United State?
Environmental Pictecrtun
Agency
trutuMrml Environmental
   lnangle Park NC
EPA 600/7 78-221
November 1978
Assessment of the Effects
of Chlorinated  Seawater
from Power Plants on
Aquatic Organisms
         <*
Interagency
Energy/Environment
R&D Program Report

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                  RESEARCH REPORTING SERIES


Research reports of the Office of Research and Development. US Environmental
Protection Agency, have been grouped into nine series  These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental  technology  Elimination of  traditional grouping was  consciously
planned to foster technology transfer and a maximum interface in related fields
The nine series are

    1   Environmental Health Effects Research

    2  Environmental Protection Technology

    3  Ecological Research

    4  Environmental Monitoring

    5  Socioeconomic Environmental Studies

    6  Scientific and Technical Assessment Reports (STAR)

    7   Interagency  Energy-Environment Research and Development

    8   "Special Reports

    9   Miscellaneous Reports

This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH  AND DEVELOPMENT series Reports m this series result from the
effort  funded under the  17-agency  Federal Energy Environment Research and
Development Program These studies relate to EPA s mission to protect the public
health and welfare from adverse effects of pollutants associated  with energy sys-
tems  The goal of the Program is to assure the rapid  development of domestic
energy supplies m an environmentally-compatible manner by providing the nec-
essary environmental data and control technology  Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects, assessments  of.  and development of. control technologies for  energy
systems, and integrated assessments of a wide'range of energy-related environ-
mental issues
                        EPA REVIEW NOTICE
This report has been reviewed by the participating Federal Agencies, and approved
for  publication Approval does not signify that the contents necessarily reflect
the  views and policies of the Government, nor does mention of trade names or
commercial products constitute endorsement or recommendation for  use.

This document is available to the public through the National Technical Informa-
tion Service  Spnngfielo. Virginia 22161

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                 NOTICE





THIS DOCUMENT  HAS BEEN REPRODUCED



FROM THE BEST  COPY FURNISHED  US BY



THE SPONSORING AGENCY.  ALTHOUGH IT



IS RECOGNIZED THAT CERTAIN  PORTIONS



ARE ILLEGIBLE,  IT IS BEING RELEASED



IN THE  INTEREST OF MAKING AVAILABLE



AS  MUCH  INFORMATION AS POSSIBLE.

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                                TECHNICAL REPORT DATA
                         (Please read ItiUructions on the reverse before completing)
 1 REPORT NO.
 EPA-600/7-78-221
                                                      3. REC
                               :'\s
4 TITUEANOSUBT'TLE Assessment of the Effects of
 Chlorinated Seawater from Power Plants on Aquatic
 Organisms
            6 REPORT DATE
             November 1978
            6 PERFORMING ORGANIZATION CODE
7 AUTHOHIS)

 R.Sung, D, Strehler, and C, Thome
                                                      8. PERFORMING ORGANIZATION REPORT NO
B PERFORMING ORGANIZATION NAME AND ADDRESS
 TRW, Inc,
 Environmental Engineering Division
 Redondo Beach,  California  90278
            10 PROGRAM ELEMENT NO,
            EHE624A
            11. CONTRACT/GRANT NO.

            68-02-2613, Task 13
12. SPONSORING AGENCY NAME AND ADDRESS
 EPA, Office of Research and Development
 Industrial Environmental Research Laboratory
 Research Triangle Park, NC  27711
            13. TYPE OF REPORT AND PERIOD COVERED
            Task Final; 5-9/78
            14. SPONSORING AGENCY CODE
              EPA/600/13
IB.SUPPLEMENTARY NOTES TjERL-RTP project officer is Michael C. Osborne, MD-61,  919/
 541-2898
i6 ABSTRACT Tne report gives a detailed review of past and present research efforts on
the effects of chlorinated seawater .fjrom power plants  on aquatic organisms. It inclu-
des: (1) a characterization of chemical species contained in power plant seawater
discharges;  (2) a review of the amperometric titration method for residual chlorine
determinations in seawater: and (3) an analysis of the  toxicity of compounds formed
by chlorination of seawater.  The review concluded that (1) the toxicity of chlorinated
seawater effluent is due primarily to various oxidant residuals produced by chlori-
nation, rather than to residual chlorine itself;  (2) the amperometric titration method
is adequate to determine safe oxidant levels when identification of specific  com-
pounds is not required;  (3) bromoform is a principal contributor to toxicity in  power
plant discharges (because of volatility and degradability, bromoform is not expected
to be as toxic as chloroform); and (4) other compounds suspected of causing toxicity
have not been clearly  identified. Further studies into the actual components present
in chlorinated power plant seawater discharges are necessary to determine exactly
which compounds are  responsible for the toxicological effects.
17.
                             KEY WORDS AND DOCUMENT ANALYSIS
                DESCRIPTORS
 Pollution             Toxicity
 Sea Water            Oxidizers
 Chlorination          Bromoform
 Electric Power Plants
 Aquatic Animals
 Electrical Measurement
18. DISTRIBUTION STATEMENT
 Unlimited
                                          b IDENTIFIERS/OPEN ENDED TERMS
Pollution Control
Stationary Sources
Amperometric Titration
c. COSATi Field/Group
           06T~
           11G .
                                          19. SECURITY CLASS (TMs Rtpon)
                                          Unclassified
20 SECURITY CLASS (Thispage/
Unclassified
13B
08J
07C,07B
10B
08A,06C
14B
                                                                  21 NC
                                                                  22 PRICE
EPA Form >»ZO-t

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                                   EPA-600/7-78-221
                                      November 1978
    Assessment of the Effects of
Chlorinated Seawater from Power
    Plants on Aquatic Organisms
                         by

                 R Sung D Strehlwr, and C Thome

                       TRW Inc
                 Environmental Engineering Division
                 Heclonrio Beach California 90278
                   Contract No 68-02 2613
                      Task No 13
                  Proqnm Element No EHE624A
                EPA Project Olhcei Michael C Osbome

              Industrial Environmental Research Laboratory
                Office of Energy Minerals and Industry
                 Research Triangle Park NC 27711
                      Prepared for

              U S ENVIRONMENTAL PROTECTION AGENCY
                Office of Research and Development
                    Washington DC 20460

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                              EXECUTIVE SUMMARY

     This report was prepared for the U.S.  Environmental  Protection Agency
to provide a comprehensive review of available data on the effects of chlor-
inated seawater from power plants on aquatic organisms.   The report is a com-
pilation of published and unpublished research efforts,  and communication with
individuals currently involved in related studies.   Three areas  were investi-
gated: 1) chemical characterization of power plant  discharges  produced by chlor-
inating seawater, 2) the toxicity of the  compounds,identified  in (1),  to aquatic
organisms, and 3) methods for determining the presence of chlorine and/or chlor-
ine derived oxidants in seawater.
     The culmination of this effort produced the following overall con-
clusions and recommendations:
     •  The toxicity of chlorinated seawater effluent from power plant cool-
        ing systems is due primarily to the presence of various  oxidant re-
        siduals produced by chlorination  rather than to just residual  chlor-
        ine.
     t  The amperometric titration method is generally adequate  to measure
        total oxidant residuals, (which include chlorine  and bromine residuals)
        where  identification of  specific compounds  is not required.
     •  Further studies are required to determine both individual  species
        present in chlorinated power plant discharges and the  toxicity of
        the identified species on aquatic organisms.
     •  More specific analytical procedures may be  required if it  is found
        that individual compounds are significantly more  toxic at  lower
        levels than can be measured presently.
     It should be noted that each power plant presents a  unique  situation.
Site specific parameters (such as compound in the intake  water,  etc.)  as
well as the types of aquatic life which exists in the discharge area must be
considered for both analytical measurements and toxicity  studies.
                                     11

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                                  CONTENTS

Executive Summary	ii
Figures	iv
Tables  	   v
     1.  Introduction	1-1
     2.  Conclusions  and  Recommendations  	  2-1
             Conclusions	2-1
             Recommendations 	   2-2
     3-  Characterization of Chlorinated Seawater from Power
         Plants	3-1
             Cooling System Description	3-1
             Characterization of Raw Seawater	3-3
             Characterization of Chlorinated Seawater	3-11
             Comparison of Identified Chlorinated Seawater Species
             to the List of 129 Toxic Pollutants	3-21
     4.  Evaluation of Amperometric Titration for Determination
         of Residual Chlorine in Seawater	4-1
             General Method Description	4-1
             Iodine Chemistry	4-3
             Limitations and Interferences 	   4-5
             Interferences Particularly Related to Seawater	   4-7
     5.  Toxicity of Compounds Formed by Chlorination of Seawater. .   5-1
             Definition of Toxicity	5-1
             Identification of Potentially Toxic Species 	   5-5
             Identification of Toxic Levels and Aquatic Organisms
             Affected	5-7
             Comparison of Toxic Levels with Levels Expected from
             Power  Plant Discharges	5-18
             Qualitative Analysis of the Toxicity and Measurment of
             Pollutants Formed in Chlorinated Seawater 	 .   5-20
References                                                             6-1
Bibliography                                                          7-1

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                                  FIGURES
Number                                                                Page
  ]     Approximate amount of seawater required by a once-through
        cooling system for steam electric power plants	3-2
  2     Schematic Flow diagram of power plant 	   3-4
  3     Flow diagram of a typical once-through cooling system using
        seawater	3-5
  4     Principle species of bromine and bromamine	3-17
  5     Degradation processes for chlorine in saline waters  	   3-18
  6     Chlorine substitution reaction	3-20
  7     Toxicity of chlorine to marine organisms	5-23
                                     IV

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                                   TABLES

