parameters.
Turbidity or Clarity Terms like translucent, hazy, and opaque are qualitative terms
indicating the amount of suspended material.
Solids Their color and approximate volume percent in the sample container after a short
settling period without centrifugation.
Surface film Visual examination of the sample surface for oils, congealed materials
(lubricants), or other floating matter.
The visual observation of these characteristics should be performed in a well-lighted area

(preferably the laboratory) with a white-to-neutral-colored background in order to see through
the sample. This will provide for consistent results between analysts. Notations should be made
in the Remarks or Comments section of the sample log.
7.3 Monitoring Frequency
Sampling and analysis frequencies are discussed in the tables in Section 5. Emergency diesel
generators fall into the category of intermittent systems. They are typically operated on a
monthly surveillance schedule and are sampled at the time of operation. Unless plant experience
indicates otherwise, it is important that these systems be sampled while they are operating or
shortly after operation is terminated. Otherwise, the sample might not be representative. Note
that diesel operation is likely to change any microbiological populations due to temperature
fluctuations.
Investigative Parameters are used to assess changes in the chemistry of CCW systems when there
is no apparent cause for the change that can be found through analysis of the Control and
Diagnostic Parameters. As such, there is no recommended sampling frequency.
7.4 Investigative Parameters
Investigative Parameters are typically not used until an anomalous result in the CCW system
shows up. At that time, the cause of the change can be determined by using these parameters,
although an actual value for the system might not exist.
Simulation methods can be used to assess what the ideal values of these parameters might be
when this type of situation arises. One such method is to use the makeup water source and add
7-8
fresh inhibitor solution to the systems existing concentration, and then measure the value of the
Investigative Parameter. This would then be compared to the value presently in the system.
Another method might be to evaluate the presence of a potential contaminant based on chemical
analysis of the system additives, provided by the manufacturer (for example, using the
specification sheet, which provides information on potential contaminants).
Perhaps the best way to describe how to evaluate the results of Investigative Parameter analyses
is through the following examples:
Case 1: A CCW system has a sudden decrease in the concentration of chromate. The chemistry
analysis for chromate uses the colorimetric diphenylcarbazone method. It is also noted that the
color of the sample has a green tinge. The initial response is to look for leaks and increased
makeup causing the chromate concentration to drop. In parallel, some chemical analyses might
be appropriate.
Analysis of the sample for total chromium by atomic absorption analysis would show if the
concentration of total chromium has changed. If it has not, analysis for TOC would be indicated.
Chromium can exist in two different oxidation states in CCW systems: +3 (chromic ion) and
+6 (either chromate or dichromate ion). Carbonaceous materials can be oxidized by chromate,
changing its oxidation state to +3. The source of TOC might be a different makeup water source,
chemical additive contamination, or maintenance activities.
Case 2: Routine measurement of specific conductivity in a system that uses hydrazine is

2535 S/cm. A sudden increase in the conductivity of the CCW sample to 55 S/cm is
observed, as well as an increase in the sulfate concentration from 2045 ppb. It seems apparent
that there is ingress of raw water. Sodium, calcium, and magnesium analysis would help to
identify if the increase in sulfate is commensurate with the amount of these ions present in the
system. A calculation could also be performed to determine if the sulfate increase from raw
water alone could account for the increase in conductivity.
7-9
8
ADDITIONAL MONITORING TECHNIQUES
8.1 Corrosion
The control of corrosion is the primary purpose of the CCW treatment program. Although this is
the goal, it is often not easy to directly confirm satisfactory corrosion control; however, the
treatment programs that are typically used in nuclear CCW systems have a well-regarded history
of good corrosion control.
The corrosion rates targeted in CCW systems are dependent on the alloy. Carbon steel usually
has the highest corrosion allowance. Corrosion rate targets for copper alloys are limited by the
secondary effect of inducing pitting corrosion of carbon steel. When copper alloys corrode,
copper ions are transported in the water and might deposit on carbon steel surfaces as copper
metal. This initiates small galvanic corrosion cells on the carbon steel and creates pits.
Stainless steels are limited to very low general corrosion rates, consistent with the higher
corrosion resistance of these materials. It is important to note that pitting attack on any metal is
unacceptable.
There are several methods available to determine corrosion rates. Methods without heat transfer
involve inserting a metal specimen in the sample stream and measuring corrosion rate. This is
done by either determining weight loss or by measuring an electrochemical phenomenon related
to corrosion (linear polarization resistance or electrical resistance).
Corrosion rate measurements are done under ideal conditions and do not represent a direct
correlation with system conditions. Although corrosion rate measurements can provide helpful
data, they might not reflect what is actually happening in an operating system. Industry
experience has shown that corrosion rates will be low if inhibitor levels are consistently
maintained, pH is held within recommended ranges, microbiological growth is controlled, and
leakage is minimized.
An alternative to direct corrosion rate measurements is an integrated monitoring and inspection

program. This is a qualitative evaluation of the existence of a corrosion problem. Although the
results are not quantitative, they might provide more realistic information about plant corrosion
conditions than does a corrosion rate monitoring program.
8-1
Additional Monitoring Techniques
8.1.1 Monitoring Techniques
Corrosion Coupons
Corrosion coupons are metal specimens that are carefully prepared, weighed, and inserted into
the water stream. They are exposed for a period of time (recommended minimum 90 days),
removed, and re-weighed to determine a weight loss [43]. The weight loss is used to calculate a
corrosion rate for the specific metal alloy. The corrosion rate is expressed in mils per year (mpy)
or millimeters per year (mm/yr).
Corrosion coupons are fairly easy to use. Although they do not exactly duplicate system
geometry or heat transfer conditions, they provide a relatively repeatable means of estimating the
rate of corrosion that will occur using a given material under a given set of conditions.
Typically, a corrosion coupon rack is only operated at a single-flow rate. Actual system flows
might vary over time and a coupon rack does not duplicate this condition. Corrosion conditions
in the actual system, thus, might not be the same as predicted by the coupons. The corrosion rates
determined by coupons are, therefore, only a guide as to what is occurring in the CCW system.
When a corrosion coupon is inserted into a system, the initial corrosion rate is high until the
protective film is formed. The corrosion rate then decreases over time and approaches an
equilibrium value. If a corrosion coupon is exposed for a short period of time (for example,
<30 days), the measured corrosion rate will be significantly higher than if the corrosion coupon
is exposed under the same conditions for a longer period of time (for example, 90 days or more).
There are advantages and disadvantages to shorter and longer exposure periods:
A short exposure period can provide a rapid indication of the success of the corrosion control
program.
A shorter exposure period allows fluctuations in corrosive conditions to be observed but
yields corrosion rates that are higher than actually occurring in the system.
A longer exposure period is more representative of actual system conditions but does not
provide any information on the impact of system upsets on corrosion rates.
A 90-day exposure period is often considered to be a valid compromise. The exposure period is
long enough to allow for mature protective film formation but short enough to allow observation
of any short-term upsets in corrosion rates. Longer exposure periods can be used in CCW
systems but should be consistent from one test period to the next in order to eliminate exposure
period as a variable in the test. The exposure period can also be impacted by ALARA
considerations.
Another valuable use of corrosion coupons is to remove the coupon after a period of exposure
and visually inspect it. This will determine if a uniform protective film is being formed,
therefore, detecting pitting attack.
8-2
Some suppliers provide pretreated (passivated) coupons. This consists of immersing the coupon
in a strong corrosion inhibitor solution and coating the surface with a tightly adherent protective
layer. This reduces the initial corrosion of the bare metal surface and produces a lower overall
corrosion rate. The use of pretreated coupons is not covered in the ASTM standard. Pretreated
coupons in CCW systems interfere with the basic purpose of the corrosion coupon, which is to
verify that the corrosion inhibitor is forming a passive film before corrosion can occur.
If acceptable from the standpoint of mechanical strength, the corrosion coupon rack should be
constructed of plastic (PVC) piping because PVC does not corrode. If the rack must be
constructed of a metallic material, stainless steel is the best, although carbon steels and other
non-copper alloys can be used. Carbon steel can corrode and accumulate corrosion product
deposits that can affect flow velocities. However, because corrosion rates are typically low in
CCW systems, carbon steel coupon racks can provide satisfactory service. Copper-bearing alloys
can result in copper plating out on a carbon steel coupon. This can cause galvanic corrosion and
produce an erroneous result.
Although corrosion coupon monitoring can be simple and relatively inexpensive in non-nuclear
applications, this is often not the case in nuclear plants. This is due to the high cost of the system
modifications required to install corrosion coupon racks and the large number of CCW systems
in many plants.
Acceptable corrosion rates in CCW systems are lower than would be established strictly to
achieve acceptable equipment life based on metal loss due to general corrosion. In a CCW
system, corrosion products (foulants) are not routinely and continuously discharged from the
system as they are in an open recirculating system. The prevention of fouling, therefore, becomes
a driving force in corrosion rate guidelines.
When adequate inhibitor levels, pH levels, and microbiological control are maintained in a
system, it should be possible to achieve the corrosion rates on corrosion coupons shown in Table
8-1. These measurements are desirable in some circumstances but are not requirements.
Table 8-1
CCW Corrosion Coupon Rate Guidelines, Mils per Year (mpy)
Carbon Steel Copper Alloy Stainless Steel

Good <0.3 <0.2 <0.1
Marginal >0.3 to 0.5 >0.2 to 0.3
Poor >0.5 >0.3 >0.1
Electrochemical Means
Linear Polarization Measurements [44]: Linear polarization operates on the principle that a
voltage impressed across the conductive interface boundary will result in a current flow that is
directly proportional to the corrosion occurring on the metal electrode surface.
8-3
Available designs include models with two electrodes and three electrodes. The probes can be
inserted into a section of pipe or installed in a bypass-type corrosion coupon rack. Probes with
elements that are flush with the piping wall are also available. Most often, probes are used in a
corrosion coupon rack installation because the probes are more readily accessible for
examination and replacement.
The method is applicable to all natural or treated waters. Since the linear polarization method
depends on solution conductivity, errors can be introduced when dealing with low-conductivity
waters (for example, deionized quality). The equipment manufacturer should be consulted on
probe designs applicable to a specific water.
Temperature and flow influence the corrosion rate measured by the probes. Changes in flow or
temperature will cause changes in the apparent corrosion rate in the piping or coupon rack. If
fouled, probes will produce erroneous results, especially if deposits bridge the opening between
the probes.
Electrical Resistance [44]: This technique measures the resistance of a section of wire that is
exposed to the cooling water. As the wire corrodes, its cross-sectional area decreases, thus
causing an increase in resistance. The resistance increase over time is converted to a corrosion
rate.
Electrochemical Noise (ECN)
Electrochemical noise [45] corrosion monitoring derives information on the corrosion rate and
mechanism from naturally occurring fluctuations of potential and current. Three electrodes are
used. A zero-resistance ammeter is connected between two of them, and the third is used as a
reference electrode to monitor the potential of the first two. Potential and current density
measurements are typically taken once a second, and a single data record typically covers 5
minutes.
The calculated corrosion rate has the same relation to actual metal loss of the equipment as does
the rate calculated from Lindar Polarization Resistance (LPR). In addition, ECN is a more
sensitive method than LPR, and generally has somewhat wider variation around the mean. In
addition, various calculated parameters have been proposed as localization factors, which
indicate whether the corrosion is general or localized (pitting, crevice, cracking, and so on).
8.2 Fouling
Fouling in CCW systems will most likely be the result of either corrosion or microbiological
growth. Control of both of these mechanisms will prevent fouling of the system. There are no
specific guidelines for the amount of fouling allowed in CCW systems. It should be minimal and
not interfere with heat transfer. For plant performance monitoring purposes, the assumption
should be verified that fouling on the CCW side is minimal. Fouling must be limited below the
amount that would cause the fouling factor to be raised above design assumptions in heat
exchanger sizing calculations. It might be possible with installed plant equipment (temperature,
8-4
pressure, and flow gauges) to assess relative fouling in certain portions of the system. Flow
monitoring can also be performed using hand-held, adjacent-to-line, acoustic flow monitors.
Measurements made over several months can assess changes in flow or temperature differentials.
One of the most effective methods of determining the extent of fouling is through visual
inspection of open system components. This can be done any time a system component is taken
out of service for scheduled maintenance. The exposed system surfaces can be visually examined
with small magnifiers, and samples of corrosion or fouling deposits can be taken and analyzed. It
is critical that if microbiological fouling is suspected, personnel disassembling the equipment
notify the visual inspectors prior to opening the system so that they can help to minimize
inadvertent contamination. Maintaining a record of these inspections (video or photographs) as
part of the work control process will help to provide an historical database of observations. This
can assist in long-term assessment of system health.
8.3 Microbiological Growth
Control of biological growth is important in CCW systems because of its impact on heat transfer
and corrosion. The accumulation of slime masses will cause direct fouling of heat exchange
surfaces. Biological growth might also result in MIC-related failures. In addition, nitrifying and
denitrifying bacteria will consume nitrite corrosion inhibitors and produce byproducts that are
either less effective as corrosion inhibitors or are corrosive.
The goal of a bacterial monitoring program is to control bacterial populations on surfaces within
the system. If feasible, it would be preferable to measure the organisms that colonize on a surface
(sessile organisms) rather than measuring the free floating (planktonic) organisms, particularly if
the treated system might have creviced conditions or biological deposits. In some cases,
determining sessile counts is feasible without modifying existing plant systems.
Most microbiological testing is performed on the bulk water in the CCW system (planktonic
organisms). The tests for planktonic bacteria are easier to perform than tests for sessile bacteria.
Note that planktonic bacteria results might not have a direct relationship to sessile organisms.
Sessile organisms, rather than planktonic organisms, cause problems such as MIC or
denitrification in CCW systems. In many cases, however, planktonic bacteria tests do provide a
good indication of trends in general microbiological control.
8.3.1 Colony Counting Techniques
Various methods to measure planktonic bacteria are available. Due to differences in measurement
technique, acceptance criteria for biological growth must be established for the technique used.
The standard total aerobic plate count method will yield results in colony-forming units per
milliliter of sample (CFU/ml). Other methods, such as adenosine triphosphate (ATP), will yield
results in different units such as grams/ml of ATP or relative light units (RLUs).
Appropriate limits need to be established as part of the site-specific strategic plan. For bulk water
total aerobic plate counts, a limit of 103 (1,000) CFU/ml is often used. However, it should be
8-5
noted that this is an arbitrary figure and some systems have operated successfully at higher
bacterial levels.
These guidelines for aerobic bacteria suffer from the limitation that there might not be a
relationship between the bacteria in the bulk water and microbiological deposits (sessile bacteria)
on surfaces. Although valuable in many cases, bulk water testing can be considered a crude
screening test.
The typical total aerobic plate count limit of 103 CFU/ml represents a measurable but low level
of total aerobic bacterial activity. Part of the total microbial activity in a system might consist of
anaerobic bacteria, fastidious bacteria, molds, algae, and protozoa. The aerobic techniques will
not quantify this activity.
Tests are also often performed for sulfate-reducing bacteria (SRB) or total anaerobic bacteria. If
measured by Most Probable Number (MPN) plate count techniques, it is recommended that SRB
be maintained at zero in the bulk water. The SRB limit of zero is based on the assumption that
any measurable SRB activity in the bulk water means that there are active SRB colonies in
biofilms or underneath deposits.
Adenosine Triphosphate (ATP)
This is a bioluminescence method of determining the concentration of living organisms [46].