Number                                                               Page
  1     Typical  Design Free C10 and C^ Residue Concentrations,  .  .    3-6
  2     Concentration of Major Ions in Seawater
        (g/Kg Seawater) Normalized to 35%0 Salinity 	    3-8
  3     Chemical  Species in Seawater	3-9,3-10
  4     The Major Chemical  Species in Seawater	    3-12
  5     Minor Constituents  of Seawater	    3-13
  6     Dissolved Organic Compounds in Seawater 	    3-14
  7     Potential Interferring Oxidants 	    4-4
  8     General  Categories  of Toxic Effects 	    5-2
  9     Techniques Generally Used for Conducting Toxicity Tests  .  .    5-3
 10     Terminology Used for Expressing Results of Toxicity Tests  .   5-4,5-5
 11     A Preliminary List  of the Chemical Constituents Identified
        in Chlorinated Seawater 	    5-6
 12     Summary  of Data on  Toxicity of Chlorine to Marine Organisms   5-8 - 5-12
 13     Summary  of Toxicity of Various Chemical  Species to Marine
        Organisms 	   5-13-5-16

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                                SECTION 1.0
                               INTRODUCTION

     Large volumes of cooling water are required by power plants.   Often  this
requirement is met by locating the power plant near a major body of water.
Because of the favorable conditions for aquatic organism growth within  the
cooling water system, most power plants are confronted with biofouling  pro-
blems.  Bacterial  and algoid slimes, and higher order aquatic  organisms often
attach themselves  to surfaces within the cooling circuit, thus reducing cool-
Ing system flow rates and heat transfer efficiencies.   The use of  chlorine
has been the most»'common method for controlling biofouling.
     Chlorine when used in this and other applications, may present toxico-
logical problems to aquatic organisms in the receiving waters. The toxicity
of chlorine and chlorination derived oxidants from power plant cooling  water
discharges are presently being investigated by the various researchers.  The
impetus for these  investigations are: 1)  PL 92-500 Section 307(a) of the  toxic
substances control act, which requires that each pollutant be  individually
studied, assessed  and regulated and a settlement between EPA;  and  2) the
environmental groups relating to toxic material discharges.
     This report was prepared under the direction of the EPA to provide a
portion of the base from which regulations may be promulgated. The main  ob-
jectives of this study are the characterization of seawater, evaluation of
amperometric titration for determining residual chlorine in seawater, and
the assessment of  toxicity from seawater chlorination.   To meet these ob-
jectives, this report includes a state-of-the-art review of available data
from past studies  on the aforementioned topics.  In addition,  current on-
going research studies investigating various aspects of the characterization
of chlorinated seawater, toxicity or measurement techniques were either iden-
tified or contacted.
                                   1-1

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                                  SECTION  2.0
                                                                        I
                           CONCLUSIONS AND RECOMMENDATIONS

     During the course of this  study it has become  evident  that  additional
chlorinated seawater research should be initiated.   This  section will  high-
light the conclusions which were reached in each  of the subject  areas  (chlor-
inated seawater characterization, amperometric  titration  and  toxicity)  and pre-
sent recommendations for further research.
Conclusions
     Characterization of Chlorinated Seawater
     •  The chemical compounds  present in  seawater  power  plant discharges
        are dependent upon several  factors:  1)  chemical species  present in
        intake water, 2) chlorine dosage,  3) reaction  duration,  4)  pH,  5)
        temperature, and 6) light exposure-
     •  A complete chemical analyses of individual  species  present  in  chlor-
        inated seawater have not been performed.  The  requirement for  site
        specific information calls  for each power plant discharge to be an-
        alyzed separately to eliminate potential  sources  of extraneous  in-
        fluence.
     •  Many of the compounds suspected or identified  to  be present in
        chlorinated seawater are either contained in the  list of 129 toxic
        substances, or are potentially toxic although  not presently included
        in this list.
     Amperometric Titration
     «  The amperometric titration  method  is presently considered the  best
        available method for analyzing oxidants  in  all water  types  by  a
        majority of researchers.   This method can determine chlorine resi-
        duals quantitatively, however,  only  in fresh water.
     •  Many compounds in chlorinated seawater  interfere  with the ampero-
        metric titrations in the measurement of  free and/or combined chlor-
        ine residuals.
                                   2-1

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     •  Current technology indicates that the amperometric titration method
        can measure reliably concentration of residual  oxidant up to a de-
        tection limit of 0.01 mg/1,  which is half the toxicological  limit
        identified by Mattice as causing chronic toxicity to marine  organ-
        isms in power plant discharge,
     Toxicity of Chlorinated Seawater
     0  Chlorination of seawater has been shown to cause toxic reactions in
        various aquatic life forms.   The specific compounds causing  the toxic
        effects, however, have not been  quantified.
     •  Bromoform, a by-product of seawater chlorination, has been identi-
        fied as a major contributor  to  toxicity in power plant discharges.
        However,  preliminary assessment by various researchers indicated
        that bromoform may not be as toxic as chloroform because of  its
        volatility and degradability in seawater.  Further study is  necessary
        to substantiate this claim.
     •  Other brominated compounds  suspected to cause toxicity have  not been
        clearly identified due to lack  of specific analytical techniques.
Recommendations
     •  Continue research into characterization of chlorinated seawater.
     •  Based upon specific chemical species identified in the characteri-
        zation studies, begin toxicological  studies,  using continuous flow-
        through system.
     •  Develop more sophisticated  analytical techniques such as GC/MS which
        will measure quantitatively  those compounds identified as toxic to
        aquatic organisms.
     •  Revise terminology used in  chlorinated seawater measurements; rather
        than specifying free or residual  chlorine measurements the appropri-
        ate terminology should be total  oxidant or chlorine derived  oxidants
        measurements instead.
     •  Compile and evaluate toxicity data of other biocides other than
        chlorine  for condenser tube  biofouling control.
     •  Conduct bench scale studies  to  evaluate control  technologies for the
        removal of organics that react  with  chlorine  to cause toxicity.

                                    2-2

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Evaluate alternative analytical methods for chlorine residual  measure-
ment, if research indicates that chlorine residuals specifically ac-
count for the toxicity of the power plant discharge.
Evaluate the effects of dechlorination (using sulfur dioxide or sodium
sulfite) on potential toxicity reduction.
                            2-3

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                                 SECTION 3.0
         CHARACTERIZATION OF CHLORINATED SEAWATER FROM POWER PLANTS

      An important consideration  in  the  assessment of  the  amperometric  titra-
 tion method as well  as  the  evaluation of  toxicity of  chlorinated  seawater  is
 the understanding of the nature  and characteristics of chlorinated  seawater
 from power plants.   To  this end, the section  is  divided  into:  (1)  power
 plant cooling system description;  (2) characterization of raw  seawater;  (3)
 characterization of  chlorinated  seawater;  and (4) comparison of  identified
 chlorinated seawater species to  the list  of 129  toxic pollutants.   The fol-
 lowing is  a detailed discussion  on  these  areas.
 Cooling System Description
      Most  power plants,  whether  fossil fuel or nuclear, require large  amounts
 of water to dissipate waste heat.   The  source of the  water used  is  generally
 nearby natural water bodies; therefore, coastal  power plants  usually use
 seawater for cooling.
      The typical power  plant cooling circuit  is  a once-through system  de-
 signed for an 11°C (20°F)  temperature rise across the condenser  coils.   This
 requires a water retention  time  of  approximately 5  to 10  minutes  within  the
 cooling circuit.
      The amount of water required  by a  once-through cooling system  is  depen-
 dent mainly upon the facility  size  in terms of gross  generating  capacity.
 Figure 1 is a graphic presentation  of the  approximate amount of  seawate'r re-
 quired by  a once-through cooling system for power plants  of various  gross  gen-
 erating capacities.   It was developed by  linearizing, using the  least  square
 method, design  flow  rate data for several  coastal  power  plants of dif-
 ferent design gross  generating capacities  as  reported by  Hergot et.al. (1)
 and Yu et al. (2)
     The inherent drawbacks of cooling systems using water from natural
sources are the  formation and growth of  various biological species on
channel walls and condenser tubes.   In extreme instances  this  growth can
cause plugging of the condenser tubes and  reduces flow in the  intake and
                                     3-1

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     2400
    2000
o

I    1600
2
     1200«
E
CD
     800.
     400-




       0


       0.
                  10
20
                                    30
40
50
•ar
                          Cooling water f!ow,r3te (m /sec)
                   200
                                400
                 600
          800
                          Cooling Water  Flow Rate  (10J GPM)
     Figure 1.  Approximate amount of seawater required by a
                once-through cooling system for steam electric
                power plants.
           1000
                                3-2

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                                SECTION 3.0
         CHARACTERIZATION OF CHLORINATED SEAWATER FROM POWER PLANTS

      An  important  consideration in  the  assessment of  the amperometric titra-
 tion  method  as  well  as  the  evaluation of  toxicity of  chlorinated seawater  is
 the understanding  of the  nature and characteristics of chlorinated seawater
 from  power plants.   To  this  end,  the section  is  divided into:  (1) power ,
 plant cooling system description;  (2) characterization of  raw  seawater; (3)
 characterization of  chlorinated seawater; and  (4) comparison of identified
 chlorinated  seawater species to the list  of 129  toxic pollutants.  The fol-
 lowing is a  detailed discussion on  these  areas.
 Cooling  System  Description
      Most power plants, whether fossil  fuel or nuclear, require large amounts
 of water to  dissipate waste  heat.   The  source  of the  water used is generally
 nearby natural  water bodies; therefore, coastal  power plants  usually use
 seawater for cooling.
      The typical power  plant cooling circuit  is  a once-through system de-
 signed for an 11°C (20°F) temperature rise across the condenser coils.  This
 requires a water retention  time of  approximately 5 to 10 minutes within the
 cooling  circuit.
      The amount of water  required by a  once-through cooling system is depen-
 dent  mainly  upon the facility  size  in terms of gross  generating capacity.
 Figure 1  is  a graphic presentation  of the approximate amount of seawater re-
 quired by a  once-through  cooling  system for power plants of various  gross  gen-
 erating  capacities.   It was  developed by  linearizing, using the least square
 method,  design flow  rate data  for several coastal  power  plants of  dif-
 ferent design gross  generating capacities as  reported by Hergot et,al. (1)
 and Yu et al.  (2)
     The  inherent  drawbacks  of  cooling  systems using  water  from natural
sources are the  formation and growth of  various biological  species  on
channel walls and  condenser  tubes.  In extreme instances  this  growth  can
cause plugging of  the condenser tubes and  reduces flow in  the  intake  and
                                     3-1