ATP is present in all living organisms and is not limited to bacteria. The analysis makes use of
bioluminescence to measure living organisms with a photometer. ATP monitoring is a method of
determining levels of biological activity not based on culturing organisms, but rather on
measuring a cellular component. An advantage of the ATP technique is that it detects all
microbiological species (often referred to as the total biomass) rather than specific groups of
organisms (for example, aerobic bacteria, anaerobic bacteria algae, mold, and so on).
Total ATP is a measurement of all ATP in the sample. This includes background as well as ATP
due to live organisms. Free ATP is a measurement of the background ATP in the sample.
Microbial ATP (Total minus Free) is the ATP due only to live organisms.
ATP monitoring eliminates the need for extended incubation times associated with traditional
culture-based monitoring procedures (including dipslides). This reduces service time and
provides the real time assessment of microbial loading in an industrial system. Therefore, ATP
analysis is a rapid technique that produces results in a few minutes. In addition, it detects both
aerobic and anaerobic organisms, as well as algae and fungus, and for this reason does not suffer
the limitations of culturing methods. Because ATP in the cell decays rapidly when the organism
dies, ATP is a measure of live organisms. It is not truly quantitative for actual bacteria
populations because different microbial species (bacterial, algal, or fungal species) contain
different amounts of ATP and healthy organisms produce more ATP than stressed organisms.
There is no single ATP reading that can be universally used as an indicator of whether
microbiological activity is low or high. Each type of ATP measuring equipment (referred to as
ATP luminometers) will provide different results. Each site will have to establish ATP guidelines
8-6
based on the test and equipment being used. ATP can be made more quantitative by utilizing
ATP standards. This is because ATP reagents differ from batch to batch and change in reactivity
over time. Therefore, the use of ATP standards is helpful in determining that both instruments
and reagents are operating satisfactorily.
Currently, ATP tests are performed with the use of a self-contained pen that allows for the
rapid measurement of Total or Free ATP. ATP luminometers will provide a read-out in RLUs.
Using RLUs as a quantitative indicator of microbiological activity is flawed because:
Variations exist between luminometers and, as different luminometers are used, the obtained
values can vary
The pens rely on an enzyme that can change over time and storage conditions, both of which
can have a dramatic effect on the results, giving a false indication of good system control
Different manufacturers pens will have differing concentrations of enzyme and components,
leading to different light output from the devices, even if the ATP levels are the same
By converting the readings to standard units of ng/ml (ppb) of ATP, the results will be
transferable between plants, meters, and pen batches, and over time. This makes the data
generally applicable, instead of being limited to only one site.
The principle of running an ATP standard is based on the measurement of a standard

concentration of Adenosine Triphosphate (typically 1 nanogram of ATP per ml of water), used
as an assurance of reagent and instrument function. The concentration of ATP in the standard
represents the quantity of ATP expected from an ideal pure culture population of 1 x 106
bacteria/ml. The standard should be refrigerated and used before the expiration date. An ATP
quality test standard is performed by using the ATP standard in place of a water sample.
Therefore, the representative pen (for Total ATP) is dipped into the vial containing the ATP
standard (as opposed to the water sample) and the bioluminescence (RLU) is measured with the
ATP meter. Knowing that the vial in question represents 1 ng of ATP/ml, the measured RLU
from the meter is equal to 1 ng of ATP/ml. To convert a water sample RLU, the measured water
sample RLU result is divided by the ATP standard measured RLU.
For an example, if the 1 ng/ml ATP standard yields a result of 1000 RLU and the water sample
yields a result of 500 RLU, the result recorded for the water sample is 0.5 ng/ml (500 RLU/1000
RLU). This should be done for the Free ATP test as well as for the Total ATP test. If both the
Free and Total ATP tests are to be determined on the same water sample, it is important to test
the Free ATP first. The Total pen contains a lysing agent, which will convert cellular ATP in the
water sample to Free ATP and cause an artificially high Free ATP reading.
Dip Slides
Dip slides or paddle testers are a semi-quantitative method of testing for total aerobic bacteria.
Some testers contain a medium for total aerobic bacteria on one side of the paddle and a medium
for yeast and mold on the other side of the paddle. The main drawback with dip slides is that the
sampling technique has a significant impact on the results. The results are particularly affected
8-7
by the amount of time the slide remains in the water. Another drawback is that the bacteria might
not be able to grow on the particular nutrient media or at the particular incubation temperature.
This is a good tool, however, for routine approximations of the presence of aerobic bacteria.
Total Aerobic Plate Counts
Total Aerobic Plate Counts [47] are determined by pour plate, spread plate, or a membrane
filtration method. It provides an approximation of total numbers of aerobic bacteria by measuring
the number of aerobic bacteria that can grow rapidly under the conditions provided. Many
aerobic organisms are unable to grow on the nutrients provided or at the particular incubation
temperature. Additionally, clustered groups of bacteria will count as a single Colony Forming
Unit. Plate counts are more quantitative than dip slides, but require a higher skill level to
perform. The method is not specific for any particular type of bacteria.
PetriFilm
This is a proprietary version of the total aerobic plate count where the incubation media is
contained in a dry form on a film. The advantages are ease of use and compactness [48]. The
technique requires less skill level than the Total Aerobic culturing techniques described but
might still require serial dilutions.
Test Kits
A variety of bacterial test kits are available. These allow the determination of specific types of
aerobic, anaerobic, and facultative anaerobic bacteria that might be of interest in a CCW system.
Included might be slime-forming bacteria, nitrifying bacteria (for example, Nitrobacter),
denitrifying bacteria (for example, Nitrobacter agilis), sulfate-reducing bacteria (for example,
Desulfovibrio desulfuricans), anaerobic acid producing bacteria, and so on.
8.3.2 Sessile Bacteria Monitoring Techniques
Sessile bacteria accumulate on surfaces, while planktonic bacteria are those that are free floating
in the water. The sessile bacteria are of more concern than the planktonic bacteria, thus, it might
be advantageous to monitor for sessile bacteria. There are several techniques for doing this.
Stainless Steel Corrosion Coupons
Stainless steel corrosion coupons can be used in a corrosion coupon rack as a surface to culture
sessile organisms. The coupon can then be removed after a period of time, swabbed (or agitated)
to remove the biofilm, and the organisms cultured or tested for ATP (biomass/cm2). Another
variation is to sandwich two stainless steel coupons together to simulate a crevice.
8-8
Screened Coupons
Screened coupons are similar to corrosion coupons except that a rigid stainless steel screen
substitutes for the corrosion coupon. The screen accumulates biofilm. The accumulation of
biofilm can be evaluated qualitatively, or the biofilm can be removed and colony-counting or
ATP techniques can be used to estimate the relative amount of biofilm.
Glass Bead Holders
Glass bead holders contain glass beads that provide a surface for biofilm formation. After a
suitable incubation period, several glass beads are removed and the biofilm is physically
removed (usually ultrasonically). Colony-counting or ATP techniques can then be used to
estimate the relative amount of biofilm.
Metal Specimen Holder
This is a flow-through device that holds metal plugs or buttons, which provide a surface for
bacterial colonization. One trade name for such a device is the Robbins Device. The plugs can be
removed for examination while the holder is in place. Microscopic examination of the biofilm or
biomass can indicate the unique characteristics of the microflora. The microflora can also be
enumerated and characterized using colony-counting or ATP techniques. The amount of biofilm
or biomass can be determined by using gravimetric techniques. Plugs of multiple metallurgies
can be used in this device to test the impact of metallurgy on colonization.
Inspections
While not an on-line monitoring technique, inspections represent an important opportunity to

evaluate the extent of sessile bacteria accumulation and collect samples (for example, swabs) for
identifying sessile bacteria species.
8.3.3 Monitoring for Specific Microbial Species
Monitoring for specific microbial species might be warranted for two conditions:
To identify specific bacteria types relative to a particular treatment approach (for example,
nitrifying or denitrifying bacteria in a nitrite-treated system)
To determine the most appropriate biocide treatment regimen
8-9
8.4 Non-Chemistry Monitoring
8.4.1 Inspections
Closed cooling water system inspections are a form of monitoring that provide a snapshot
assessment of equipment status and water-treatment program performance at a particular time.
Most of these inspections are performed in conjunction with normal maintenance activities. Over
the course of several inspections, trend data are collected that can be used to predict potential
problems and service life.
The objectives of any CCW system inspection should include data collection and analyses to
determine the potential for:
Loss of structural integrity caused by corrosion
Excessive leakage caused by corrosion
Decreased flow capacity caused by corrosion and/or deposition
Reduced heat transfer caused by corrosion and/or deposition
Inspections performed to characterize the corrosion and deposition present in the CCW system
should be designed to identify the forms of corrosion and deposition, their cause(s), and the rate
of degradation that can be used in calculating equipment residual life assessments. Inspection
planning, sample collection, and inspection documentation are important parts of the inspection
process. Inspections are discussed in detail in other EPRI publications [49,50].
Inspection techniques will vary depending upon the type of CCW system equipment (piping,
heat exchangers, valves, pumps, etc.) and its accessibility.
8.4.2 Nondestructive Evaluations (NDEs)
A number of mechanical techniques can be used for on-line inspections of service water systems
[49,50]. Three of the more common methods are ultrasonic testing (UT), eddy current testing,
and radiographic testing. These techniques are also suitable for off-line inspections.
Ultrasonic Testing
Ultrasonic testing is a nondestructive method for characterizing flaws or wall thickness in

metallic piping and components, usually from the outside surface. UT methods might be useful
for detecting localized corrosion, provided appropriate inspection locations are selected and
inspection grids are sufficiently fine. Small wall losses might not be detected by UT.
Because UT could be applied from either the outside or inside of the component, it can be used
where access is limited. For CCW system applications, inspections are most commonly
performed from the outside. A major advantage of ultrasonic testing is that the system does not
need to be de-watered. Often, the system can be examined while it is operating.
8-10
All materials can be inspected by UT; however, some very coarse-grained materials (for
example, stainless steel welds or castings) might be difficult to inspect. Geometric discontinuities
or dissimilar metal joints will produce UT reflections that will require interpretation by an
experienced operator. Fortunately, piping and components are fairly standard configurations that
are relatively easy to inspect.
There are automated forms of UT testing that scan an area of piping. This can detect
irregularities in pipe thickness and detect localized corrosion or pitting. UT methods (manual or
automatic) do not provide information on the character or thickness of deposits.
Electromagnetic Automatic Scanning
This technique also provides a map of thickness variations in the scanned area of the piping. The
technique does not provide information on the character or thickness of deposits.
Eddy Current Testing
Inspection of tubing or pipes by eddy current methods relies upon the capability to detect
changes in the patterns of currents induced in the part being examined. Applying an alternating
current (the exciting current) to a coil in the vicinity of the part to be inspected causes other
currents (eddy currents) to flow in the part as a result of electromagnetic flux. Cracks or other
flaws will disturb the flow of the eddy currents and these disturbances can be detected
electronically.
Eddy current testing is typically performed on non-magnetic materials, usually thin-walled heat
exchanger tubing. Most often eddy current testing is done from the ID of the pipe or tube, thus,
access to the ID is required. De-watering of the system is generally necessary and, as with UT,
the success of the eddy current method is strongly dependent upon the training and skill of the
operator (and signal interpreter).
Radiographic Testing
Radiographic testing (RT) is not typically used in CCW systems. In certain cases, it might have
some application. RT consists of penetrating the structure with ionizing radiation and capturing
an image of the structure on a film or electronic sensor (typically displayed on a viewing screen
or television monitor). RT provides information on the character or thickness of deposits.
Depending on the configuration of the scan, RT might miss pitting corrosion.
8.4.3 Leakage
The corrosion and deposition characteristics of CCW systems change rapidly if they are not truly
closed. Monitoring of system leakage is therefore an important part of the CCW monitoring
program. Note, however, that small pinhole leaks and cracks might self-seal and not be detected
by leakage monitoring. Leakage monitoring might be accomplished by metering system makeup
8-11
or by measuring the loss of chemicals over a period of time. The latter can be accomplished by
chemical testing or conductivity measurements. In some cases, system leakage can be detected
by tracking head tank level if makeup to the system is manual rather than automatic.
Chemical treatment selection and application, dosage and demand, should always be controlled
and adjusted, taking into consideration the relative and actual makeup water use rate and amount.
Closed system losses should be trended and acted upon accordingly.
8.4.4 Heat Transfer
Performance monitoring is typically part of the engineering program. It can be used to confirm
that conditions in the CCW system are not degrading heat exchanger performance. System health
reports should show trends of system parameters such as temperature, flow, pressure, and heat
exchanger efficiency as a function of time. They should also evaluate any seasonal effects that
might present themselves in the data.
8.5 Trending
The logging and trending of data is an important part of the CCW system monitoring program.
The data to be trended will depend on the system design, chemical treatment program, and
monitoring in place. Data to be trended might include Control Parameters, Diagnostic
Parameters, and system losses.
The purpose of trending is to detect, and often anticipate, problems caused by system leakage,
microbiological growth, or the accumulation of system impurities.
Logging of system parameters is important to provide a historical database for comparison