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     2400
     2000' •
0
I    1600
01

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   discharge channels.   Conditions  such  as  these  require  unit  shutdown and
   drainage, and  the chemical  and/or manual  removal of  the  fouling organism.
   In less  severe cases  biological  growth in the  form of  slime develops on
   the condenser  tubes,  causing  a degradation of  the heat transfer character-
   istics of the  condensing  unit which reduces  the overall  generating capacity
   of the facility.
        To  counteract these  problems, various methods have  been  used in an at-
   tempt to control  and/or curtail  biofouling problems.   The most successful
   and widely applied method of  biofouVing  control is chlorination.  The  first
   documentation  of the  successful  application  of chlorination in a commercial
   power plant was in 1924,  and  the development of high-capacity chlorination
   equipment commenced in 1930.  Since that time  chlorination  for biofouling
   control  in power plants has enjoyed widespread use.
       The  basic power plant consists of a  boiler,  turbine/generator  and  cool-
   ing system.  A simplified diagram of this basic system is shown  in  Figure  2.
   Basically the steam/condensate loop is a  closed system, and the  cooling water
   circuit  is  an  open  loop.   A simplified diagram of a typical once-through
   cooling system is given in Figure 3.   Water from  a natural  water  body  is
   brought into the circuit through an intake channel;  it is divided into  par-
   allel streams and then chlorinated.  The  chlorinated water passes through  a
   bar rack  system in order to remove large  debris,  such as  seaweed, kelp  and
   larger marine animals; it is pumped through the condenser and  acts  as  a heat
   sink as it  passes through the condensers   (typical  design  calls for  an  11°C
   (20°F) temperature rise.  From the condenser it once again combines  into a
   single stream and passes through a common discharge  channel  back  to  the natu-
   ral water body.  Table 1 gives a summary  of design chlorine concentrations
   at  the points identified as chlorine application  and chlorine  residue  in
   Figure 3.   The Environmental Protection Agency has established guidelines
   for the discharge of free chlorine to  receiving water bodies;  these  guide-
   lines allow 0.5 mg/1 maximum and 0.2 mg/1 average  concentration  for  up  to
   two hours per day from any one unit (3).   Many state standards are more
   stringent than the federal standards.
   Characterization of Raw Seawater
       There  are two basic terms used to describe seawater.  The terms are
   salinity  and chlorinity.  By definition,  salinity  is the  content  of  dissolv-
   ed salts  1n seawater; and chlorinity is the content  of halogen ions  other
 ,  than fluoride in seawater.  A great deal  of information about  the chemical

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                                          STEAM
to
I
                       BOILER
                                         CONDENSATE
                    REF. 2
                                                                                                OCEAN
                                         Figure 2.   Schematic flow diagram of power plant

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CO
I
en

                           POINTS  OF  CHLORINE
                           RESIDUE
                         DISCHARGE
                           (SEA)
                                                                   CHLORINE APPLICATION
                                                                         POINTS
- \












1
\

2



3


4

CONDENSERS


/* ~>
C^

™* f ~\
(j
PUM


/"*
G

07
                                                                      e——
                                                                             BAR
                                                                             RACKS
INTAKE
(SEA)
                    Figure 3.   Flow diagram of a.typical  once-through cooling system using seawater

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       TABLE  1.   TYPICAL DESIGN FREE C12 AND C12 RESIDUE CONCENTRATIONS
Type of             C12 Concentration  at           Clp Residue  Concentration
Chlorlnatlon        Point of Application           Downstream of Condenser
Continuous          0.50 ppm free C12*             0.25-0.5 ppm*

Intermittent        1.5 - 4.0 ppm free C12         1.0 ppm
* Inlet water temperature greater than 277°K (40°F)

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 nature of a given water sample is conveyed by the numeric values of these
 terms.

     The salinity of seawater varies only slightly in the major oceanic
water masses throughout the world.   The extreme in salinity values  as iden-
tified by Todd (4) range from a low of 33.5%0 for Subartic water in the North
Pacific to a high of 36.4%0 for Mediterranean water in the North Atlantic.
Smith (5) presented data which indicates that the mean value of salinity
for seawater is 35%0-   This value will be used to normalize information
which will  be presented in Tables 2 through 6.
     Strickland (6) discussed the Knudsen equation which establishes a re-
lationship between chlorinity and salinity.  The equation is as follows:
                          Sa  =  0.030  +  1.8050 Cl
                             where:
                               Sa is salinity
                               Cl is chlorinity
     By this relationship, assuming that the salinity of typical seawater
is approximately 35.0%0 then the chlorinity of typical seawater is  approxi-
mately 19.4%0.
     Tables 2 through 6, which are modified versions  of data presented by
Smith (5),  give an overall characterization of the most probable components
of seawater.  Table 2 gives a list of eleven species  which are the  major ions
found in seawater as well  as their respective concentration ranges.  The data
presented is normalized to a salinity of 35%0 which corresponds (as per
Knudsen equation) to a chlorinity of 19.4%».  As can be seen in the  table the
average value of chloride is 19.353 g/kg which corresponds to approximately
19.4%0.  The data presented in this table reveals that approximately 86% of
the total dissolved solids in typical seawater are sodium and chloride ions,
and that approximately 98% of the total dissolved solids are made of four
major ions (sodium, chloride, magnesium, and sulfate).
     Table 3 presents a list of the chemical  species  found in seawater   It
lists Individual elements  and then the most connion chemical form in which
they are found in seawater.  This table shows that certain elements, such
as carbon nitrogen and magnesium, are found in several forms; whereas,
others, such as chlorine and bromine are typically found in only one form.
                                    3-7

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    TABLE  2.   CONCENTRATION  OF MAJOR  IONS  IN SEA WATER (g/Kg SEA WATER)
              NORMALIZED TO  35%  SALINITY

Ion
Chloride
Sodium
Magnesium
Sulfate
Calcium
Potassium
Bicarbonate*
Bromide
Boron
Strontium
Fluoride
Ave. Value
19.353
10.76
1.297
2.712
0.4123
0.399
0.145
0.0673
0.0046
0.0078
0,0013
Range
-
10.72 -
1.292 -
2.701 -
0-4088
0.393 -
0.137 -
0.0666
0.0043
0.0074
0.0012


10.8
1.301
2.724 :
- 0.4165
0.405
0.153
- 0.0680
- 0.0051
- 0.0079
- 0.0017
* The values reported for bicarbonates are actually titrated alkalinities.
           (Reference 5, page 4)
                                   3-8

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TABLE 3.  CHEMICAL SPECIES IN SEA WATER

Element
Hydrogen
He! i urn
Lithium
Boron
Carbon
Nitrogen
Oxygen
Fluorine
Neon
Sodium
Magnesium
Aluminum
Silicon
Phosphorus
Sulfur
Chlorine
Argon
Potassium
Calcium
Titanium
Vandium
Chromium
Manganese
Iron
Cobalt
Chemical Form
H20
He(g)
LI+
B(OH)3, B(OH)4
HC03> C03", C02, MgHC03, NaHC03°, MgC03°, organic compounds
NCC, N0~, NH0, N?(g), organic compounds
J f- J ? t-
HoO, 02(g), S04 , organic compounds
F", MgF+, CaF"1"
Ne(g)
Na+, NaS04, NaHC03°
Mg2"1", MgS04°, MgHCOj, MgC03°
A1(OH)3
Si(OH)4, SiO(OH)3
H2P04, HPO2-, POJJ-
•SOj", NaS04, MgS04°, CaS04°
cr
Ar(g)
K+, KS04
Ca2", CaS04°, CaHC03
Ti(OH)4
V02(OH)2"
Cr(OH)2, CrOH2"1", Cr02, Cr04T HCr04, H2Cr04
Mn2+, MnS04°, Mn(OH)3 4
Fe(OH)3, Fe(OH)2
C°2+» CoS04° (Continued)
                    3-9

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                             TABLE 3.  (Continued)

Element
Nickel
Copper
Z1nc
Germanium
Arsenic

Selenium
Bromine
Krypton
Rubidium
Strontium

Molybdenum

Silver
Cadmium
Iodine
Zenon
Cesium
Barium
Lanthanum

Tungsten
Gold

Mercury
Thallium
Lead
Radon
Radium
Chemical Form
Ni2*, NiS04°
Cu , CuS04°, CuOH*
Zn2+, ZnS04°, ZnOH+ .
Ge(OH)4°, GeO(OH)3
H3AsO~, H2As04, HAsO^", AsO^"
?
SeOj
Br"
Kr(g)
Rb+
Sr2+, SrS04°
o
MOO;
?-
AgClo, AgCr ,
CdCl , Cd2+, CdS04 °
10', I"
Xe(g)
Cs+
Ba2+, BaS04°
La3+, La(OH)2+
9_
woj
Ulttlultil
fiUw i A j nuv* i f\
7-
HgCK, HgCU
_ j tt
Tl4
Pb2+, PbS04°, PbOH+
Rn(g)
Ra2"*", RaSO.0
Uranium
U02(CO-
                                      3-10