purposes. Trending of these parameters is important to anticipate changes in system conditions.
Calculations can be used as part of the trending regimen to assist with system evaluation. One
valuable calculation is the conductivity-to-nitrite ratio in a nitrite-treated system. This can help
detect whether a nitrite decrease is due to system leakage or microbiological activity. A leak will
decrease both conductivity and nitrite and the conductivity-to-nitrite ratio will remain constant.
Microbiological activity will decrease nitrite but leave conductivity unchanged, resulting in an
increasing ratio. The nitrite-to-molybdate ratio can serve the same purpose in a nitrite/molybdate
system.
8.6 Chemical Analysis
The wide variety of corrosion control agents, biocides, and pH adjust chemicals do not allow a
comprehensive list of chemical analyses and detection ranges. However, each combination of
chemicals provides analytical challenges, which need to be effectively addressed in order to
successfully monitor trends of inhibitors, biocides, and contaminants. This section addresses
some general chemical analysis concepts that are important for the analytes and some specific
methods of analysis. This is not an all-inclusive list of methods that can be used for analysis, but
8-12
it includes the more frequently used methods. Any method should be matrix-tested to ensure that
measurement results are not masked or biased by the presence of high concentrations of
corrosion inhibitors.
8.6.1 Ion Chromatography (IC)
This technique is routinely used to monitor concentrations of control agents such as nitrite, as
well as contaminants like nitrate, chloride, fluoride, and sulfate (anions), or sodium, calcium, and
magnesium (cations). The determination of nitrite will be mostly unaffected by all other species
because nitrite is the major ionic species in the solution. However, because the concentration
range of this ion can be so broad (500 to >1500 ppm), it will also act as an eluent in the
chromatography process. This can have several effects on the analytical process, most notably,
variability of the detection limit and the retention time of the analyte.
The retention time shift should be determined by comparing the system chromatogram with
chromatograms of standards used to calibrate the instrument, as long as the standards are run in
the inhibitor matrix. The shift of retention time can also cause a broadening or sharpening of the
chromatographic peak (dependent upon the eluent strength relative to the calibration). The
detection limit is affected by the detector response to the inhibitor in the system, as well as the
way the peak shape has deformed due to the presence of other ions in the system. Thus, if a
conductivity detector is used, the detection limit will most likely increase at higher
concentrations of anionic materials (due to higher conductivity). However, the limit of detection
of the contaminant analytes is not nearly as important as being able to reproduce values close to
the Action Levels. Thus, it would be important to establish a quality check for each inhibitor
system at the upper end of the inhibitor concentration, ensuring that Action Level values can be
achieved.
For analysis of cations, the impact that borate or phosphate (added as part of the inhibitor
package) can have on complexing with the metals should be evaluated under matrix match
conditions.
8.6.2 Ion Selective Electrodes (ISE)
This method of analysis is based on the electrochemical potential change of a half-reaction based
on the concentration of a specific ion when measured against an electrode, which is selective for
the half-reaction of that ion. Because the method measures potential and not an intrinsic
parameter of the particular ion, it is subject to many different types of interferences, most notably
other ions of similar charge and reduction potential. This method should also be verified
applicable in the concentration used for the CCW system, for the ions being determined.
Major solution constituents, such as nitrite, can be effectively assessed because the contaminant
concentrations are generally insufficient to alter the potential for the nitrite electrode. This has
been used as an alternative to ion chromatography for chloride, fluoride, and sulfate analysis.
There are ion selective electrodes for metal ions as well.
8-13
Ammonia analysis by electrodes can be performed using one of two different types. Ammonium
ion is detected as described previously and the sample is made acidic with hydrochloric acid.
This method suffers from interference from sodium ion. Thus, analysis of systems where the
corrosion inhibitor is added as sodium salt will need to be assessed for the extent of interference.
The second electrode method is by gas sensing electrode (GSE). In this technique, a membrane
that is sensitive to the passage of ammonia gas is immersed in a sample that has had sufficient
NaOH added to it to convert all of the ammonia to gas.
8.6.3 Atomic Absorption (AA) and Inductively Coupled Plasma (ICP)
Both of these methods are very useful at determining total metal ion concentration in solution.
Analysis for iron, copper, magnesium, calcium, chromium, molybdenum, and sodium can all be
routinely performed using these methods. Both methods measure an element-specific
characteristic based on atomic structure of the metal, making the analysis very specific for an
individual element. For the types of matrices that are experienced in CCW systems, there are
few, if any, matrix effects that would affect the analytical result. It is important to note that, in
each of these analyses, the result is for total metal content. This analysis does not yield
information about the oxidation state of the material being examined, nor does it identify
molecular species. This is best described by two different analyses.
Chromate is a good anodic corrosion inhibitor. It is also a strong oxidizing agent. If a CCW
system containing chromates were to experience an intrusion of oil, it is likely that the oil would
be partially oxidized to carbon dioxide and water, while the chromate would be reduced to Cr+3.
Depending on the concentration of Cr+3 and the pH, the Cr+3 might precipitate. The Cr+3 does not
provide any anodic inhibition at all. Analysis of the water after the event would only indicate the
total chromium, which would be a mixture of the two species. Such a result would lead to an
erroneous conclusion about the appropriate level of corrosion inhibitor.
Molybdates are also good anodic inhibitors. However, this species can also be converted to
MoO3, which has no corrosion inhibitor value at all. This species can form small particulates that
can become suspended. If total molybdenum analysis is performed, it again might indicate a
satisfactory inhibitor level, when in fact it is low.
In each of these instances, a spectrophotometric test is available for the specific molecular
species, which provides the inhibitor function. It might be advisable to use the alternate test on a
certain frequency (for example, annually) to ensure that no degradation occurs. This will be
verification that the AA or ICP methods are fairly reproducing the inhibitor concentration
required.
8.6.4 Ultraviolet/Visible Spectroscopy (UV/Vis)
UV/Visible spectroscopy is useful for measuring the specific electronic transitions from
valence shell electrons in molecular species. Hydrazine, silica, phosphate, boric acid,
molybdate, nitrite, nitrate, and chromate are all species that can be determined by this method.
8-14
Chloride, fluoride, and sulfate can also be determined, but this practice has become less common
with the advent of ISEs and IC units. In general, a chromogenic agent, which has molecular
absorbance at a specific wavelength, is used in the analysis. These molecular bands are very
broad and interferences from other colored matter in the same wavelength range are
interferences. Sample turbidity can also provide interference in these analyses, so sample
filtration might be necessary prior to analysis to ensure accurate measurements.
8.6.5 pH and Conductivity
These two methods of analysis measure the total effects of all the dissolved matter in the solution
on the parameter of hydrogen ion concentration (pH) and solution electrical conductivity. These
tests are used as measures of gross contamination or loss of corrosion control agent. Together,
these can be used on a more frequent basis than the element- or inhibitor-specific tests to ensure
that system chemical composition remains relatively the same. This parameter is useful because
the intrusion of an unknown contaminant will most likely affect these two tests, which would be
a warning to begin an investigation.
One particular intrusion, which would not necessarily show up as affecting these two analyses,
would be from solvents or oils. In these cases, odor, color, or TOC would be helpful in
diagnosing the source of the contaminant.
Care must be taken when performing pH on inhibited glycol coolants. In the case of coolants
greater than 50% volume glycol, pH values are not actual values according to the accepted
definition, but are apparent pH values, which are useful in interpretation of coolant condition
[37].
8.6.6 Vendor Test Kits
Most vendor test kits are made for field use as a first-order measure of the concentration of a
particular analyte. The methods are almost always based on sound analytical methods that have
been modified for a portable test kit. In almost all cases, the analyst is asked to interpolate scale
readings (using a mini-meter) or judge a color against a standard set of colors (using a color
comparator). For systems that are relatively stable, with no contaminant ingress and little change
in process, these might be acceptable for routine analyses. However, if these are used for CCW
systems, other laboratory methods should be used on a routine basis to ensure that trends are not
developing that might prove harmful to the system.
Vendor test kits can suffer from a myriad of interferences, the most notable are colored
contaminants. A specific example occurs with the analysis of glutaraldehyde (a di-aldehyde).
The reagent used is sensitive to the glutaraldehyde molecule yielding a certain color. Partial
decomposition products of glutaraldehyde will also yield a color with this material, but not of
exactly the same wavelength. The analyst must then discern, visually, whether or not the color of
the material being tested is the same as that of the standard.
8-15
8.6.7 X-Ray Fluorescence (XRF) of Filtered Material
XRF is a routinely used method of analysis for metals. It is very effective for analysis of
insoluble materials filtered from a system. The instrument produces a highly focused electron
beam on the solid material on the filter surface and this results in the production of characteristic
x-rays of the elements. Most commercial instruments have the capability of analyzing in the
range of 320 keV. This is the region for the K x-ray lines for all of the first-row transition
elements and molybdenum. The K x-ray lines are the most sensitive for any element. This
region can also be used for L lines of some of the higher atomic number elements, such as lead.
This can potentially be used to differentiate between insoluble and dissolved metals. It is very
important to ensure that the sample point and process provide a representative flow for the
sampling of particulates in the fluid medium.
8-16
9
TROUBLESHOOTING AND CORRECTIVE ACTIONS
9.1 Introduction
This section is intended to provide general guidance for some of the more common chemistry
trends that might be observed in closed cooling water systems. A separate section is included for
each of the most popular chemical treatment programs encountered in the nuclear industry, but it
is not intended to be a comprehensive list. Treatment programs covered in this section include
nitrite, nitrite-molybdate, molybdate, chromate, hydrazine, glycol, and pure water.
Due to the differences among closed cooling water system designs, materials of construction,
fluid interface type, makeup water sources, etc., some of this information might not be applicable
in a particular situation. It might be necessary to develop system-specific troubleshooting
guidance to supplement this information.
This information should be useful as a starting point in developing a site-specific comprehensive

closed cooling water treatment and monitoring program. Several examples of troubleshooting
flow charts are also provided as an alternate way of presenting the information provided in this
section. The end-user might find these examples useful if it is desired to include such
troubleshooting charts in site-specific procedures.
Each system has a corrosion inhibitor decay curve (concentration versus time), the slope of
which is a composite effect of inhibitor decomposition and dilution. Changes to this curve can
provide early warning of system leakage increases or contaminant ingress.
9.2 Nitrite-Treated Systems
9.2.1 System Leakage
Symptoms
Decreasing pH
Loss of nitrite
Excessive makeup
Loss of conductivity (following makeup water additions to the system)
Constant conductivity-to-nitrite concentration ratio
Loss of azole
9-1
Troubleshooting and Corrective Actions
Corrective Actions
Consider increasing sampling frequency for inhibitor
Locate and repair system leakage
Add inhibitor if necessary
Adjust pH if necessary
Consider use of dye or tracer to find leaks
9.2.2 Water In-Leakage
Symptoms
Possible pH change (depending on pH of water entering the CCW system)
Loss of nitrite
Loss or gain of conductivity (depending on conductivity of water entering the CCW system)
Constant or increasing conductivity-to-nitrite concentration ratio (depending on conductivity
of water entering the CCW system)
Loss of azole
Increase in storage tank level
Increase in concentrations of impurities or radioactivity (depending on which impurities are
present in water entering the CCW system)
Corrective Actions
Repair system in-leakage
Evaluate impact of contaminants from in-leakage on the system
Consider need for feed and bleed, drain and refill, or filtration
Increase inhibitor concentration if necessary
Consider need to analyze for dissolved oxygen
9.2.3 Bacterial Growth
Symptoms
ATP, total bacteria, or plate counts in excess of specified maximum
Possible decrease in pH
9-2
Possible flow restrictions

Loss of heat transfer capability
Rapid, unexplained rise in corrosion rates
Corrective Actions
Add biocide
Consider need for alternate biocide or alternating biocides
Adjust pH if required
Consider need for feed and bleed or drain and refill
Consider need for system cleaning
9.2.4 Nitrate-Forming Bacteria Growth
Symptoms
Decreasing pH
Loss of nitrite
Increase in nitrate
No significant change in conductivity (between chemical additions)
Increase in conductivity-to-nitrite ratio
Constant azole
Observation of deposit accumulation
Corrective Actions
Add biocide
Consider increasing monitoring frequency for nitrifying bacteria and/or nitrate concentration
Obtain and analyze surface samples for sessile bacteria if possible
Add nitrite inhibitor if necessary
Make pH adjustment if necessary
9-3
9.2.5 Ammonia-Forming Bacteria Growth
Symptoms
Increasing pH due to ammonia production
Loss of nitrite (nitrite might not decrease significantly; ammonia might come from the
breakdown of organic nitrogen compounds)
Increase in ammonia
Increase in conductivity-to-nitrite concentration ratio
Constant azole
Corrective Actions
Add biocide
Consider increasing monitoring frequency for ammonia-forming bacteria and/or ammonia
9.2.6 Acid-Forming Bacteria Growth
Symptoms
Decreasing pH
Constant nitrite concentration
Small increase in conductivity
Constant conductivity-to-nitrite ratio
Constant azole
Corrective Actions
Add biocide
9-4
Increase monitoring frequency for aerobic and anaerobic acid-forming, endospore-forming