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     Table 4 gives a list of major chemical  species found in seawater,  and
the probability of their occurrence given their elemental composition.   This
table in conjunction with Table 2 can be used to determine the mass  of  a giv-
en chmical species per unit mass of seawater, e.g., there would be  approxi-
mately 0.64 g of MgSO* in each kilogram of seawater.   In Table 5 a  list of
minor constituents found in seawater and their respective concentration
ranges, as well as, average concentrations are presented.  These constitu-
ents are listed in the elemental form, and it is expected that all  of these
together will make up less than 1% of the total dissolved solids in  seawater.
     Table 6 provides a list of dissolved organic substances found  in sea-
water and their expected concentration ranges.  Because of the large number
of organic compounds that are present in seawater, rather than identifying
each compound, it was decided, for the sake of brevity, to list only major
classes of organic species and the cumulative concentration of each  class.
     In his discussion of the character of seawater,  Liptak (7) noted that
there is a difference between open ocean and coastal  seawaters.  In  the open
ocean intense density stratification exists which hampers mixing between sur-
face and deep waters.  Because of this the cycling of nutrients is  hindered
(thus reducing biological activity).  Whereas, in coastal waters, because
of shallow bottoms and constant tidal and wave activity, a great deal of
mixing occurs, which stimulates the cycling of nutrients.  It is this cycl-
ing of nutrients and an abundance of suspended materials which provide  an
environment conducive to active biological formation and growth.  The pre-
sence of abundant aquatic life forms plus the conditions common to  power
plant cooling systems, such as increased ambient temperatures and large sur-
face areas available for organism attachment, create an environment  which
stimulates the occurrence of biofouling problems.
Characterization of Chlorinated Seawater
     According to Sugam et.al. (8) when seawater is chlorinated, the prin-
ciple equilibrium species formed are brominated compounds analogous  to  chlor-
inated species produced in fresh water.   In the pH range from 6 to  8 these
brominated species are HOBr, OBr", NBr.,, NHBr2> and NH^Br,  The formation of
these species occur because the bromide (Br~) present in seawater  is readi-
ly oxidized by chlorine.
                                    3-11

-------
Constituent
                 TABLE 4.  THE MAJOR CHEMICAL SPECIES IN SEA WATER
                                                                 (5)
Percentage of Constituent present as each species @
25°C, 19.375%.  Chlorinity, 1 atm.,  and pH 8.0
Chloride
Sodium
Magnesium
Sulfate
Calcium
Potassium
Bicarbonate

Bromide
Boron
Strontium
Fluoride
Na+ (97.7%); NaS04 (2.2%); NaHC03° (0.03%)
Mg2* (98%); MgS04 (10%); MgHC03 (0.6%); Mg C03° (0.1%)
SO?" (39%); NaXO" (37%); MgS04 (19%); CaS04° (4%)
Ca*+ (88%); CaS04° (11%); CaHCO* (0.06%); CaC03° (0.1%)
K* (98.8%); KSO" (1.2%)
HC03 (64%); MgHC03 (3%); CO2" (0.8%); MgC03° (6%);
NaCO; (6%); NaCO; (1%);
    J           J
B(OH)3 (84%); B(OH)4 (16%)

F" (50 - 80%); MgF* (20 - 50%)
                                     3-12

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           TABLE 5.  MINOR CONSTITUENTS OF SEA WATER

Constituent
Rubidium
Aluminum
Lithium
Barium
Iodine
Silicon
Nitrogen
Zinc
Lead
Selenium
Arsenic
Copper
Tin
Iron
Cesium
Manganese
Phosphorus
Thorium
Mercury
Uranium
Cobalt
Nickel
Radium
Beryllium
Cadmi urn
Chromium
Titanium
Average Value
120
2
185
20
63
2000
280
6.5
0.05
0.2
0.46
2
0.8
6.6
0.4
1.5
30
0.05
0.03
3
0.27
5.4
8 x 10"8
5.7 x 10"4
0.113
0.3
1
Range
89 -
0 -
180 -
5 -
48 -

134
7
190
93
80
0 -4900
0 -
1 -
0.02 -
0.052 -
0.2 -
0.2 -
--
0-1
0.27 -
0.2 -
0 -
2 -
--
2 -
0.035 -
0.43 -
4 -
--
0.02 -
0.23 -
_ „
560
48.4
0.4
0.50
35
4

62
0.58
8.6
90
40 x 10"4

4.7
4.1
43
15 x 10"8

0.25
0.43

* Excluding dissolved gases
                                      3-13

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                 TABLE 6.  DISSOLVED ORGANIC COMPOUNDS IN SEA UATER
                                                                   (5)
     Constituent
 Range
1.    Carbohydrates
2.    Proteins and Their
       Derivatives       -  Total
       •  Polypetldes and
          Polycondensates
       •  Free Ami no Acids
3.    Aliphatic Carboxylic and
       Hydroxycarboxylic Acids
4.    Biologically Active Compounds
5.    Humic Acid
6.    Phenolic Compounds
7.    Hydrocarbons
 0.2 - 8.4 mg/1
14.9 - 156.5
 6.9 -  39.1 Pg/l
 8.0 - 117.4 yg/l
 0.44 -  4.71

 1.8  - 36.64 myg/1
   Present
   3  - pg/1
   Traces
                                     3-14

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     Sugam further indicated that when chlorine in the form of hypochlorous
acid (HOC1) is added to seawater the oxidation of bromide would occur instan-
taneously as shown in the following exchange reaction:
                          HOC1   +  Br" - - HOBr  +  Cl"
     Carpenter et.al.  (9) in their discussion of the reactions of chlorine
with seawater presented the following chemical  equations  to describe  the
decay of gaseous chlorine to chloride ions.   When gaseous chlorine (C12)  is
added to seawater the following hydrolysis reaction would occur:
                          C12  +  H20 — --HOC1   +  H+  +  Cl"
     Gaseous chlorine may further react with the bromide  in  seawater  to pro-
duce the following sets of reactions (9):
                                                            Br
                               and
                          3 BrOH—-BrO ~  +  3H+  +  2Br",
                                        3
                          BrCl   + 2C12—— Br C15,
                          BrCU +  3 H90	~BrO,~  +  6H+  +  5  Cl".
                              b       L         3
     In discussing the environmental toxicity of chlorine the common  unit  of
measure is "Free Available Chlorine" (FAC).   For hypochlorous acid  this  unit
FAC can be represented as follows (10):
                          FAC  =  HOC1   +  OC1"
     Johnson (10) stated that in seawater at   pH 7.5 and temperature  of
298°K (77°F) the FAC is approximately half HOC1  and  half  OC1",  and  that  as
the pH increases to  create more  basic solution,  the FAC shifts towards the
hypochloride ion (OCT).
2Br"
Br,
c.
BrOH
+
+

+
ci2—
H90 — -
£.
ci2—
Br2 +
Br OH

BrCl
2 Cl",
+ H+

+ HOC1 ;
                                    3-15

-------
     The bromlnated species formed in seawater given the above equilibrium
shift is shown in the following equation (9).
                      Br"  +  3 CIO"	> Br03~  +  3 Cl"
     Johnson (11) in discussing the chlorination of seawater stated that
chlorine would react with the bromine present in natural seawater to produce
HOBr; likewise, the chlorine would react with the iodide present in natural
seawater to produce HOI.  These reactions will go to completion rapidly, in
addition, further oxidation of these two species will occur resulting in the
rapid formation of I03" and the slower formation of Br03 ~.
     In the presence of ammonia, bromine formed during the oxidation of bromide
by chlorine or chloramines will react with ammonia to form bromamines.   The
relative quantities of bromamines and chloramines are kinetically rather than
equilibrium controlled.  Because the presence and formation  of these halo-
amines are a function of reaction kinetics, the predominate  chloramine  is
monochloramine (NhUCl) and the predominate bromamines are dibromamine (NHBr?)
and tribromamine (NBr3) (10).   Sugam and Helz (8) reported that the conver-
sion of HOC1 to HOBr in seawater, in the absence of ami no-nitrogen, reaches
99% completion in less than 10 seconds at pH 8; at lower pH  it reaches  com-
pletion even more rapidly.  Therefore, if a total conversion of chlorine to
bromine 1s assumed, Figure 4 shows that the distribution of  bromine species
present in seawater is a function of both pH and the logarithm of the initial
mole ratio of ammonia to bromine.  The data presented identifies species
which will  be present after 1  to 2 minutes of contact time and the lines
Indicate equal  equivalent concentrations (1).
     Figure 5  is similar to the chart developed by Davis et.al,  (12) to pre-
sent the theoretical degradation of chlorine as a result of chlorinating
natural seawater.  The decay of diatomic chlorine gas occurs between levels
I and II;  this reaction occurs rapidly and  goes to completion within a few
seconds after  the addition of chlorine.  Between levels II and  III the chem-
ical composition and abundance of products formed is a function of the physi-
cal and chemical parameters of the water, including, but not limited to,
temperature, pH, ammonia, and bromine available as reaction components.  Spe-
cies found  in  level  IV  include halogenated organic constituents which may be
formed at either level  II or III or both.
                                   3-16

-------
I

~o
             o
             ID
             Oi
 o
 -h


 O

 (0


 CX>
 r*-
 »jr
 O


 z
 re
(jj

 rl-
 O

 en

OJ
            3
            •a
            c
                                                                    6

                                                                    pH
                                                                                                    10
                                          Figure 4.  Principle species of bromine and  bromamine

-------
I

CO
                           II
III
                           IV
                                                                         Cl.
HOCl.OCl", NaOCl



NH2C1, NHC12, NH2Br,

NHBr2, BrO", HBrO
                                               Halogenated Organic
                                               Constituents
                                                                          CT,  Br'
                                 Figure  5.  Degradation processes for chlorine in saline waters