bacteria
Obtain surface samples for sessile bacteria if possible
9.2.7 Increase in System Corrosion Rates
Symptoms
Increasing trends in total iron or total copper in bulk water
Increase in corrosion rates on weight loss coupons or electrochemical monitor (if used)
Visible corrosion, tuberculation, or pitting during inspections
Corrosion indications as a result of NDE evaluations
Occurrence of leaks
Corrective Actions
Consider increasing sample frequency for iron and/or copper analysis
Determine cause for increase in corrosion rates and develop corrective action plan
Evaluate effect of elevated iron and copper in system
Increase inhibitor concentrations if necessary
Review microbiological control status
9.2.8 Oil In-Leakage
Symptoms
Possible increase in sulfate and/or phosphate
Possible visible sheen on system samples
Possible unexplained decrease in TTA (oil can interfere with analytical test)
9-5
Corrective Actions
Initiate testing for TOC, oil and grease, sulfate and/or phosphate
Locate oil source and develop corrective action plan
Evaluate impact of oil in system
Remove via cleaning, feed and bleed or drain and refill
Evaluate if azole addition is necessary
9.2.9 Contaminant Ingress
Symptom
Increase in the contaminants found in the in-leakage source but not normally found in the
treated system.
Corrective Actions
Identify source of contaminant and develop corrective action plan
Evaluate effect of elevated contaminant level in the system
If elevated contaminant will result in increased corrosion rate or degraded system
performance, place the system into feed and bleed or drain and refill, or increase inhibitor
concentration(s) to compensate
9.3 Molybdate-Treated Systems
Symptoms
Loss of molybdate
Decreasing pH
Excessive makeup
Decreasing conductivity (following makeup water additions to the system)
Loss of azole
Corrective Actions
Increase sampling frequency for inhibitor as appropriate
9-6
Adjust inhibitor concentrations if necessary
Symptoms
Possible pH change depending on pH of water entering the CCW system
Loss of molybdate
Loss or gain of conductivity (depending on conductivity of water entering the CCW system
Loss of azole
Corrective Actions
Locate and repair system in-leakage
Evaluate effect of contaminants on the system
Symptoms
Possible loss of heat transfer capability
Corrective Actions
Add biocide
9-7
Symptoms
Increasing trend in total iron or total copper concentration
Visible corrosion or tuberculation during inspections
Occurrence of leaks
Corrective Actions
Increase sample frequency for iron and/or copper analysis
Determine cause for increase in corrosion rates and correct
Evaluate effect of elevated iron and copper in the system
Evaluate need for feed and bleed or drain and refill
Symptoms
Possible unexplained decrease in azole (oil can interfere with analytical test)
Corrective Actions
Initiate testing for TOC, oil and grease, and/or sulfate concentration
Locate oil source and correct
Evaluate impact of oil in the system and remove via cleaning or feed and bleed
Symptom
Increase in contaminant found in the in-leakage source but not normally found in the treated
system
9-8
Corrective Actions
Identify source of contaminant and correct.
Evaluate effect of elevated contaminant level in the system.
concentration(s) to compensate.
9.4 Nitrite/Molybdate-Treated Systems
Symptoms
Decreasing pH
Loss of nitrite and molybdate
Excessive makeup
Constant conductivity-to-nitrite or molybdate-to-nitrite concentration ratio
Loss of azole
Corrective Actions
Consider increasing the sampling frequency for inhibitor
Add inhibitor if necessary
Consider use of dye or tracer to find leaks
Symptoms
Loss of nitrite and molybdate
Constant or increasing conductivity-to-nitrite concentration ratio depending on conductivity
of water entering the CCW system)
9-9
Constant molybdate-to-nitrite concentration ratio

Loss of azole
Increase in storage tank level
Corrective Actions
Evaluate impact of contaminants from in-leakage on system
Consider need for feed and bleed, drain and refill, or filtration
Consider need to analyze for dissolved oxygen
Symptoms
Loss of heat transfer capability
Corrective Actions
Add biocide
9.4.4 Nitrate-Forming Bacteria Growth
Symptoms
Decreasing pH
Loss of nitrite
9-10
Constant molybdate
Constant azole
Increase in nitrate
Increase in conductivity-to-nitrite or molybdate-to-nitrite ratio
Observation of deposit accumulation
Corrective Actions
Add biocide
Consider increasing the monitoring frequency for nitrifying bacteria and/or nitrate
concentration
Make pH adjustment if necessary
Symptoms
Loss of nitrite concentration (nitrite might not decrease significantly; ammonia might come
from the breakdown of organic nitrogen compounds)
Constant molybdate concentration
Increasing ammonia concentration
Increase in conductivity-to-nitrite or molybdate-to-nitrite concentration ratio
Constant azole
Corrective Actions
Add biocide
Consider the need for alternate biocide or alternating biocides
9-11
Consider increasing the monitoring frequency for ammonia-forming bacteria and/or

ammonia concentration
Consider the need for system cleaning
9.4.6 Acid-Forming Bacteria Growth
Symptoms
Decreasing pH
Constant nitrite concentration
Constant molybdate concentration
Small increase in conductivity
Constant conductivity-to-nitrite and molybdate-to-nitrite concentration ratio
Constant azole
Corrective Actions
Add biocide
Increase the monitoring frequency for aerobic and anaerobic acid-forming, endospore-
forming bacteria
Obtain surface samples for sessile bacteria if possible
Consider the need for feed and bleed or drain and refill
Consider the need for system cleaning
Symptoms
Increasing trends in total iron or total copper in bulk water
Increase in corrosion rates on weight loss coupons or electrochemical method (if used)
9-12
Visible corrosion, tuberculation, or pitting during inspection

Corrosion indications as a result of NDE evaluations
Occurrence of leaks
Corrective Actions
Consider increasing the sample frequency for iron and/or copper analysis
Increase inhibitor concentrations if necessary
Review microbiological control status
Symptoms
Possible unexplained decrease in TTA/BZT concentration (oil can interfere with TTA
analysis)
Corrective Actions
Initiate testing for TOC, oil and grease, sulfate, and/or phosphate
Locate oil source and develop corrective action plan
Evaluate impact of oil in system
Remove via cleaning, feed and bleed, or drain and refill
Evaluate if azole addition is necessary
Symptom
Increase in the contaminant found in the in-leakage source but not normally found in the
treated system
9-13
Corrective Actions
Identify source of contaminant and develop corrective action plan
performance, place system in feed and bleed, drain and refill, or increase inhibitor
9.5 Chromate-Treated Systems
Symptoms
Decreasing pH
Loss of chromate
Excessive makeup
Decreasing conductivity (following makeup water additions to system)
Loss of azole if present in the system
Corrective Actions
Adjust chromate if necessary
Symptoms
Loss of chromate
Loss of azole if present in the system
9-14
Corrective Actions
Locate and repair system in-leakage
Evaluate effect of contaminants in the system
Increase chromate concentration to compensate if necessary
Symptoms
Increasing trend in total iron or total copper concentration
Occurrence of leaks
Corrective Actions
Symptoms
Possible unexplained decrease in azole if used (oil can interfere with analytical test)
Corrective Actions
Initiate testing for TOC, oil and grease, sulfate, and/or phosphate concentration
Evaluate impact of oil in the system and remove via cleaning, feed and bleed, or drain and
refill
9-15
Symptom
system
Corrective Actions
Identify source of contaminant and correct.
9.6 Hydrazine-Treated Systems
9.6.1 Hydrazine Decomposition
Symptoms
Increasing pH, conductivity
Loss of hydrazine
Increase in ammonia
Corrective Actions
Evaluate need for feed and bleed to remove ammonia and replace with fresh demineralized
water
Add inhibitor to maintain specified levels
Symptoms
Loss of hydrazine
Decrease in pH, conductivity
Increase in dissolved oxygen
9-16
Corrective Actions
Repair system leakage
Adjust inhibitor concentration as needed
Symptoms
Increased conductivity
Increase in concentration of impurities found in water entering the CCW system
Corrective Actions
Evaluate need for feed and bleed or increase inhibitor concentration to compensate if
necessary
9.7 Silicate-Treated Systems
Symptoms
Decreasing pH
Loss of silicate
Excessive makeup
Loss of azole
Corrective Actions
9-17
Symptoms
Loss of silicate
Possible turbidity
Loss of azole
Corrective Actions
Evaluate need for feed and bleed, drain and refill, or increase silicate concentration to
compensate if necessary
Symptoms
Increasing trends in total iron or total copper
Occurrence of leaks
Corrective Actions
9-18
Symptoms
Possible increase in sulfate and or phosphate
Corrective Actions
refill
Symptoms
system
Possible turbidity
Corrective Actions
Identify the source of contaminant and correct.
Symptom
9-19
Corrective Action
Add biocide
9.8 Pure Water Systems
9.8.1 System Out-Leakage
Symptoms
Excessive makeup
Changes in oxygen concentration (depending on the level in makeup water)
Changes in copper concentration
Corrective Actions
If oxygen has changed, sample at various points of the system to determine point of ingress
Symptoms
Increase in conductivity
Increase in concentrations of impurities (depending on which impurities are present in water
entering the CCW system)
Increase in dissolved oxygen content
Corrective Actions
Evaluate effect of service water contaminants on the system
Evaluate need to place system in feed and bleed or drain and refill
9-20
9.8.3 Acidophilic Bacteria Growth
Symptoms
Decreasing pH
Increase in conductivity (usually due to organic short-chain acids like acetic and formic) with
no mineral contaminant ingress
Corrective Actions
Add biocide
Increase monitoring frequency for aerobic and anaerobic bacteria
Begin monitoring sulfate concentration more routinely, looking for trends
Determine source of bacteria ingress
Symptoms
Increase in ammonia
Increasing conductivity
Corrective Actions
Add biocide
Perform system flush
Increase monitoring frequency for ammonia-forming bacteria and ammonia
Determine source of nitrogen for ammonia formation
9-21
Symptoms
Occurrence of leaks
Corrective Actions
Symptoms
Possible increase in sulfate and or phosphate
Organic odor
Corrective Actions
refill
Symptom
system
9-22
Corrective Actions
Identify source of contaminant and correct
performance, place the system into feed and bleed or drain and refill
9.9 Inhibited Glycol Systems
Symptoms
Decreasing pH
Loss of glycol
Excessive makeup
Loss of azole
Corrective Actions
Symptoms
Loss of glycol
Loss of azole
Increase in concentrations of impurities (depending on which impurities are present in water
entering the CCW system)
9-23
Corrective Actions
Place system into feed and bleed if necessary
9.9.3 Glycol Breakdown
Symptoms
Possible decreasing pH
Decrease in reserve alkalinity
Increase in glycolic and related acids
Corrective Actions
Evaluate need to drain and refill
Add replenishment package from manufacturer if appropriate
Symptoms
Occurrence of leaks
Corrective Actions
Place system into feed and bleed or drain and refill if necessary
9-24
Symptoms
Corrective Actions
Initiate testing for sulfate and/or phosphate
refill
Symptom
system
Corrective Actions
Identify source of contaminant and correct
9.10 Flow Charts
The following flow charts (Figures 9-1 through 9-5) can be used as guidance in troubleshooting a
change in CCW system chemistry:
Sudden shift in inhibitor concentration
Ingress of contaminants
Change in pH
Change in conductivity
Increase in corrosion
9-25
Specific charts might need to be developed for those systems where there are many system
interfaces and/or complex system inhibitor chemistry.
Figure 9-1
Troubleshooting Flow Chart for Sudden Shift in Inhibitor Concentration
9-26
Figure 9-2
Troubleshooting Flow Chart for Contaminant Increase
9-27
Figure 9-3
Troubleshooting Flow Chart for pH Change
9-28
Figure 9-4
Troubleshooting Flow Chart for Change in Conductivity
9-29
Figure 9-5
Troubleshooting Flow Chart for Increase in Corrosion Rate or Corrosion Product
9-30
10
METHODOLOGY FOR PLANT-SPECIFIC TREATMENT
OPTIMIZATION
10.1 Introduction
A wide range of materials and operating conditions exist in power plant closed cooling water
systems. Because of this, there is no single optimum water chemistry program that can be
specified for all cases. As such, a CCW chemistry program requires development of a site-
specific strategic plan. This program or plan should consider system design, past history,
monitoring capability, enhanced physical treatment equipment (such as sidestream filters and
sidestream demineralizers) and operating experience. Deviating from the specifications outlined
in this guideline is allowed, provided that sound technical justification and/or performance
monitoring supports the deviation and the deviation has the understanding and support of
management.
Cost-benefit analysis is seldom a major factor in the selection of a CCW chemical treatment
program. The chemical cost to treat closed systems is usually a relatively minor budget item.
10.2 Determining Chemical Treatment Needs
Chemical treatment programs for closed cooling water systems are developed from six areas:
System metallurgy and design
Makeup water quality
Operating conditions
System conditions (such as history of microbiological growth)
Previous treatment regime(s)
Compatibility and impact on other plant systems (for example, radwaste)
10.2.1 Metallurgy and Design
The selection of specific metallurgy for closed cooling water systems will be based on many
design factors in addition to corrosion resistance. Chemical treatment must be compatible with
and protect all of the system components. Even though a specific metal or alloy might make up
only a small part of the total system, corrosion and the transport of corrosion products can impact
corrosion of other components. The corrosion inhibitor(s) must preferably protect all system
10-1
Methodology for Plant-Specific Treatment Optimization
metallurgy or, at least protect the major components from the impact of corrosion of the minor
component. Because there are numerous operating factors that play a part in chemical treatment
selection, it is important that the system engineer be consulted and made a part of the selection
process.
Most closed cooling systems will contain carbon steel (piping) and one or more copper alloys
(heat exchanger tubing). In addition, one or more components containing stainless steel might be
present. Some systems use metals such as aluminum, titanium, or monel.
10.2.2 Makeup Water Source
Makeup water source selection is fundamental to proper, long-term closed system performance.
Although closed system design calls for low makeup requirements due to a lack of evaporation,
deconcentration, or significant leakage, the makeup source quality is a critical factor in the
selection of a treatment program.
Makeup water quality requirements can vary from demineralized water (typical) to potable water
(rare but used in some nuclear plants). Another potential makeup water source is condensate,
which might contain ammonia or other neutralizing amines. These amines can promote the
corrosion of copper alloys. In some cases, a requirement for high-purity recirculating water
might preclude the use of any water-soluble chemical treatment for corrosion control. In these
cases, corrosion protection is limited to system metallurgy and design, and control of dissolved
gases.
Chloride and sulfate can have a significant impact on the inhibitor concentration required for
complete inhibition. However, at the treatment levels commonly used, there is adequate
protection unless chloride and sulfate levels are significant. Table 10-1 provides data from one
study of chromate and nitrite-treated systems.
Table 10-1
Critical Concentration of Chloride and Sulfate, Above Which Pitting of Armco Iron in
Chromate or Nitrite Solutions Occurs (25oC) [12]
Inhibitor, Concentration Critical Concentration