-------
     A charge balance results as one atom of Cl  passes from level  I  to V for
each atom of Cl  that passes from level  I  to II,  or in reduction or replace-
ment reactions in which Cl" is released at any of the other levels between I
and V.
     In their discussion of the reaction  of chlorine upon various  organic spe-
cies Jolley et,al. (13) presents several  chemical  equations to  describe the
formation of various chlorinated hydrocarbons.   Portions of their  work is
presented in the following narrative.
     When chlorine reacts with organic substances such as proteinaceous mater-
ial, found in bacterial cell  walls,  a  chlorine substitution reaction  can
occur leading to the formation of N-chlorinated  proteinaceous  material.  If
the organic substance involved in this substitution reaction is an amine the
reaction formula will appear as follows:
                                               H
                          R-NH2  +  HOC1	>R-NC1  +  HOH
Likewise, if the organic substance involved is an amide the reaction  formula
will appear as follows:
                         0                        0
                     R - C - NH2  +  HOC1  —>• R - C - NCI  +  HOH
The kinetics of the formation of the N-chloro compounds is considerably slow-
er with amides than with amines.
     The major portion of soluble organic matter in cooling water  is  made up
of humic material.  Humic material is a generic type of organic substance
which is classed according to solubility.   These materials are complex poly-
mers which range  in molecular weight from several hundred to many  thousand
grams per mole.   They are made up of various aromatic and alicyclic  noieties
containing alcoholic,-carbonyl, carboxylic, and phenolic functional  groups.
Phenols and aromatic acids are readily chlorinated in aqueous  solutions by
HOC! or OC1".  Chlorine substitution reactions with phenolic compounds and
aromatic organic acids are shown in Figure 6.
                                     3-19

-------
C02H
C02H
             +  HOC!
                                                  HOH
                                          Cl
                                     C02H
      OH
              HOC!
                                          OH
             HOH
                                     Cl
      CO~H
        2
              HOC!
                               Cl
         Aromatic  Organic  Acids
 OH
               HOC1
 OH
               HOC1
      OH
            Phenolic Compounds
      C02H
      C02H
                                                  HOH
                                     OH
                                           Cl
                                                + HOH
                                     OH
             HOH
                                           OH
                                      Cl
     Figure  6.   Chlorine  substitution reaction


                      3-20

-------
     A possible pathway for chlorine substitution reactions with humic mater-
ial is the haloform reaction.   This reaction appears as follows:

                              0               0~
                          R - J - CH3	> R - C  =  CH2  + H+
                         0"                        0
                     R - C  =  CH2  it HOC!  	>R - C - CH2C1  + OH"
                              0"                0"
                          R - C - CH2C1 	>R - C  =  CHC1  +  H+
                         0"                          0
                     R-C  =  CHC1  +  HOC1	*R - C - CHC12  +  OH"
                              0                        0
                     -» -» R - C - CC13  +  OH"	>R - C-OH  +  CC13"

                          CC13"  +  H+—>HCC13

If the haloform reaction is the primary path of chlorine substitution with
humic material the principle organic species contained in chlorinated sea-
water would in all probability be chloro-organics such as chloroforms (13).
In seawater containing significant quantities of bromide ions (67 mg/1),
humic material will react more preferentially with the bromide ions to form
bromo-organics, thus impeding chloroform formation.   Since HOC1 is readily
converted to HOBr in the presence of bromide ions little or no chloroform is
expected to occur in chlorinated seawater.   The mechanisms by which bromo-
form is produced is not well understood; however, reactions similar to those
postulated for chloroform formation are likely to occur.  The predominant
species identified by Carpenter and Smith (14) are bromoform and, to a less-
er extent, chlorodibromomethane.   According to these authors, the presence
and intensity of light and particulates will affect the production of bromo-
form; whereas temperature does not appear to be a variable.
 Comparison of Identified Chlorinated Seawater Species to the list of 129
 Toxic Pollutants
      Data presented in  previous  sections of this document indicate that when
 chlorine is added to seawater,  bromide present  in the seawater is oxidized
 by the chlorine and the resulting species  formed are brominated compounds
 analogous to chlorinated species found in  fresh water.   In addition to  these
                                      3-21

-------
compounds, which are formed by replacement reactions, are a wide variety of
other species formed by a number of different types of reactions.  These re-
actions and the compounds formed are dependent on the presence of various
contaminants and/or pollutants in the intake water; therefore, the composi-
tion of the chlorinated discharge water is to a large degt?e dependent upon
the composition of the original intake water.  This fact in itself implies
that the composition of chlorinated discharge water is site and time speci-
fic.  Some of the more typical compounds that may be found in the chlori-
nated discharge waters are bromamines, chloramines, chloroforms, bromaforms,
and halogenated organic compounds.
     An example of the complexity of predicting and/or evaluating the con-
stituents found in chlorinated sea water can be shown by observing the re-
action modes and compounds formed in sea water containing N-halamines.
Kovacic et.al.  (15) in their studies of N-halamines, such as N-bromamines
and N-chloramines, indicate that they may act as a stimuli  for the formation
of various classes of organic compounds.  They attributed this to the fact
that the nitrogen and halogen act as sites for chemical  reactions and that
these reactions can occur in quite diverse manners.
     Examples of the diverse reaction modes are as follows  (15):
     •   The nitrogen component may act as a cation (bicyclic rearrange-
         ment), anion (hydrazine formation), radical (photolysis and addi-
         tion alkanes), radical cation (Hoffman-Loffer reaction), and a
         base (nucleophllic substitution).
     •   The halogen component may act as a cationic (halogenation), anion-
         ic (Grinard reaction), and radical (photolysis).
     •   When N-H is present reactions which are typical  to this structure
         may also be observed.
     The organo-chlorides formed by reactions such as those shown in Figure
6 are included in the list of 129 priority pollutants.   These priority pol-
lutants which include chlorinated species of benzene, ethane, ether, and
phenol to name a few^ could as Jolley et.al. (13) suggests  be readily form-
ed 1n a chlorinated aqueous solution provided the parent organic species
are present.  Various organo-bromides analogous to these organo-chlorides
may also be formed.  The formation of such species may,  as  Kovacic et.al.
(15) suggest , result because of the presences of organic halamines.  The
brominated species do not enjoy the notoriety that organo-chlorides have
received; however, they may be as toxic.
                                       3-22

-------
     At this time no quantitative studies of chlorinated seawater have been
completed.   Therefore, any prediction of exact compounds and their respec-
tive compositions would include a great deal of supposition.   However,
given the proper intake conditions any one or a number of substances  con-
tained in the list of 129 toxic pollutants may occur or exist in  chlorinated
discharge water from power plant cooling systems.   A preliminary  qualitative
characterization of compounds found'in chlorinated seawater  was conducted by
Bean et.al. and is presented in Section 5.0 under the heading of  "Identifi-
cation of Potentially Toxic Species".
                                     3-23

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                                SECTION 4.0

           EVALUATION OF AMPEROMETRIC TITRATION FOR DETERMINATION
           OF RESIDUAL CHLORINE IN SEAWATER
     The determination of free and combined chlorine has historically been
done with applications in drinking ajid waste waters.  The requirements and
problems associated with monitoring chlorine residuals in power plant cool-
ing waters are considerably more complex.  This is particularly true when
seawater is  used as the coolant.  The chemistry of chlorine in seawater shows
little  resemblance to that of either fresh or waste waters.
     A  number of methods for determining chlorine residuals are available.
The most widely accepted is the amperometric titration method.  This method
for the determination of free available chlorine and combined chlorine spe-
cies in water has been considered the standard for many years.  Since it was
first reported by Marks and Glass (16) in 1942 it has become the most widely
used method  for chlorine determination (17,18).  Recently the amperometric
titration method has become suspect when used for chlorine determinations
in seawaters (11,19).
     This section provides; (1) a general discussion of the amperometric
titration method; (2) a brief discussion of iodine chemistry as it relates
to chlorine  determinations in seawater; and (3) an assessment of the methods
accuracy, precision and interferences when used in seawater determinations.
Areas where  further research is required and a brief discussion of alterna-
tive methods is also included.
General Method Description
     Amperometric titration has  been used to determine total  residual  chlor-
ine and also to differentiate  between free  and combined available  chlorine
in all  types of waters.   Two  slightly different  techniques  are  employed;  a
forward titration (generally  considered  the standard),  and  a  backward  titra-
tion.   The  difference is  in the  order of chemical  additions.   In the back  ti-
tration, phenylarsineoxide  (PAO)  is  added in excess  and a biiodate  solution
is used as  the  titrant; whereas  in  the  forward titration biiodate  is added
                                    4-1

-------
1n excess and PAO is used as the titrant.   This section will  deal  only with
the standard forward titration method.  The interferences and limitations
are similar between the two methods.
     The principle  of  amperometric  titration is an adaptation of polarogra-
phic principles.  When the cell of the titrator is immersed in a sample con-
taining chlorine or other oxidants, current is generated; but as phenylarsine-
oxide is gradually added, the chlorine is  neutralized and the generation of
current ceases.  The determination of free available chlorine is done between
pH 6.5 and 7.5.  In this pH range reaction of combined chlorine is slow.  For
the determination of combined chlorine, potassium iodide (KI) and buffers are
added in the proper amount to buffer the solution to pH 3.5 to 4.5 and acti-
vate the slower reacting species.  Monochloramines react more readily than
dichloramines; this tendency provides a means for determining the two species.
The addition of a small amount of KI (in the neutral pH range) enables an
estimation of monochloramine concentration.  Reducing the pH to the acid range
while increasing the KI concentration allows for the separate determination
of dichloramine content.
            i
     Phenylarsine oxide (PAO) is used as the reducing agent (the titrant in
forward titrations, and added in excess in back titrations) for free chlor-
ine or \2 determination by the following reactions (20):
         C6 H5 As 0 + C12 + 2H20 ~*-C6 H& As 0(OH)2 + 2 HC1
         C6 H5 As 0 +  I2 + 2H20—*-C6 H5 As 0(OH)2 + 2 HI
The PAO is stable even in dilute solutions.  A special amperometric cell is
used for detection of the end point.  The  cell unit is connected to a micro-
ammeter and recorder for end point determination.  The cell unit generally
consists of a noble metal electrode and reference electrode.
     Numerous variations of amperometric titration setups are in use in dif-
ferent labs or produced by different instrument manufacturers.  Instrument
manufacturers have provided automated titration apparatus for the chlorine
determination for many years.  Primary application has been to drinking and
waste waters.  The analytical requirements are for the measurement of mini-
mum chlorine residuals in drinking and waste waters as applied to disinfec-
tion.  Power plants cooling waters however, are required to be monitored for
maximum chlorine residuals for the protection of aquatic organisms near the
discharge point.  This fact makes it necessary for power plant monitors to
analyze chlorine residuals more accurately at lower levels.
                                     4-2

-------
Iodine Chemistry
     The use of iodide salts in the determination of chlorine species is
primarily to catalyze normally sluggish or negligible response to certain
oxldant fractions.  The salts are also employed to control  ionic strength,
to retard volatilization, or to serve other functions.   The iodide salts
are used in all the generally accepted analytical methods.   Therefore,  er-
rors introduced by imperfect iodine behavior will effect all methods.
     The generalized iodide - halogen produced oxidant reaction can be
written as:
         R-X + 21" + H"1" — »-I2 + R - H + X"
where X represents a halogen atom.  For strong oxidant  (e.g., HOC1 , HOBR
or NH2 Cl) the reaction proceeds to the right even at neutral pH.  For  more
inert oxidant  (e.g., NHC12) the reaction is accelerated only by the addi-
tion of I" and H+ ions.  It is this principle which allows  for the selective
determination of different oxidant fractions.
     It is important to note that all bromine oxidant species, which may
be present in chlorinated seawater, are unstable with respect to the iodine
species.  They are all capable of reacting quantitatively with I" to form
Io, \2~ and lOo". although the reaction rates for several  oxidant species
conversions are not known.  The relative concentrations of iodine species
is represented by the following equation:
In amperometric titrations this is extremely important because the elec-
trode is most sensitive to I2 (2l)
     Many potential sources of error may enter into the analysis of chlor
ine produced oxidants at low concentrations due to iodide reactions with
chlorinated seawater.  Among these potential sources of error are: those
from naturally occurring iodate in the seawater ; other oxidants; volatili
zation and reaction with organic matter.  Only the first two will  be dis-
cussed here.  Volatilization is considered a technique error and can be
minimized by proper handling and prompt analysis of the sample.   Organic
matter is a more common interference in wastewaters than in seawater.

                                     4-3

-------
     Natural seawater contains about 0.06 mg/1  of elemental iodine.   Fresh
water lakes and rivers contain considerably less (on the order of 0.002 mg/1).
Wong and Brewer (22) have reported that the primary iodine species in oxygen-
ated surface seawater is I03~.  Thus if the analysis is performed by a method
which measures I03~, then a background level will be measured.  In the case
of amperometric titration 10," is too inert to be detected, however,  when  the
KI solution is added the I03" will react to form I2 which will be detected.
Fabian (23) and Carpenter, et.al. (19) both report this occurrance and Fabian
presents rate equations for the reaction.
     There are many potentially interferring oxidants which can occur in
chlorinated seawater.  Table 7 lists some of these.  Fortunately these will
react only slowly under normal analytical procedures.  However proper tech-
niques must be employed at all times if gross interferences are to be mini-
mized.
                     TABLE 7.  POTENTIAL INTERFERRING
                               OXIDANTS
                          S2082"              Br C12
                    NBr
                    Br2
HOBr                NHBr
                          Mn04                Br2
                                                  2
                          OBr"                NH2Br
                          Br03"               HNO
                          Mn04"               Cu+22
                          Mn02                Fe+3
                          Br C10"
                                    4-4

-------
Limitations and Interferences
     The limitations and interferences to which the amperometric titration
method is subject are dependent upon the specific chemical  species  present
in the water being analyzed.   The species which may be found in chlorinated
seawaters have been identified in Section 3.0.   Those interferring  compounds
associated with the iodide chemistry have been  discussed in the preceding
paragraphs.  This section consists of a review  of the accuracy and  precision
of the method; the specific chemical interferences; the mechanisms  by which
they affect the determination and the specific  interferences as they relate
to seawater chlorination.
     Accuracy and Precision
     The amperometric titration method requires a high degree of operator
skill for accurate results.  The method is susceptible to mechanical  as well
as chemical interferences.  Crecelius, et al.,  (24) in an as yet unpublished
study, reports errors caused by different methods of handling and treating
samples.  The order of addition of chemicals  was of major significance in
introducing errors to the analysis.  Crecelius  recommended the mixing of KI
with buffer before addition of the sample.  Other mechanical errors may be
introduced by exposure to light and volatilization of sample and reagents.
These all may be minimized by proper analytical techniques and careful and
prompt analysis of the sample.
     Due to the highly unstable nature of chlorinated water samples only
limited testing of the procedure by multiple  laboratories have been under-
taken.  One such study, reported in Standard  Methods (17), involved the ship-
ping of solid synthetic unknowns.  The individual laboratories mixed the sol-
ids following instructions and then immediately performed the analysis.  Re-
sults of this study (which involved only fresh  water and therefore  shoul'd be
considered to represent the best accuracy and precision obtainable  by the
method) indicate that the relative error, between laboratories, for the de-
termination of free chlorine was 25% and for  total  available chlorine was 8.5
to 8.8%.  Standard deviations, among the laboratories were 42.3% for free
chlorine and 12.5 - 24.8% (dependent upon concentration) for total  available
chlorine.  These values were for levels of chlorine from 690 to 1830 vg/1-
Components present in chlorinated seawaters which cause interference to the

                                    4-5

-------
 method may  act  to  both  reduce efficiency and increase the standard deviation.
     Several alternative methods exist for the determination of chlorine,
 some of these methods are: chlorine flux monitor, membrane probe amperome-
 try, specific ion electrode, iodometric methods, DPD (and other colorime-
 trlc methods) and others.  Each is considered less accurate or reliable than
 the amperometric titration method.  The DPO-Ferrous titrimetric method has '
 been mentioned as valuable in that it detects only free chlorine.   However,
 1n seawater where Br" is present, this selectivity is reduced.  It may not,
 by present analytical methods, be possible to determine only free chlorine
 residuals in seawater.
     Further research into the accuracy and precision of amperometric titra-
 tion, and other analytical methods, are required.  Studies specifically
 directed to monitoring chlorine in seawaters are needed, and only recently
 have programs been undertaken,  A report, prepared for EPRI by the Public '
 Service Electric and Gas Company and the University of Maryland, which is
 near release,looks critically at many of these methods as they relate to
 seawater.   In addition, a recent study, currently under investigation by
 the power industry, evaluates the accuracy and precision of the ampero-
 metric titration method at four selected power plants utilizing different
 types of waters for cooling.   Two of these cooling waters are from fresh
 water sources; one from esturine waters; and one from seawaters.  Eight
 to ten participants, all using their own amperometric instruments, are
 analyzing identical samples at each of the four sites.   Data are currently
 being compiled and, unfortunately, are not available for incorporation in
 this report.  The development of more precise methods for chlorine deter-
minations are also necessary if it is concluded that chlorine is the major
 toxic material needing monitoring.  Section 5.0 of this report presents
 toxicological  data and makes some recommendations as to which compounds are
 toxic and at what levels.
     Chemical  Interferences
     Standard  Methods (17) identifies compounds  which interfere with  the
analysis of chlorine compounds by the amperometric titration  method.   The
Interferences  identified are for fresh or wastewaters and  do  not include
                                   4-6

-------
compounds found in seawater.  Accurate determinations of free chlorine are
not obtainable in the presence of nitrogen trich^onne (NCl^) or chlorine
dioxide (17).  Both of these species titrate partially as free chlorine.
NCK also titrates partially as dichloran.ine ciusing positive errors to both
these fractions.   Seawater nitrogen however, is rarely in the form of NCK.
During each determination organic chloraniines are also partially titrated.
Mono- and di-chloramines interfere in a positive manner with each other (17).
     Copper and silver (as sulfate and ions respectively) can cause inter-
ference.   Copper interferes by plating out on the electrodes and has been
noticed after heavy copper sulfate treatment in reservoirs.   Silver ions
act to poison the electrode (17).  Concentrations of these metals in sea-
water are generally very low, thus have little interference.
     At pH 7 and no KI (the conditions traditionally used for free chlorine
detenmnations) other free halogens, specifically bromine are detected.  Be-
cause seawaters contain relatively high concentrations of bromide ions,
which when chlorinated form free bromine, this is of major importance (25).
At these conditions bromamines and HpOo give non-quantitative responses also
(25).  Bromamines are common chlorinated seawater constituents where amines
are present in feed waters.  The bromamine reaction in the titration is
relatively slow; this may reduce the interference and accounts for the non-
quantitative nature of the interference.  The presence of H^Op has not been
confirmed in any significant quantities however.
     Other compounds which have been reported to cause interferences in-
clude Br CL" and Cl  On"".   These give non-quantitative results at pH 4.2 with
250 mg/1  KI added.   Free bromines, chlorine, chloramines, bromamines and
Hp02 are also determined (25).   The non-quantitative nature of many of these
interferences make them impossible to remove.
Interferences Particularly Related to Seawater
     Many of those compounds identified in Section 3.0 as typical of chlor-
inated power plant seawaters are also compounds which interfere with the
amperometric titrations.   Some of these, specifically bromamines, are the
dominant species in chlorinated seawaters.   These interferences make it
impossible to clearly separate free chlorine and bromine from the interfer-
                                    4-7

-------
ring species.  The non-quantitative nature of these interferences make even
the determination of total oxidant by the amperometric titration method a
formidable task.
     The data available on the amperometric titration method, as it is ap-
plied to determinations in seawater, does not allow for quantitative deter-
minations of accuracy and precision.  There are at present no accepted methods
for eliminating the effects of the interferring compounds.  It is likely that
totally new procedures will need to be developed if the acutal quantities of
free chlorine residuals need be known.  Section 5.0, which discusses the tox-
idty of various compounds from chlorination of seawater, indicates that many
other compounds are also toxic.  The amperometric titration method may be suf-
ficient to determine levels of total oxidants (primarily bromine and halo-
genated amines) that are potentially toxic in cooling water discharges.
These values, however, should not be confused with free chlorine residuals.
                                    4-8

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                                SECTION 5.0