Cl- SO4=
CrO4= 145 ppm 7 ppm 37 ppm
CrO4= 360 ppm 18 ppm 81 ppm
NO2- 33 ppm 127 ppm 14 ppm
NO2- 67 ppm 280 ppm 37 ppm
NO2- 333 ppm >1213 ppm 304 ppm
10-2
There are a few things that should be noted about Table 10-1. First of all, the material used in
these studies was Armco iron6 and not carbon steel. The data are therefore not directly applicable
to carbon steel. In addition, only chromate and nitrite inhibitors are covered. Molybdate-based
inhibitor systems were not part of this study. It is reasonable to expect molybdate-based systems
to behave similarly. What the table shows is that the inhibitors offer reasonable protection from
the effects of chloride and sulfates as long as adequate inhibitor levels are maintained.
The impact of chloride and sulfate on carbon steel in nitrite-treated systems was addressed by
Conoby and Swain [51]. This study concluded that the weight ratio of sodium nitrite to
impurities should be kept above one to avoid attack on carbon steel. In addition, the minimum
inhibitor concentration should exceed the sulfate concentration by 250500 ppm and equal the
chloride concentration at low levels of aggressive ions. This should be given consideration in
those systems that use potable water for makeup.
10.2.3 Operating Conditions
Some CCW systems are characterized by high metal skin temperatures. Reductions in heat
transfer and restrictions in coolant flow from mineral, microbiological, or corrosion deposits
cannot be tolerated in these systems.
The conditions under which the system operates have an impact on selection of the chemical
treatment agents. Normal circumstances demand that treatment components remain active and
effective indefinitely, with supplementary treatment requirements limited to treatment of the
makeup water.
Careful consideration must also be given to low-flow and stagnant-flow conditions. In order for
corrosion inhibitors to protect metal surfaces, there must be sufficient contact between the
inhibitor and the metal surface. This is made more difficult by low- and stagnant-flow
conditions. In these cases, higher inhibitor concentrations might be required than would be
required under normal flow conditions.
Many CCW systems have side loops or redundant loops that are operated infrequently. Some
examples of these are cooling loops for radwaste equipment, heating and cooling systems
(sometimes part of one system), and letdown degassifier coolers. These loops might remain
inactive for weeks to months and will be stagnant at their ambient temperature. The
concentration of inhibitor might change (depending on the inhibitor and length of time apart
from the main loop), but the concentration of contaminants remains constant. In addition, the
amount of suspended corrosion products might increase. Thus, when the side loop is put back
into service, the concentrations for all these parameters will change slightly. Knowing when
these side loops are put into or taken out of service can provide important information to the
chemist when trying to understand changes in inhibitor or contaminant concentrations.
6
American Iron Co., 99.899.9% purity.
10-3
10.2.4 System Conditions
System cleanliness is important for both new construction and older installations. New systems
should be thoroughly cleaned and flushed before use in order to remove debris, mill scale, oil
and grease, and other foreign materials that could interfere with proper application of specific
corrosion inhibitors. With regard to existing systems, the results of previous inspections should
be incorporated into treatment decisions.
Corrosion deposits from various corrosion mechanisms, mineral scales, and foulants such as
biomass, affect changes in piping and heat exchanger performance. Metal loss and reduced heat
transfer might be the most significant, but friction increases and reduced-flow rate capacity are
also important.
The presence of biological deposits is another aspect of system conditions that has an impact on
treatment selection. For example, the presence of biological deposits might limit the use of
nitrite-based corrosion inhibitors because these inhibitors are a nutrient source.
Cleaning methods include in-place chemical cleaning with acids, alkalis, dispersants, solvents,
and chelating or sequestering agents. High-pressure water and various mechanical methods, such
as brushing or scraping, can also be used to clean and restore closed system piping and heat
exchangers to good operating condition.
Program selection should take into account the performance of past inhibitor programs. Expected
plant-life and life extension issues are also factors that should not be overlooked.
Many CCW systems do not have optimum sample locations. Often sampling must be done from
low-point drains. These are usually satisfactory for sampling soluble species. Samples collected
for analysis of insoluble species might not be entirely representative.
10.2.5 Previous Treatment Regime
The selection of chemical treatment for a closed cooling water system must take into account any
previous treatment regime. The nature of the protective film, any deposits, and any residual
treated water remaining in the system, can adversely affect replacement inhibitor performance.
A transition plan is required any time there is a conversion from one program to another. (This is
not limited to CCW systems.) An example is the conversion from a chromate- to a nitrite-based
program. Chromate and nitrite are not compatible, so it is important that the chromate be
thoroughly removed from the system before the nitrite is introduced.
Converting from one type of treatment program to another can also release suspended solids (for
example, corrosion products) into the system. This possibility should be considered and
contingency plans developed to deal with this situation. Either sidestream filtration or feed and
bleed will be required to remove suspended solids. Feed and bleed can significantly increase the
load on radwaste.
10-4
Plants Hatch, Perry, and Surry have experienced significant levels of dissolved solids in CCW
water following conversion from a nitrite to a molybdate program. Waterford 3 converted from
nitrite to molybdate and did not experience any significant problems. Clinton did not experience
any significant problems converting from nitrite to molybdate but had sidestream filtration in
place shortly after the conversion.
10.2.6 Compatibility
Seals, packing, flexible couplings, vibration dampers, expansion joints, piping, hoses, and any
other system components containing materials other than metals might not require chemical
corrosion protection but must be compatible with the treatments to be used to protect the rest of
the system. Fiberglass and plastic pipe of various types are generally impervious to water
treatment chemicals at use levels. These materials could be adversely affected, however, if
exposed to higher concentrations of chemicals often used in pretreatment, cleaning, and initial
passivation procedures. Compatibility of nonmetallics with chemicals is discussed in Section 2
and Table 2-2.
Compatibility of closed cooling water system chemical treatment components is essential. The
compatibility issue must be addressed whenever the inhibitor chemistry is changed and each time
a treatment regime is designed. One area of potential incompatibility that is often overlooked is
the accidental, incidental, or deliberate mixing of two or more systems. Cross-connections are
always a possibility. Incompatibility can become a health and safety issue whenever the
possibility of a cross-connection with a potable or other domestic water system exists. Isolation
techniques or backflow prevention is a prime consideration in these cases.
Incompatibility of treatment and treatment components can result from differences in ionic
charge, oxidation/reduction potential, or general reactivity such as neutralization or adsorption.
pH becomes a factor because most inhibitor components or regimes work best within a specific
pH range. Therefore, chemical treatment ingredients must be compatible with one another and
effective in the same operating environment of pH, temperature, and other characteristics of a
particular system. These characteristics include flow rates, operating cycle, and the presence of
glycol or other antifreeze compounds (glycol and chromate are incompatible).
10.2.7 Impact on Other Plant Systems
The chemicals used in a CCW system can have an impact on other plant systems, especially
radwaste treatment systems. In many cases, this is due to the high ionic loading that can be
placed on radwaste ion exchange systems. There is also the possibility that activation products
will be produced. Many of these effects are discussed in detail in Section 4 for each specific
corrosion inhibitor.
There are other plant systems that might be impacted by CCW systems. These include industrial
waste treatment systems and sewage treatment systems. Industrial waste treatment systems could
be impacted by components such as dispersants and impurities such as iron and copper. Sewage
treatment systems can be impacted by biologically active substances such as biocides and
10-5
chromates. There is also the possibility that leakage might occur from or to primary or secondary
loops in nuclear power plants.
10.2.8 Plant Life Extension Experience and Issues
Plant life extension involves demonstrating adequate management of aging effects on plant
systems and components, as required by 10 CFR 54.21. Closed-cycle cooling water systems are
specifically required to be evaluated in accordance with ID number XI.M21 of NUREG-1801,
Generic Aging Lessons Learned (GALL) Report.
Therefore, maintaining conditions to minimize corrosion and microbiological growth in CCW

systems is essential for effectively mitigating many aging effects. Several plants have met this
requirement by ensuring that their CCW chemistry programs were aligned with Revision 0 of the
EPRI Closed Cooling Water Chemistry Guideline (TR-107396).
For those systems not in compliance with the guidelines, comprehensive justifications need to be
incorporated into the stations site-specific CCW chemistry program.
10.3 Environmental Impact and Health Effects
All chemicals have potential health effects. These effects must be considered as part of an overall
chemical handling program. Environmental impact considerations are also an important part of
program selection; however, they are not the only consideration. If chromates are to be used in
CCW systems, it is especially important that system leaks are minimized and plans are made for
the containment and handling of CCW system water during equipment repair. Water drained
from systems treated with nitrite or molybdate should not be reused in the system unless steps
are taken to eliminate biological effects. Reusing water that has been drained from the system
increases the potential for biological contamination.
10.4 Nonchemical Treatment Considerations
These considerations include pure demineralized water systems and mechanical treatment
methods such as sidestream filters and/or demineralizers. Pure water systems were discussed in
Sections 4 and 5. Sidestream filters and demineralizers can be effective for removing suspended
and dissolved solids from the CCW water and preventing deposition.
10-6
11
REFERENCES
1. Nuclear Energy Institute (NEI). Steam Generator Program Guidelines, Document 97-06,
Rev. 1 (January 2001).
2. Chromate Substitutes for Corrosion Inhibitors in Cooling Systems. EPRI, Palo Alto, CA:
1987. NP-5569.
3. Service Water System Chemical Addition Guideline. EPRI, Palo Alto, CA: 1996. TR-106229.
4. Generator Cooling System Operating Guidelines: Cooling System Maintenance and

Performance Guidelines During Start-Up, Operation, and Shutdown. EPRI, Palo Alto, CA:
2001. 1004004.
5. Fundamentals, The Handbook CD, American Society of Heating, Refrigeration and Air-
Conditioning Engineers (ASHRAE), Atlanta, GA, 2001.
6. The NALCO Water Handbook. McGraw Hill, New York, NY, 1988, p. 38.10.
7. Corrosion Basics. NACE International, Houston, TX (1984).
8. H. H. Uhlig. Corrosion and Corrosion Control. John Wiley & Sons, 1985, p. 265.
9. Butler & Ison. Corrosion and Its Prevention in Waters. Reinhold Publishing Corp., New
York, NY 1966, p. 165.
10. Investigation of the Effects of Corrosion-Inhibiting Treatment on Mechanical Seals in

Recirculating Hot Water Systems, NACE International, Houston, TX. 7G181.
11. PMC Specialties Group Bulletin CORTT-7565-PH, Effect of pH on the Effectiveness of

COBRATEC TT-100 in Preventing Copper Corrosion.
13. Corrosion Handbook, ASM International, Materials Park, OH.
14. OE 7031, Stress Corrosion Cracking in Closed Loop Component.
15. Molybdate: The Versatile Inhibitor, Paper 444, Corrosion 89, National Association of
Corrosion Engineers International (1989).
16. M. J. Pryor and M. Cohen, J. Electrochemical Society, Vol. 100, p. 203 (1953).
11-1
References
17. R. May, G. E. Betz, private communication.
18. H. H. Uhlig and P. F. King, J. Electrochemical Society, Vol. 106, p. 1 (1959).
19. W. D. Robertson, J. Electrochemical Society, Vol. 98, p. 94 (1951).
20. G. H. Cartledge, Corrosion, Vol. 24, p. 223 (1968).
21. M. Meziane, F. Kermiche, C. Flaud, Effect of Molybdate Ions as Corrosion Inhibitors of

Iron in Neutral Aqueous Solutions, British Corrosion Journal. Vol. 33, No. 4 (1998).
22. F. A. Cotton and G. W. Wilkinson. Advanced Inorganic Chemistry: A Comprehensive Text.

Wiley Interscience Publishers, 1966.
23. C. M. Mustafa, S. M. Shahinoor, and I. Dulal, British Corrosion Journal. Volume 32, No. 2,
p. 133 (1997).
24. Technical Information Report No. 10-298, Oxidation and Degradation Products of Common
Oxygen Scavengers, Calgon Corporation, Pittsburgh, PA.
25. Corrosion Inhibitors, National Association of Corrosion Engineers, Houston, TX (1973).
27. Drew Principles of Industrial Water Treatment, Drew Industrial Division, Ashland Chemical
Company, p.66 (1985).
28. E-Mail communication, Bruce Strickland, PMC Specialties, June 11, 2003.
29. E-Mail communication, Bruce Strickland, PMC Specialties, June 12, 2003.
30. United States Nuclear Regulatory Commission. IE Circular No. 80-11, May 1980.
31. Moccari, Corrosion Inhibitor Evaluation for Materials Used in Closed Cooling Systems,
Materials Performance, p. 54, September 1999.
32. Holm, et al., Surface Analytical Investigation of Triazole Inhibitor Layers on Brass,
Proceedings of the International Water Conference, p. 70 (1991).
33. Personal communication between S. Mathis and R. Litman and visit to Millstone III (1999).
34. J. S. Lee, R. I. Ray, K. L. Lowe, J. Jones-Meehan, and B. J Little, An Evaluation of

Microbial Growth and Corrosion of 316L SS in Glycol/Seawater Mixtures, Biofouling. Vol
19 (Supplement), pp 151160 (2003).
35. Dow Chemical Company, HVAC Focus, Winter 2001.
36. American Society for Testing and Materials. 2001 Annual Book of ASTM Standards,
Designation: D 4985-00a, Standard Specification for Low Silicate Ethylene Glycol Base
11-2
References
Engine Coolant for Heavy Duty Engines Requiring a Pre-Charge of Supplemental Coolant
Additive (SCA), Volume 15.05.
Designation: D 1287-91 (Reapproved 1997), Standard Test Method for pH of Engine
Coolants and Antirusts, Volume 15.05.
38. R. G. Eagar and A.B. Their, Control of Microbiological Fouling with Glutaraldehyde,
Technical Paper TP 87-1, Cooling Tower Institute Annual Meeting (1987).
39. J. W. McCoy. The Chemical Treatment of Cooling Water. Chemical Publishing Company,
New York, NY 1974, p. 89.
40. The NALCO Water Handbook. McGraw Hill, New York, NY, 1988, p. 22.15.
41. OE 15981.
Designation: D 1121-98, Standard Test Method for Reserve Alkalinity of Engine Coolants
and Anitrusts, Volume 15.05.
Designation D 2688-94 (Reapproved 1999), Standard Test Methods for Corrosivity of
Water in the Absence of Heat Transfer (Weight Loss Methods), Volume 11.01.
Designation G 96-90 (Reapproved 1996), Standard Guide for On-Line Monitoring of
Corrosion in Plant Equipment (Electrical and Electrochemical Methods), Volume 03.02.
45. K. A. Selby and D. W. Townley, Corrosion Rate Monitoring in Power Plant Systems:
Methodology and Applications, EPRI Service Water Reliability Improvement Seminar
(July 2000).
46. J. W. Mc Coy. Microbiology of Cooling Water. Chemical Publishing Company, New York,
NY 1980, p. 117.
47. American Public Health Association. 9215 Heterotrophic Plate Count, Standard Methods for
the Examination of Water and Wastewater, 18th Edition, p. 9-32 (1992).
48. 3M Company, Minneapolis, MN.
49. Service Water System Corrosion and Deposition Sourcebook. EPRI, Palo Alto, CA: 1993.
TR-103403.
50. Guide for the Examination of Service Water System Piping. EPRI, Palo Alto, CA: 1994.
TR-102063.
51. J. F. Conoby and T. M. Swain, Materials Protection. Vol. 6, No. 4, p. 55 (1967).
11-3
A
POSITION PAPER ON IMPURITY CONCENTRATION
LIMITS FOR CLOSED COOLING WATER SYSTEMS
A.1 Executive Summary
This position paper pertains to auxiliary closed cooling water (CCW) systems in nuclear power
plants. Examples are component cooling systems, emergency diesel generator jackets, enclosure
coolers, and lubricating oil coolers. The water used in these systems is of very high quality,
typically deionized water or condensate. Nuclear Steam Supply System (NSSS) suppliers
provide specifications concerning allowable impurity limits for the CCW water. However, the
current impurity limits are inconsistent among the NSSS suppliers and, in some cases, are
unrealistically conservative. (Chloride and fluoride limits vary from 10 ppm to 150 ppb.) This
paper establishes the basis for new limits that will assure protection of CCW system materials
but, at the same time, will be reasonable and achievable. Data and experience were gleaned from
a number of recognized industry leaders in the fields of metallurgy and corrosion. Only stainless
steel degradation is addressed, and primarily stress corrosion cracking (SCC) of stainless steel.
The following impurity limits are recommended: *