         TOXICITY OF COMPOUNDS FORMED BY CHLORINATION OF SEAWATER

     This section identifies and discusses the various chemical  species
formed, their relative toxicities, and the specific marine organisms af-
fected by the addition of chlorine to seawater.  Particular emphasis is
placed on those chemical species identified as typical of or likely to be
present in power plant cooling water discharges as delineated in Section
3.0.
Definition of Toxicity
     Prior to introducing and discussing toxicity it is necessary to become
familiar with the terminology commonly used in the field of toxicology.
There are several ways to define and categorize toxic effects, as well as,
a number of techniques used for conducting toxicity tests.  Likewise, the
results of these toxicity tests are expressed several different ways.  The
following tables: 8, 9, and 10, originally presented by Burton (26), sum-
marizes the most commonly used methods of categorization, testing technolo-
gies and the terminology used to report results.
     Table 8 identifies the general categories of toxic effects.  By simpli-
fying the information contained in this table it is possible to form two
general categories of toxic effects:
     •   Acute toxicity which is generally lethal
     •   Chronic toxicity which may be either lethal or sublethal.
     The other categories listed are used more as descriptive words to iden-
tify the degree and effects of toxicity on the test organism.
                                    5-1

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                TABLE 8.  GENERAL CATEGORIES OF TOXIC EFFECTS
         Acute - Involving a stimulus severe enough to bring about a re-
              sponse speedily, usually within two to seven days for fish.
         Subacute - Involving a stimulus which is less severe than an acute
              stimulus, which produces a response in a longer time, and may
              become chronic.
         Chronic - involving a stimulus which is lingering or continues for
              a long time, often used for periods of about one tenth of the
              life span or more.
         Lethal - causing death, or sufficient time to cause it, by direct
              action.
         Sublethal - below the level which directly causes death.
         Cumulative -  brought about, or increased in strength, by succes-
              sive additions at different times or in different ways.
         Delayed - symptoms do not appear until an appreciable time after
              exposure-, often the response is triggered by occurrence of
              some other stress.
         Short-term -  acute but more indefinite
         Long-term - chronic but more indefinite.
     Table 9 gives the four techniques generally used for conducting toxi-
city tests.  These are laboratory tests that may or may not produce similar
results as in a natural marine environment.   It is recommended that only the
continuous flow or flow-through technique be used for chlorine toxicity stu-
dies with macroinvertebrates and fishes, with exception to chlorine decay stu-
dies where exposure periods are relatively short.
                                    5-2

-------
                TABLE 9,  TECHNIQUES GENERALLY USED FOR CONDUCTING
                          TOXICITY TESTS
         Static Technique - test solutions and test organisms are placed in
              test chambers and kept there for the duration of the test.
         Static Recirculation Technique - similar to the static technique
              except that each test solution is continuously circulated
              through an apparatus to maintain water quality by such means
              as filtration, aeration, sterilization and returned to the
              test chamber.
        Static Renewal Technique - similar to the static technique except
              that the test organisms are periodically exposed to fresh
              test solution of the same composition usually once every 24
              hours by transferring the test organisms from one test cham-
              ber to another.
         Continuous Flow or Flow-Through Technique - test solutions flow in-
              to and out of the test chambers on a once-through basis for
              the duration of the test.  Two procedures can be used: (1)
              large volumes of the test solutions are prepared before the
              beginning of the test and these flow through the test cham-
              bers and (2) fresh test solutions are prepared continuously
              or every few minutes in a toxicant delivery system.
     Table 10 presents the terminology most commonly used for expressing the
results of toxicity tests.  It should be noted that time and concentration
are inseparably linked in toxicity tests; hence, time should be stated in
order to give meaning to the toxicity data being reported, e.g. 24-h LD50,
which is the dose of a toxicant which is lethal  to 50% of the test organ-
Isms in 24 hours.  The ILC50 term is ambiguous and should incorporate two
additional terms to fully express the test results, e.g.  96-h ILC50 (3,180)
where the 3 would represent the number of exposures and the 180 would be the
total exposure time.
                                    5-3

-------
   TABLE 10.  TERMINOLOGY USED FOR EXPRESSING RESULTS OF
              TOXICITY TESTS
LC50 - median lethal concentration of a toxicant in solution which
     is lethal to 50% of the test organisms.
LC50 - median effective concentration of a toxicant in solution at
     which a response other than death occurs to 50% of the test
     organisms.
LD50 - median lethal dose of a toxicant within the organism which
     is lethal to 50% of the test organisms.                     ,
ED50 - median effective dose of a toxicant within the organism at
     which a response other than death occurs to 50% of the test
     organisms.
LT50 - median lethal time.  Used for mortality time in fixed concen-
     trations.
                                                                 i
ET50 - median effective time.  Used for response time other than
     death in fixed concentrations,
TLm, TLm, TLjjg, TL50 - median tolerance limit.  Term used primarily
     by U.S. pollution biologist.  Equivalent numerically to LC50.
LL50 - median lethal level.  For tests which yield mortality data
     where neither concentration or dose applies, e.g. tests with
     temperature.
EL50 - median effective level.   For tests which use a response
     other than death where neither concentration or dose applies,
     e.g., tests with temperature.                                ,
ILC50 - intermittent lethal concentration of a toxicant in solu-
     tion which is lethal  to 50% of the test organisms during in-
     termittent exposure tests.
                                                (Continued)
                           5-4

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                     TABLE 10.  (Continued)
         Other terminology - usually used to describe the concentration at
              which toxicity ceases or the point beyond which 50% of the
              population can live for indefinite time:
                   Incipient lethal level
                   Ultimate median tolerance limit
                   Lethal threshold concentration
                   Median threshold concentration
                   Asymptotic lethal concentration
                   Asymptotic threshold concentration
                   Others
Identification of Potentially Toxic Species
     It should be noted that chlorine, itself, is toxic to most aquatic or-
ganisms.  For this and other reasons chlorine is perhaps the most widely
applied chenical for biofouling control in power plant cooling systems.
White (20) reported that current biofouling practices for various cooling
circuits  in power plants involve two simultaneous types of chlorination:
continuous and intermittent.  Continuous, low level  chlorination (concentra-
tion typically 0.25 to 0.50 mg/1 (ppm) ) is used to control hard shell  or-
ganisms;  and intermittent chlorination (concentration typically 1.0 mg/1
(ppm) ) is used to control  soft form organisms.  These chlorine concentra-
tions within the cooling circuit will  normally control and/or curtail  bio-
fouling problems.
     As noted in Section 3.0 (Characterization of Chlorinated Seawater) it
is difficult, at best, to predict the  products formed by chlorinating  natur-
al seawater.   This is due to a number  of controllable and uncontrollable
factors which include: (1) the chemical composition of the seawater (espe-
cially ammonia and organic amines); (2) the amount of chlorine added;  (3)
the reaction duration; and (4) pH and  temperature.   However as noted,  the
equilibrium species formed are expected to be predominantly brominated  com-
pouj\ds analogous to chlorinated species produced in fresh water.
   *>                                5-5

-------
     Preliminary  studies conducted by Sugam  (8)  and  Johnson (11) indicated
that brominated compound, such as organic and  inorganic bromamines, are formed
1n chlorinated seawater and that these brominated  species may have toxic ef-
fects.  Their work  has been substantiated by the preliminary results of Bean
et.al.  (27)  in their analysis of chlorinated seawater discharged from a sys-
tem similar  to a  power plant cooling circuit.
     A cursory list of the chemical compounds  which  Bean et.al.   (27) Identi-
fied as being present in chlorinated seawater  is given in Table 11.  Because
this 11st is preliminary it is expected that the number and types of compound
identified will greatly increase as more data  become  available.
     The toxicity of the various chemical species  (particularly brominated
compounds) which  may be formed as a result of  seawater chlorination has not
been established; however, Bean (27) found that  the  principal constituents
found 1n chlorinated seawater is bromoform which is  one of the compounds
identified in the list of 129 priority pollutants.   Various other brominated
substances lisrted in Table 11 such as bromo biphenyls are also contained in
the same list, and  bromonaphthalene which have a chlorinated analog are also
contained in this list.
         The fact that those compounds identified  by Bean et.al.  (27) are so
closely linked to species that have been previously  identified as being tox-
ic 1s indicative, that the conclusion reached  by Sugam and Johnson, of many
of the brominated species formed will be toxic may be indeed correct.

           TABLE  11.   A  PRELIMINARY LIST  OF  THE CHEMICAL CONSTITUENT
                       IDENTIFIED IN CHLORINATED SEAWATER
       1.
       2.
       3.
       4.
       b.
       6.
       7.
       8.
       9.
Bro.no form
Tri we Uiyl benzene
Naphthalene
Bromotriii.e thy 1 benzene
2-Mothylnaphthalene
1 ••f'.L'tbyl naphtha! ene
Riphenyl
Broinotetraline
Broniotetroniclhyl benzene
10.   Dimethyl naphthalenes
11.   Bromonaphthalene
1?.   Bromomethylnfiphth.il cues
13.   Bromobiphcnyls ami
     Broiiiodimethyl naphthalenes
14.   Phcnanthrene
If).   bron;othmethyl naphthalene
16.   Phthaliite Ester;
17.   Pyrene
18.   Bromoaceval
                                       5-6

-------
Identification of Toxic Levels and Aquatic Organisms Affected
     This sub-section presents information on the to;
-------
                            TABLE  12.  SUMMARY OF DATA ON TOXICITY OF CHLORINE TO MARINE ORGANISMS
I
ro

Data Point and Descriptive
Scientific Name Name
Plants:
N.G. Phytoplankton
N.G. Phytoplankton
Chlorophyta
Chiamydomonas sp.
Dunaisella terliolecia
Chrysophyta
Asterionella Japonica
Asterionella japonica
Chaetoceros decipiens
Chaetoceros didymum
Delonula confervacea
Skeletonema costatum
Skeletonema costal um
Thalassiosira nordenshoikii
Thalassiosira Pseudonana
Thalassiosira pseudonana
Thalassiosira pseudonana
Thalassiosira rotula
Chrysophyceae
Monochrysis lutheri
Rhodomonas baltica