Table A-1
Recommended CCW Impurity Limits
Impurity Degradation Mechanism Proposed Upper Limit

Chloride Stainless Steel Stress Corrosion 10 ppm @ < 180 F
Cracking (SCC)
Fluoride Stainless Steel Stress Corrosion 10 ppm @ < 180 F
Cracking
* Providing that these additional criteria are also met:
-- Material stresses are kept below 90% of the yield strength.
-- Dissolved oxygen is kept below 8 ppm.
-- pH is kept greater than 7.
SCC is much more likely in vertical exchangers than in horizontal exchangers. This is due to
evaporation and increasing temperatures in the vapor zone, below the top tube sheet. The CCW
system heat exchangers under consideration, however, are normally horizontal and are not prone
to this failure mode (Ref. 1).
A-1
Position Paper on Impurity Concentration Limits for Closed Cooling Water Systems
To avoid sediment buildup in the bottom of exchangers, periodic flushing is recommended and
filtration is beneficial. Also the use of chlorinated solvents should be prohibited.
While it is not possible to be 100% certain that SCC failures will not occur in the CCW systems,
the above impurity levels are conservative and represent a very low, acceptable risk.
A.2 Introduction
Nuclear power plants in the United States are supplied by four nuclear steam supply system
(NSSS) vendors. These are Babcock & Wilcox, Combustion Engineering, General Electric and
Westinghouse. Each of these vendors has a different overall plant design, however, the auxiliary
closed cooling water (CCW) systems and their materials of construction, are similar. The CCW
systems under consideration are distinct from the primary system and include component cooling
systems, emergency diesel generator jackets, enclosure coolers, and lubricating oil coolers. The
water used in these systems is of very high quality, typically deionized water or condensate. The
materials of construction cover a wide range of alloys from low carbon steel to stainless steel.
This paper pertains only to stainless steel and considers, primarily, degradation by stress
corrosion cracking (SCC). Chloride and fluoride ions are known to cause SCC. A good practice
is to keep them as low as possible to avoid failures. The current impurity limits for these halides,
set by the NSSS vendors are, however, inconsistent and, in some cases, are unreasonably low.
The goal of this paper is to establish chloride and fluoride limits that will assure the protection of
system materials, but at the same time, be reasonable and achievable.
A.2.1 Current Impurity Limits
Nuclear Steam Supply System (NSSS) vendors provide specifications and guidelines concerning
impurity concentration limits for specific closed cooling water systems of nuclear power plants.
The current specifications for chloride and fluoride impurity concentrations in the Component
Cooling Loop of the Auxiliary Coolant System are shown in the Table A-2.
Table A-2
Impurity Concentration Levels Allowed by NSSS Vendors
Westinghouse General Electric Combustion Babcock &

Engineering Wilcox
PWR BWR PWR PWR
Chloride 150 ppb 10 ppm 1 ppm 1 ppm
Fluoride 150 ppb (none provided) (1 ppm total for all 1 ppm
halides)
A-2
A.2.2 Role of Water Quality in SCC
There is abundant evidence in the literature that chloride and fluoride play a primary role in
causing SCC in stainless steel materials. Other factors, however, such as stress, temperature, pH
and oxygen level, are also important. Maintaining an effective chemistry control program in an
operating CCW system will reduce the chance of SCC.
A.3 Technical Position
SCC is a complex phenomenon that is affected by several factors in addition to chloride/fluoride.

A tensile stress is required. Dissolved oxygen and temperature are very important. As the oxygen
level and temperature decrease, the tendency for SCC decreases. Except for very alkaline
conditions (caustic solutions), the probability of SCC decreases as the pH increases. In CCW
systems, many of these factors are such that the probability of SCC is low. This is discussed
below and references are provided.
A.3.1 Factors Affecting SCC of Stainless Steel Materials
Under nuclear power plant CCW conditions of operation, SCC of Type 304 and 316 Stainless
Steel is influenced by many interrelated factors. These factors include:
Metal alloy composition
Temperature
Stress Levels
Chloride concentration
Component surface conditions
pH
Oxygen
Other ionic species (such as sulfate, fluoride)
Microorganisms
Corrosion inhibitors/chemical additives
The parameters that are controlled in a CCW system include pH, microorganisms, ionic
contaminants, and inhibitors. The pH in the CCW system water is controlled by the use of
chemical additives. Chemicals such as chromate, nitrite or molybdate (carbon steel corrosion
control) and azoles (copper alloy corrosion control) are added to reduce corrosion in the systems.
Biocides are added as needed to reduce microbe populations. Monitoring of other parameters
(that is, chloride, fluoride, sulfate), and heat exchanger performance, when possible, and taking
prompt corrective actions when necessary, will provide assurance that detrimental corrosion is
mitigated.
A-3
Stress. CCW systems are designed such that stress levels do not exceed 33 % of material yield
strength. CCW system components will not exceed 90 % material yield strength even under
accident conditions of operation.
By establishing and maintaining a CCW system chemistry control program, there can be
reasonable assurance that corrosion and SCC are under control in the CCW system components.
It has been documented (Ref. 2,3,4) that with chloride concentration levels maintained below
200 ppm, SCC is not a major concern. Documented data also indicates that for an alkaline range
(pH > 7.0), SCC is minimized (Ref. 6). Chemical additives, such as nitrite, molybdate, chromate,
etc., provide a corrosion boundary for carbon steel to enhance the CCW components resistance
to corrosion. Operating temperatures and component surface temperatures in the CCW for the
majority of the system are <180F. SCC is minimized at these temperatures.
Although some references indicate that fluoride concentrations in the CCW water are not
detrimental to system components and will not cause significant corrosion or SCC. (Ref. 9),
fluoride is considered a stainless steel corrodent for purposes of this document. For pure water
CCW systems (BWR), soluble impurity concentrations are limited and controlled by the CCW
water-conductivity limit. The GE specification for conductivity of a pure water CCW system is
3.0 S/cm.
The GE specification for chloride concentration limit in a nitrite corrosion inhibitor solution is
<10 ppm.(Ref. 10)
Sensitization. Sensitization is a state of reduced corrosion resistance of austenitic stainless steels

caused by a depletion of chromium in the grain boundary area. It occurs when high carbon
containing stainless steels (~.08%C) are heated in the temperature range 950-1450F. It is often
observed after welding, in the heat- affected zone. Sensitized stainless steel is very susceptible to
intergranular corrosion and SCC. Intergranular SCC of sensitized Type 304 stainless steel has
been observed in the laboratory in pure water with 1-2 ppm oxygen in the temperature range 122
- 212F (Ref. 6). However, sensitization can be avoided if low carbon grades of stainless steel
(~.03%C) are used, for example, Types 304L and 316L. It is expected that these low carbon
grades will be in place in the CCW systems under consideration and, hence, sensitization will not
be an issue.
A.3.2 Failure Modes with Stainless Steel System Materials
SCC of Stainless Steel Tubing in Heat Exchangers
The closed cooling water system heat exchangers in nuclear power plants are normally
horizontal with the cooling water on the outside of the tubes. Experience indicates that there are
three distinct failure modes of tubing when cooling water is on the shell side and that these are
influenced by the metallurgy in use. The three failure modes are:
Underdeposit-pitting corrosion and crevice corrosion and/or microbiological influenced

corrosion (MIC) of the lower tubes due to crud buildup in the bottom of the exchanger
A-4
Mechanism: The flow around the baffles on the shell side tends to deposit sediment and
entrained matter in the cooling water in the bottom of the heat exchanger, often to the extent that
the lower tubes are covered. Under deposit pitting/crevice corrosion and/or MIC, are common
failure modes for Type 304 and Type 316 stainless steel and copper alloy tubes, covered by
sediment/crud in such heat exchangers. Highly alloyed stainless steel tubing (that is, 6%
molybdenum) is resistant.
Crevice corrosion of stainless steel tubes at stainless steel tubesheets, from the shell side
Mechanism: The tube to tubesheet crevice is a tight stationary crevice where crevice corrosion is
likely for Type 304 tubes, in Type 304 tubesheets, in waters with > 150-200 ppm chlorides. It is
also likely for Type 316 tubes, in Type 316 tubesheets, in water with > 1000 ppm chlorides. For
these alloys in clad tubesheets, the carbon steel under the cladding is galvanically protective to
stainless steel and prevents crevice corrosion, even when the chloride concentration exceeds the
150-200 ppm limits for Type 304, and the 1000 ppm limits for Type 316. For copper alloy
metallurgy, crevice corrosion in solid or clad tubesheet-to- tube crevices is not a problem.
Stress corrosion cracking of stainless steel tubes in stainless steel tubesheets
Mechanism: SCC is a location-specific failure mode. The residual stresses from rolling the tubes
into the tubesheet are high enough for SCC to occur. Eight (8) ppm of oxygen is adequate. If
chlorides were able to reach critical concentrations in the crevice, SCC might occur.
To avoid SCC, the following limits are proposed: chlorides < 10 ppm, tube inlet temperatures <
180F, oxygen < 8 ppm, pH > 7, and residual stress < 90% of yield.
Chloride Ion Concentration in the Crevice
Evaporation from hot surfaces is a leading mechanism for concentrating chlorides and initiating
SCC. Stainless steel tubes in vertical heat exchangers, used in the chemical industry, suffer SCC
in the vapor pocket just below the top tubesheet. Stainless steel downcomer piping suffers SCC
just above the liquid level. Insulated stainless steel piping has suffered SCC when wet by rain or
overhead leaks that filter through the insulation and evaporate from the hot surface. Time is a
major factor. In many cases, 3 to 7 years are required for initiation of SCC from chloride
concentration on hot surfaces. The higher the chlorides in the water or moisture evaporated from
hot surfaces, the shorter is the time for initiation of SCC. There are no well accepted
mathematically certain guidelines.
SCC has been encountered in vertical heat exchangers, in waters with as low as 14-ppm
chlorides, although it took seven years for the SCC to occur (Reference 8).
However, in horizontal heat exchangers, with water on the shell side, the tubes are covered and
there is no hot wall to evaporate water and concentrate chlorides. The literature mentions
possible chloride ion concentration in crevices by occlusion and other mechanisms, so
concentration by other than evaporation cannot be ruled out. Experience, however, suggests that
the proposed 10 ppm chloride upper limit for Type 304 or Type 316 tubes in solid tubesheets, in
A-5
horizontal heat exchangers with cooling water on the shell side, would be ultraconservative for
both SCC and crevice corrosion.
Experience also suggests that it would be wise to include a prohibition against the use of carbon
tetrachloride and other chlorinated solvents in degreasing after tube rolling operation. Use of
chlorinated solvent degreasers has resulted in SCC failures of heat exchangers when placed in
service.
For clad stainless steel tubesheets, the carbon steel would protect stainless steel from SCC as
well as from crevice corrosion. SCC is not a problem with copper alloy tube and tubesheets.
Summary
The proposed guidelines should include recommendations that:

Periodic flushing out of sediment that collects in the bottom of such units is recommended.
Well-maintained filters in closed cooling water systems are beneficial.
The use of chlorinated solvents for degreasing after tube rolling operations be prohibited.
For Type 304 tubes in solid stainless steel tube sheets, and Type 316 tubes in solid stainless
steel tubesheets, the proposed 10-ppm chloride limit is believed to be ultraconservative
insofar as prevention of SCC and crevice corrosion is concerned.
For clad tube sheets, for more highly alloyed stainless steel tubes, and for copper alloy
metallurgy, much higher chloride ion concentrations could certainly be tolerated.
A.4 Side Effects or Risks
Recommendations in this document are based on sound information and judgment. If the
recommendations are followed, the likelihood of SCC is very small. Even if SCC were to occur,
there are factors that still keep the risk of unexpected and damaging failures at a safe level. First,
under the closed system conditions discussed here, SCC requires a long initiation time and
proceeds very slowly. This will allow an inspection program to uncover the presence of cracking
before failures occur. Secondly, it is very unlikely that the primary system will be contaminated
via a failure in the closed cooling water system.
A.5 Strategy
This position paper provides materials, corrosion, and chemistry control data, to support
increasing the limits for closed cooling water impurity (Chloride and Fluoride) concentrations.
The operating conditions (Stress and Temperature) of the Component Cooling Water and
Emergency Diesel Jacket Cooling Water Systems are considered the most detrimental for the
systems materials of construction, corrosion control, and water chemistry control. The strategy
is that, when operating each plants closed cooling water systems with an appropriate chemistry
control program, the system materials of construction are provided with protection (that is,
corrosion is under control and SCC is minimized). This provides an assurance of system and
A-6
component integrity and reliability. The other auxiliary systems should receive adequate
protection also, since they operate with less stress, lower temperature, and less detrimental
conditions.
A.6 Recommendations
The impurity limits for CCW system water chemistry should be established at 10 ppm for
chloride and 10 ppm for fluoride. The current chloride and fluoride limits can be increased
from 0.150 ppm (W) and 1.0 ppm (B&W) to 10 ppm, based on information from ASM and
NACE documents (referenced in Section A.7)
Periodic flushing is recommended to avoid sediment buildup in the bottom of exchangers.
Well-maintained filters are beneficial (cost/benefit evaluation will be needed to support any
system modifications).
It is recommended that the use of chlorinated solvents for degreasing or other cleaning of
CCW components be prohibited.
A.7 References
1. Shell and Tube Heat Exchangers, A Symposium on Shell and Tube Heat Exchangers.
Materials/Metalworking Technology Series AMERICAN SOCIETY FOR METALS, 1981
2. Metals Handbook Ninth Edition, Volume 11, Failure Analysis and Prevention. Prepared
under the direction of the ASM Handbook Committee, 1985
3. Metals Handbook, Volume 1, Tenth Edition, Properties and Selection: Irons, Steels, and
High Performance Alloys. ASM international, 1989
4. Handbook of Corrosion Data. ASM International, 1989
5. Critical Temperatures for Chloride Stress Corrosion Cracking of Type 300 Stainless Steel, C.
P. Dillon, Materials Performance, December 1996
6. G. Cragnolino and D. D. MacDonald, Intergranular Stress Corrosion Cracking of Austenitic

Stainless Steel at Temperatures Below 100oC, A Review, NACE, Corrosion 38. Vol. 38,
No. 8 (1982).
7. Stress Corrosion Cracking of Sensitized Type 304 Stainless Steel in Oxygenated Pure Water
at Elevated Temperatures (Review), S. Szlarska-Smialowska and G. Cragnolino, Corrosion-
NACE Vol. 36, No. 12, December, 1980
8. Arthur H. Tuthill, P.E., correspondence to Tim Eckert, EPRI, Dec. 23, 1996
9. Localized Corrosion in Halides Other than Chlorides, Materials Performance, June 1993
10. General Electric Chemical and Radiochemical Specifications
A-7
B
CHEMISTRY-RELATED PROBLEMS IN CLOSED
COOLING WATER SYSTEMS
B.1 Corrosion Mechanisms
In the discussion that follows, it is assumed that the reader has a basic familiarity with the
corrosion process, including an understanding of the corrosion cell, galvanic series, and so on. It
is also assumed that the reader has a basic understanding of microbiologically influenced
corrosion (MIC). There are numerous references available for those readers who are interested in
obtaining additional information. The discussion that follows is directed toward the specific
types of corrosion most pertinent to closed cooling systems.
B.1.1 General Corrosion
General corrosion refers to a more or less uniform loss of metal from the surface of the metal
exposed to the corrodent (in this case, closed cooling water). Anodic and cathodic areas are not
fixed; therefore, any location can act as an anodic area at one moment and a cathodic area the
next. This shifting of anodic and cathodic areas results in uniform loss of metal over the entire
surface. Piping systems are designed with an allowance for general corrosion.
B.1.2 Localized Corrosion
Localized corrosion results when metal wastage is concentrated in a relatively small area. It is
promoted by a separation between the cathodic and anodic areas. The metal loss forms a
penetration rather than general thinning. It is, therefore, much more likely to cause an
unexpected metal failure than is general corrosion.
Pitting Corrosion
Pitting is defined as localized corrosion where the depth is greater than the diameter of the
affected area. Pitting is usually observed when the passive film breaks down on corrosion-
resistant alloys. Pits can grow and then become inactive, or they might continue to propagate all
the way to through-wall penetration.
Pitting corrosion is an autocatalytic process. Once a pit is formed, the environment inside the pit
becomes much more aggressive than the bulk water. Chloride ions are attracted to the pit by
positively charged metal ions. The metal chloride solution reacts with water to produce
B-1
Chemistry-Related Problems in Closed Cooling Water Systems
hydrochloric acid, which is much more corrosive than the bulk water. The insoluble corrosion
products build up and isolate the pit from the bulk water even more.
The presence of copper ions in the water can also lead to pitting. The copper ion can plate out on
a steel surface as copper metal. This sets up a localized galvanic cell and forms a pit.
Crevice Corrosion
Crevice corrosion is a broad term that encompasses at least three specific types of corrosion:
Oxygen concentration cells
Ion concentration cells
Underdeposit corrosion
In crevice corrosion, the diameter of the affected area is greater than the depth. Typical situations
in which crevice corrosion occurs are underneath deposits or underneath components, such as
weld backing rings. In each of these types of corrosion, the separation of anodic and cathodic
areas critical to localized corrosion is provided by a geometric discontinuity. This separation
keeps the solution inside the crevice stagnant, which sets up a difference in ionic and oxygen
concentration between the solution in the crevice and the bulk water. Once the area within the
crevice becomes anodic, the same basic mechanisms described for pitting become active.
Stress Corrosion Cracking (SCC)
A metal becomes susceptible to SCC when it is simultaneously put under tensile stress and
exposed to a corrosive environment. The required stress is generally 50% or more of the yield
strength, although some material-environmental pairs might crack at much lower stresses.
Corrosion texts contain lists of materials and environments where SCC has occurred, and the
lists are constantly expanding as previously unexplained failures are attributed to SCC. The two
most common SCC-susceptible material-environment pairs used in cooling systems are stainless
steels exposed to waters high in chloride and some copper alloys exposed to ammonia.
Galvanic Corrosion
When two dissimilar metals are connected and exposed to a water solution, the less noble metal
becomes anodic and the other cathodic, to set up what is termed a galvanic corrosion cell. The
anode deteriorates rapidly, while the cathode is given greater corrosion resistance than it
normally would have as a result of the electron transfer. If the anodic area is relatively large
compared to the cathodic area, the rate of corrosion will be low. With a small cathode, the
overall reaction is limited by the number of electrons that can be accepted at the cathode.
The opposite situation (large cathodic area and small anodic area) results in rapid dissolution of
the anode. In this case, the large cathodic area readily accepts all available electrons from the
anodic area.
B-2
Manganese deposits can also play a part in galvanic corrosion. This is characterized by pitting
attack underneath the manganese deposits.
Microbiologically Influenced or Induced Corrosion (MIC)
Microbiologically Influenced or Induced Corrosion is one of the main problems in closed

cooling water systems. The mechanisms for MIC are discussed in Section B.3.
Flow-Accelerated Corrosion (FAC)
Flow-Accelerated Corrosion or FAC (sometimes referred to as erosion-corrosion) exacerbates

the general corrosion phenomenon. FAC is the removal of corrosion product films by the action
of the environment. In CCW systems, this is most often caused by water velocity and
impingement. It is usually a localized form of corrosion because it depends on the geometry of
the system to direct water flow. Bends in pipes, elbows, tees, pump impellers, and valves are
especially susceptible.
Removing the corrosion product film greatly increases the corrosion rate above what it would be
without erosion. On the other hand, erosion would not be as significant without corrosion taking
place.
Carbon steels and copper alloys are susceptible to flow-accelerated corrosion. The addition of a
half percent or more of chromium to carbon steel, increases its resistance to attack. Under closed
cooling water system conditions, stainless steels are virtually immune to the problem.
If FAC is a suspected mechanism in high-flow areas of CCW systems, the EPRI

CHECWORKS software [1] can be used to assess the corrosion observed.
Erosion
Erosion and FAC are two separate mechanisms. Erosion is strictly mechanical interaction with a
metal. The erosion phenomenon that is most often a problem is inlet end tube erosion in heat
exchangers.
Copper alloy heat exchanger tubes are often subjected to erosion conditions, especially at the
inlet end where the turbulence is greatest. Tube blockages can create high fluid velocities and
impingement on the tube wall, which will remove protective films quickly. Some suggested
maximum velocities are shown in Table B-1. Although these velocities are for condenser tube
alloys in seawater, the data should also generally apply to other types of heat exchangers and
other types of waters.
B-3
Table B-1
Suggested Critical Velocity Limits for Condenser Tube Alloys in Sea Water [2]
Material Recommended Maximum Velocity

Feet/Second Meters/Second
Copper 3 0.9
Admiralty brass 5 1.5
Aluminum brass 8 2.4
90-10 copper nickel 10 3.0
70-30 copper nickel 12 3.7
Type 316 stainless steel No maximum velocity limit
Titanium No maximum velocity limit
B.2 Impact of Corrosion
B.2.1 Failures
Corrosion in closed cooling systems will eventually lead to failures, most likely to take the form
of through-wall penetration. If this occurs, the system is no longer closed, and the water that
leaks out of the system must be replaced along with any treatment chemicals. The cost of
replacing water and treatment chemicals can become excessive. In extreme cases, a critical piece
of equipment might be lost, bringing about an unscheduled outage.
B.2.2 Fouling
Active corrosion within a closed cooling water system can be of significant consequence long
before actual failures occur due to the generation of corrosion products. These corrosion products
cannot easily be blown-down as in an open cooling water system. Unless a cleanup program is
undertaken, the corrosion products that are generated within the closed cooling water system
remain in the system. When they accumulate on heat transfer surfaces, a loss of efficiency will
result. Accumulations in low-flow or stagnant areas of the system can become breeding grounds
for deleterious bacteria that can contribute to MIC.
The formation of deposit tubercles has a secondary damaging effect. The tubercles become a site
for localized underdeposit corrosion.
B-4
B.3 Microbiological Organisms
Microbiological organisms will be found in virtually all closed cooling water systems. If not
controlled, these organisms can cause both corrosion and fouling of equipment in the system.
Microorganisms are usually classified according to their ability to grow in the presence or
absence of oxygen. Organisms that require oxygen in their metabolic processes are termed
aerobic, and those that require oxygen-free environments are termed anaerobic.
Microorganisms are also classified according to whether they are free-floating in the bulk water
(planktonic bacteria) or are attached to component surfaces (sessile bacteria). Sessile bacteria are
part of slime masses. These are of much more concern in cooling systems than are planktonic
bacteria. Growth of sessile organisms can contribute to fouling through the accumulation of
slime masses. Metal-oxidizing bacteria such as Gallionella sp. also contribute to severe fouling
by producing tubercles (nodules) on carbon steel pipe ID surfaces. Tubercles can literally plug
the pipe completely and stop flow. Tubercles are composed of ferric hydroxide/oxide formed as
a result of oxidation of the ferrous metal by the metabolism of metal-oxidizing bacteria. Slime
masses and tubercles can indirectly contribute to corrosion by providing sites for underdeposit
corrosion.
Although one would tend to perceive closed systems as being depleted in oxygen, this is not
necessarily the case. Oxygen can enter with makeup water as well as other sources. Many
systems require significant quantities of makeup water due to the loss of water from leaks. Also,
many closed systems use tanks that are open to the atmosphere and/or have in-leakage of air at
seals.
B.3.1 Nitrogen Biogeochemical Cycle
Nitrogen is uniquely positioned in natures biogeochemical cycle of elements because there are
so many microorganisms that have the ability to alter forms of nitrogen. The existence of life has
an absolute need for the many end products of nitrogen metabolism by microorganisms;
however, there are many problems that also result. A major problem occurs when denitrifying
bacteria remove fertilizing nitrates from the soil. Another problem occurs where nitrite is used as
a corrosion inhibitor and microorganisms convert it to nitrate. Undesirable transformations occur
in natural and man-made environments, for example, waste treatment processes producing
unpleasant odors, corrosive gases, and pH modifications. Many products of nitrogen
transformations are very corrosive to metals and concrete. All of these are of interest. The
following steps provide a summary of these microorganisms and the transformations they have
the ability to perform.
Step 1. Fixation of Molecular Nitrogen
The natural reservoir for the N2 in our environment is the atmosphere. No substantial amounts
are found in geological deposits. Atmospheric N2 is not readily available to biological systems,
and is accessible to the biological ecosystem only through the process of nitrogen fixation.
B-5
Nitrogen fixation is a process that requires a substantial amount of energy input. Small amounts
of combined nitrogen are introduced to the ecosphere by volcanic activity, by atmospheric
lightning discharges, and ionizing radiation. Chemical fixation of molecular N2 by man (Haber-
Bosch synthesis) is limited but assuming an increasingly important role in the global nitrogen
cycle.
The primary mechanism of biogeochemical cycling of the element N is highly dependent on the
activities of microorganisms. The first step involves nitrogen fixation by a very specific group of
bacteria, usually found in soil environments (rhizosphere) or in aquatic environments (fresh or
seawater). These bacteria include Rhizobium sp. (which accounts for the largest contribution of
combined N2) in terrestrial habitats. In aquatic habitats, cyanobacteria (blue-green algae) such as
Anabena sp. and Nostoc sp. are the most important in nitrogen fixation processes.
Step 2. Ammonification
The first biologically active compound resulting from N2 fixation is the formation of organic
nitrogen (NH2), which is immediately converted to NH3 and incorporated into amino acids and
other nitrogen-containing biochemicals, usually essential to microbiological metabolism and
subsequently to the metabolism of higher life forms. Many microorganisms, plants, and animals
are capable of ammonification through the reaction:
2(NH2) + CO + H2O + urease enzyme system 2NH3 + CO2
The incorporated amino group can be transferred through transamination to form other amino
acids, proteins, and other nitrogen-containing compounds by one group of organisms, and is
subsequently used as sources of carbon, nitrogen, for synthesis and energy by other groups of
organisms.
Free ammonia in solution, or as a gas, will exist as a byproduct of this process. The amount
depends on the ability of the environment to contain or trap the ammonia. When the environment
is favorable for containment, many of the potential problems mentioned earlier can take place.
Step 3. Nitrification/Nitrosification
Nitrification is a process performed by autotrophic/chemolithotrophic bacteria that utilize nitrite

(NO2) or ammonia (nitrosification) as an energy source, and CO2 as the primary carbon source.
The reaction is:
Nitrite-oxidizing bacteria (nitrifying) NO2 + O2 NO3-

Nitrobacter sp. (also heterotrophic)
Nitrospina sp.
Nitrococcus sp.
Nitrospira sp.
B-6
Both nitrite- and ammonia-oxidizing groups are frequently called nitrifying bacteria. These
microorganisms live in a wide range of environments and often show a tendency to attach to
surfaces (sessile) forming tight clusters of cells commonly called cysts, and some produce
biofilm. They are aerobic or micro-aerophilic bacteria.
Ammonia-Oxidizing Bacteria (nitrosifying bacteria)
Ammonia-oxidizing bacteria in contained environments (for example, CCW systems with

minimal amounts of O2) can produce either alkaline or acidic byproducts that contribute to
increased potential for MIC, especially with the corrosion of non-ferrous metals such as copper
alloys.
Nitrosomonas sp.
NH3 + O2 HNO3 Acidic byproducts
Nitrosovibrio sp.
Nitrosococcus sp. NH3 (low O2) NO2 Neutral/weak acidic byproducts
Nitrosomonas sp.
Nitrosopira sp. NH3 + O2 NO/NH2OH Alkaline byproducts
Nitrosolobus sp.
Step 4. Nitrate Reduction/Denitrification
This process includes at least three different metabolic pathways. The microorganisms that are
involved with these reactions are chemosynthetic/heterotrophic (require an organic energy
source). They are diversified by the characteristic that some are aerobic, micro-aerophilic,
facultatively anaerobic, or anaerobic and, thus, have optional metabolism pathways. The
metabolic pathways are defined by the chemical metabolites produced. Microorganisms often
associated with MIC assimilate nitrate nitrogen to organic nitrogen/ammonia. These include
(those in bold print are significant contributors to MIC):
Aeromonas sp. Edwardsiella sp.
Arthrobacter sp. Clostridium sp.
Enterobacter sp. Escherichia sp.
Thiobacillus sp. Pseudomonas sp.
B-7
Assimilation of Nitrate Nitrogen
A metabolic pathway is: Bacteria NO3 + metalloprotein/reduced cofactors/catalysts NO2

NO intermediates (?) NH2OH NH3 amino acids proteins/ATP microbiological
metabolism.
This pathway is always associated with a significant increase in the amount of biomass produced
and might result in biofouling problems. This pathway is also very common with metabolism of
yeast, fungi, and all higher plants.
Dissimilation of Nitrate Nitrogen
A metabolic pathway is: Bacteria NO3 + reductase enzyme catalyzed reduction NO2 ?
and possibly ammonification.
This is a pathway that can occur under both aerobic and anaerobic conditions. It is an alternative
pathway to O2 respiration for some microorganisms. In most cases, this process is associated
with an increase in NO2 concentration, often NH3, and biomass. Although not directly involved
with corrosion, the metabolic pathway increases the potential for MIC. Typical microflora
include:
Aeromonas sp. Enterobacter sp.
Arthrobacter sp. Eschericia sp.
Bacillus sp. Micrococcus sp.
Citrobacter sp. Nocardia sp.
Denitrifying Bacteria
These microorganisms are responsible for the actual removal of nitrogen compounds, as such,
from the microenvironment. The byproducts of this metabolic pathway are usually metabolites
for other pathways or a release of gas that contributes to gassing problems in closed loop cooling
systems. The process is essentially an anaerobic function at a site with excessive deposition of
nitrate sludge and other organic biomass, usually in a system where nitrite oxidation by
microorganisms had occurred for an extended time. The gassing problem can be justification for
bleed and feed or flush and fill procedures. Denitrification does not directly increase the potential
for corrosion (MIC); however, it does increase difficulties in maintaining stable operating and
control conditions.
A metabolic pathway is:

denitrifying bacteria NO3 denitrification NO2 NO NO2 (gas) +/- N2 (gas)
B-8
Typical microflora include:
Alcaligenes sp. Hyphomicrobium sp.
Bacillus sp. Pseudomonas sp.
Nitrosomonas sp. Thiobacillus sp.
Step 5. Recycling and/or Short Cuts
It is important to remember that this biogeochemical cycle is a continuously recycling process. It

does not typically reach an endpoint. Some stages are limited by the accumulation of byproducts
that either affect the metabolism of the microorganisms or change the microenvironment. It is a
dynamic process where several stages of the cycle can occur simultaneously. Several of the
stages are reversible and there are short cut pathways that bypass the dominant pathways. The
recycling process ensures that all living organisms are supplied with a form of nitrogen necessary
for their existence. This is particularly significant when one considers that the primary nitrogen
reservoir exists as a non-metabolizable compound, N2.
This diversity contributes to potential problems in both terrestrial and aqueous environments.
The diversity has provided situations where great benefits are obtained but, when not managed,
the nitrogen biogeochemical cycle can contribute to problems such as environmental pollution,
MIC, plugging and fouling, biofouling, and loss of heat transfer in cooling water systems.
Suggested Reading
Microbial Ecology, Fundamentals and Applications Fourth Ed.. By R. M. Atlas and R. Bartha,
Chapter 11, Biogeochemical Cycling: Nitrogen, Sulfur, Phosphorus, Iron, and Other Elements.
Pub. Benjamin/Cumming Science. Imprint - Addison Wesley Longman. Inc., Menlo Park, CA,
1998.
B.3.2 Aerobic Mechanisms
Iron and Manganese Bacteria
Pseudomonas sp. bacteria are aerobic slime-formers. They contribute to MIC by scavenging
oxygen and forming deposits that can harbor sulfate-reducing bacteria (SRB). Pseudomonas sp.
can also reduce Fe+3 to Fe+2, which can contribute to corrosion by exposing bare metal.
Gallionella sp. bacteria are associated with the pitting of carbon and stainless steels. They are
obligate-aerobic iron bacteria that excrete high levels of iron and manganese in their waste.
The morphology of stainless steel pits caused by these microbes is characterized by a small
opening leading to a cavernous corroded area. Corrosion deposits on carbon steel are
hemispherical. Deposits can be voluminous enough to occlude carbon steel pipes. Crenothrix sp.,
Leptothrix sp., Clonothrix sp., and Sphaerotilus sp. are aerobic, filamentous iron-oxidizing
B-9
and/or manganese-oxidizing bacteria. They oxidize soluble iron to the insoluble Fe(OH)3.
Hemispherical tubercles, which are typically brown or reddish brown, are formed by these
bacteria. Black tenacious deposits of MnO2 can also be formed.
Sulfur-Oxidizing Bacteria
Thiobacillus sp. and Ferrobacillus sp. are aerobic bacteria that oxidize sulfide to sulfate and
form sulfuric acid. They often coexist with sulfate-reducing bacteria. They appear to be much
less damaging to metals than they are to concrete. Thiothrix sp. and Beggiatoa sp. are aerobic
bacteria that oxidize H2S to elemental sulfur. The yellow sulfur reaction product is often visible
when these bacteria are present. Their major contribution to MIC is the formation of slime in
which SRB can live.
B.3.3 Anaerobic Mechanisms
Sulfate-Reducing Bacteria
The sulfate-reducing bacteria (SRB), Desulfovibrio sp. and Desulfomaculum sp., are responsible
for the largest economic impact of all the bacteria associated with MIC. These anaerobic bacteria
convert sulfate to sulfide. The sulfide is very aggressive to cast iron, carbon, and low-alloy
steels, stainless steels, high-nickel alloys, and copper alloys. The pitting of copper alloys is
significantly increased in the presence of as little as 0.2 ppm sulfide. SRB damage to stainless
steel and carbon steel is indicated by the presence of black iron sulfide (FeS). Pitting in high-
nickel and copper-based alloys can often be attributed to sulfide attack. The presence of SRB in
deposits can readily be detected by a simple field test. The addition of an acid (for example, 10%
citric acid) to the deposit will liberate hydrogen sulfide gas (rotten egg odor) if SRB have been
present.
Nitrifying and Denitrifying Bacteria
Nitrifying bacteria such as Nitrosomonas sp. and Nitrobacter sp. oxidize nitrite to nitrate.
Denitrifying bacteria reduce nitrite and nitrate to nitrogen gas and ammonia. These bacteria
include facultative anaerobic bacteria such as Pseudomonas sp and others listed in Section B.3.1.
B.3.4 Microbiologically Influenced/Induced Corrosion (MIC)
Microorganisms working in conjunction with traditional corrosion mechanisms can significantly

alter the kinetics of the reaction, hence, the name microbiologically influenced/induced (MIC)
corrosion. The corrosion-inducing aspect of the MIC name usually refers to the establishment of
a deposit or crevice by microbiological growth, thereby initiating corrosion that otherwise would
not occur. Microorganisms influence corrosion in many ways, such as:
The excretion of metabolic byproducts that accelerate corrosion
Concentrating halides, which rapidly corrode ferrous materials
B-10
Interfering with the cathodic half-reaction under oxygen-free conditions, resulting in

increased anodic dissolution
Oxidation of metal anions to less soluble forms (for example, Fe+2 to Fe+3) by iron-oxidizing
bacteria
Destruction of protective coatings
Destruction of corrosion inhibitors
B.3.5 Impact of Microbiological Fouling
Slime-forming bacteria secrete a sticky film that provides them with protection from the
environment and reinforces their attachment to system surfaces. This film, in its pure state, feels
slippery to the touch and will curl and peel if allowed to dry. The biofilm collects other particles
from the water and can grow into a very thick film. Formation of biofilms inside heat exchanger
tubes can lead to a rapid degradation in performance. In severe cases, the fouling becomes so
extensive that the deposit can only be removed by shutting down and cleaning the equipment.
B.4 References
1. CHECWORKS Flow-Accelerated Corrosion: User Guide. EPRI, Palo Alto, CA: 1997.
TR-103198-P1.
2. F. L. LaQue. Marine Corrosion Causes and Prevention. John Wiley & Sons, p. 147.
B.5 Bibliography
Sourcebook for Microbiologically Influenced Corrosion. EPRI, Palo Alto, CA: 1989. NP-5580.
Detection and Control of MIC: An Extension of the Sourcebook for MIC in Nuclear Power
Plants. EPRI, Palo Alto, CA: 1993. NP-6815D.
MIC Training Course, EPRI-PSE, Edition 8/02, Charlotte, NC.
Service Water System Corrosion and Deposition Sourcebook. EPRI, Palo Alto, CA: 1993.
TR-103403.
Guideline for the Evaluation and Treatment of Corrosion and Fouling in Fire Protection
Systems. EPRI, Palo Alto, CA: 1999. TR-109633.
A Practical Manual on Microbiologically Influenced Corrosion, Volume 1, NACE International,

Houston, TX: 1993.
A Practical Manual on Microbiologically Influenced Corrosion, Volume 2, NACE International,

Houston, TX: 2002.
B-11
The Nalco Water Handbook, Nalco Chemical Company, McGraw-Hill, Inc., New York.
Betz Handbook. GE Betz, Trevose, PA.
Fontana and Greene. Corrosion Engineering. McGraw Hill, Inc., New York. 1978.
James W. McCoy. Microbiology of Cooling Water. Chemical Publishing Company, New York,
NY 1980.
B-12
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PLANT SUPPORT ENGINEERING

Final Report, April 2004

EPRI Project Manager

(A) MAKES ANY WARRANTY OR REPRESENTATION WHATSOEVER, EXPRESS OR IMPLIED, (I)

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ORGANIZATION(S) THAT PREPARED THIS DOCUMENT

Water Technology Consultants, Inc.

This report was prepared by

Water Technology Consultants, Inc.

This report describes research sponsored by EPRI.

Results and Findings

Challenges and Objectives

Ms. Debra J. Bodine, Chairperson Tennessee Valley Authority

2 DESCRIPTIONS OF CLOSED COOLING WATER SYSTEMS .............................................2-1

3 PROBLEMS IMPACTING CHEMISTRY IN CLOSED COOLING WATER SYSTEMS..........3-1

4 TECHNICAL BASIS OF TREATMENT CHEMICALS USED FOR CORROSION

5 TREATMENT PROGRAM AND MONITORING RECOMMENDATIONS ..............................5-1

6 TECHNICAL BASIS OF CHEMICALS USED FOR MICROBIOLOGICAL AND

Foulants Generated Within the System ................................................................6-13

7 TECHNICAL BASIS OF MONITORING PARAMETERS.......................................................7-1

8 ADDITIONAL MONITORING TECHNIQUES .........................................................................8-1

8.6.4 Ultraviolet/Visible Spectroscopy (UV/Vis) .........................................................8-14

9 TROUBLESHOOTING AND CORRECTIVE ACTIONS .........................................................9-1

9.5 Chromate-Treated Systems.......................................................................................9-14

10 METHODOLOGY FOR PLANT-SPECIFIC TREATMENT OPTIMIZATION ......................10-1

A POSITION PAPER ON IMPURITY CONCENTRATION LIMITS FOR CLOSED

B CHEMISTRY-RELATED PROBLEMS IN CLOSED COOLING WATER SYSTEMS ........... B-1

B.1.2 Localized Corrosion ........................................................................................... B-1

Figure 2-1 Typical Closed Cooling Water System......................................................................2-2

The guidance provided here is targeted at reducing corrosion, microbiologically influenced

1.2 Terms and Definitions

1.2.1 Control Parameters

1.2.2 Diagnostic Parameters

Diagnostic Parameters are important to monitor program effectiveness, identify programmatic

1.2.3 Investigative Parameters

1.2.4 System Ranking by Tiers

1.2.5 Remaining Plant Systems

1.2.6 CCW Action Levels

CCW Action Level 1

The normal operating ranges recommended in this guideline represent a conservative

CCW Action Level 2

1.3 Contaminant Specifications

The scope of the Closed Cooling Water Chemistry Guideline is to:

1.7 Management Responsibility and Program Ownership

1.7.1 Water Chemistry Management Philosophy

1.7.2 Generic Management Considerations

Assessment of the effectiveness of chemistry control in minimizing component

Utility personnel responsible for plant design in chemistry-related areas should:

Procedures should include:

1.7.3 Training of CCW Chemistry Control Personnel

1.8 Roles and Responsibilities of Plant Personnel

1.8.2 System Engineering

2.1 Purpose of Closed Cooling Water Systems

A closed system is defined as a heating or refrigerating piping system in which circulating

2.2 Closed Cooling Water System Design

Descriptions of Closed Cooling Water Systems

2.3 Variations of Closed Cooling Water System Design

Descriptions of Closed Cooling Water Systems

2.4 System Materials

Descriptions of Closed Cooling Water Systems