Concen-
tration
(mg/1)

0.1
0.03

1.5
0.11

0.4
0.2
0.14
0.125
0.8
0.095
0.6
0.195
0.075
0.2
0.5
0.33

0.2
0.11

Duration
(min)

240
N.G.

5-10
1,440

0.27
2
1,440
1,440
0.6
1,440
1.7
1,440
1.440
6.8
0.3
1,440

1,440
- 1,440

Effect

71% decrease in productivity
50% decrease in photosynthesis

Decreased grwoth
50% decrease in growth

50% decrease in growth
50% decrease in growth
50% decrease in growth
50% decrease in growth
50% decrease in growth
50% decrease in growth
50% decrease in growth
50% decrease in growth
50% decrease in growth
50% decrease in growth
50% decrease in growth
50% decrease in growth

50% decrease in growth
50% decrease in growth
(Continued)

-------
                                              TABLE  12.   (Continued)
tn
  Phaeophyta
     Macrocystis  pyrifera
Invertebrate animals:

  Cnidaria
     N.G.
     Bimeria franciscana

  Annelida
     Phragmatopoma  californica
     Phragmatopoma  californica
  Mollusca
     Crassostrea  virginica

     Crassostrea  virginica
     Crassostrea  virginica
     Ostrea edulis
     N.G.
     Mylilus edulis
     Mylilus edulis
     Mytilus edulis

     Crepidula and  Littorina
     Acartia tonsa

     Acartia tonsa

     Acartia tonsa
     Acartia tonsa
     Acartia tonsa
     Eurylemora affinis
     Eurylemora Affinis
                                          Giant kelp
Sea anemone
Hydroid


Polychaete worm
polychaete worm


Oyster

Oyster
Oyster
Oyster larvae
Oysters
Mussel
Mussel
Mussel

Gustropods
Copepod

Copepod

Copepod
Copepod
Copepod
Copepod
Copepod
                      5-10        5,760       50%  decrease in photosynthesis
   1.0        21,600       No  effect
   2.5           180       Slight  decrease in  growth


   0.2             5       17% decrease  in sperm motility
   0.4             5       70% decrease  in sperm motility


   0.2           N.G.       ".46% decrease in ciliary beat
                            rate
   1.0       20-90         Pumping threshold
   0.18      4,320         50% decrease  in time open
   0.5           2         Swimming stopped
   2.5          10         No  effect  (30°C)
   1.0      21,600         100% mortality
   2.5       7,200         100% mortality
0.02-0.05     N.G.         Young won't attach-attached
                            ones will  move
   0.2        N.G.         Stops growth
   0.75          2         30% mortality @ 20°C after
                            96 hr
   0.75          2         70% mortality @ 25°C after
                            96 hr.
   1            120         50% mortality
  10.0           0.7       50% mortality
   2.5           5         90% mortality-after 3 hr.
   1            300         50% mortality
  10.0           2         50% mortality
                                            (Continued)

-------
                                    TABLE 12.  (Continued)
  Pseudodiaptomus  coronatus
  Pseudodiaptomus  coronatus
  Balanus improvisus
  N.G.
  Elmlnlus modestus
  Elminius modestus
  Corophlum sp.

  Gamnarus tlgrinus
  Melita nilida
  Mellta nilida
  Callinecles sapidus
  Callinecles Sapidus
  Crangon septemspinosus
  Crangon septemspinosus
  Crangon septemspinosus
  Palaemonetes pugio

Ectoprocta
  Bugula sp.
  Bugula sp.
Echinodermata
  Strongylocentrotus  pur-
   puratus
  Urechis caupo
  Urechis caupo
Chordata
  Botryllus sp.
  Molgula sp.
Copepod
Copepod
Barnacle larvae
Barnacles
Barnacle nauplii
Barnacle nauplii
Tube dwelling
 amphi pod
Amphipod
Amphipod
Amphipod
Blue crab
Blue crab
Sand shrimp
Sand shrimp larvae
Sand shrimp larvae
Grass shrimp
Sea urchin

Echiuroid
Echiuroid
 2.5
10
 2.5
 1.0
 0.5
 1
10

 2.5
 2.5
 2.5
10
 0.1
 0.15
 5
10
 2.5
 2.5
10


 0.125

 0.2
 0.4


10
 1
    45
     5
     5
21,600
    10
    10
   410

   180
   120
     5
 1,140
 5,760
   900
    10
     5
   180


 2,880
 1,440
     5
     5


 1,440
 4,320
50% mortality
50% mortality
80% mortality-after 3 hr.
Most dead
Threshold mortality
Heavy losses-no growth
No mortality after 24 hr.

25% mortality after 96 hr.
50% mortality
Some mortality
50% mortality
50% mortality
50% mortality
42% mortality
55% mortality
98% mortality-after 96 hr.


100% mortality
100% mortality


1-6% fertilization success

78% fertilization success
0% fertilization success
                                              100% mortality
                                              100% mortality
                                                                                            (Continued)

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                                               TABLE  12.   (Continued)
en
i
Vertebrate animals:
Pleuronectidae
Limanda ferruglnea
Pleuronectes platessa
Pleuronectes platessa
Pleuronectes platessa
Pleuronectes platessa
Pseudopleuronectes
americanus
Pseudopl euronectes
americanus
Pseudopl euronectes
americanus
1 Salmonidae
Oncorhynchus gorduscha
Oncorhynchus gorduscha
Oncorhynchus gorduscha
Oncorhynchus kisutch
Oncorhynchus tshawytscha
Oncorhynchus tshawytscha
Oncorhynchus tshawytscha
Oncorhynchus tshawytscha
Oncorhynchus tshawytscha
N.G.
Atherinidae
Menidia mem'dia
Menidia menidia



Yellowtail flounder
Plaice larvae
Plaice larvae
Plaice larvae
Plaice larvae
Winter flounder

Winter flounder

Winter flounder eggs


Pink salmon
Pink salmon
Pink salmon
Coho salmon
Chinook salmon
Chinook salmon
Chinook salmon
Chinook salmon
Chinook salmon
Young salmon

Atlantic silverside
Atlantic silverside



2.5
0.028
0.05
0.075
0.25
2.5

10.0

10.0


0.05
0.5
0.25
0.08
0.1
0.25
1.0
0.5
0.25
0.05

0.58
1.2



1,440
5,760
460
75
4,320
15

0.3

20


5,760
7.5
15
7,200
60
130
23
7.5
30
33,123

90
30



50% mortality
50% mortality
50% mortality
50% mortality
Mortality threshold
50% mortality

50% mortality

No mortality
\

50% mortality
50% mortality (13.6°C)
50% mortality (13.6°C)
50% mortality
Distressed-no mortality
Mortality threshold
Mortality threshold
50% mortality (11.7°C)
50% mortality (11.7°C)
Threshold mortality

50% mortality
50% mortality
(Continued)

-------
                                            TABLE 12. (Continued)
Clupeldae
Alosa aestl vails
Alosa aestivalis
Brevoortia tyrranus
Brevoortia tyrranus
Brevoortia tyrranus
Brevoortia tyrranus
Brevoortia tyrranus


Blueback herring
Blueback herring
Atlantic menhaden
Atlantic menhaden
Atlantic menhaden
Atlantic menhaden
Atlantic menhaden
larvae

0.67
1.2
0.22
0.7
0.21
1.2
0.5


60
15
60
10
300
30
3


50% mortality
50% mortality
50% mortality
50% mortality
50% mortality
50% mortality
0 mortality

CJl
I
ro
Gasterosteidae
   Gasterosteus aculeatus

Ameiuridae
   Ictalurus catus
Cyprinidae
   Notemigonus chrysoleucas
Bothidae
   Paralichthys sp.
Mugilidae
   Mugil cephalus

Miscellaneous
   N.G.
                                     Threespine stickle-  0.09-0.13
                                      back
                                     White catfish
                                     Golden shiner
                                     Flounder
                                     Striped mullet
                                      juveniles
                                     Marine fish
 0.1
0.03-0.23
 0.3
 0.3
 r.o
             5,760       50% mortality
2,880       50% mortality
5,760       50% mortality
    5       Threshold mortality
    5       Threshold mortality
    1       Slight irritant response

-------
    TABLE 13.  SUMMARY OF THE TOXICITY OF VARIOUS CHEMICAL SPECIES TO MARINE ORGANISMS
OJ

Chemical
Compound
Chlorine





-



Chlorine





Chlorine

Chlorine






Test
Organism
Mussels

Barnacles &
sea anemones


Tunicates &
bryozos


Oncorhynchus
kTsutch
0. tshawytscha

0- gorbuscha
0. kisutch
Kuhlia
sandvicensis
Crassostrea
virgTmca
(oyster)



- -
Concen-
Test tration
Conditions (ppm)
CB.FS 2,5

1.0

10.0

10.0

10.0

CB.LS 0.08-0.1

=0.05

0.05
0.05
LS 1.0
10.0
CB.LS 0.01-0.02


0.2
. 0.01-3.0
0.01-0.05

Remarks
Total kill, 5-8 days, constant
exposure, all organisms
Some barnacles, all anemones
alive after 15 days.
All tunicates and bryozos killed,
1 hr/day exposure.
Incomplete kill of adult mussels
& anemones, h r/day exposure.
Some barnacles survived, 4 hr/day
exposure.
"Critical level" for 3-day exposure,
all species.
"Lethal limit," up to 23 days,
all species.
Maximum nonlethal .
Maximum nonlethal .
Slight irritant response. Violent
irritant response. (2 min exposure)
Sensitive to initial exposure, reduce
pumping and close valves; later develop
tolerance.
Reduce beat frequency of cilia, 21-22 C.
Causes no injury to tissue.
Interfers with normal functioning.
(Continued)

-------
                            TABLE 13.  (Continued)
    Chlorine
tn
    Chlorine

    Chlorine
Chlorine




Chlorine



Chlorine
                         Elminius         SB,LS
                          modestus
                          (barnacle
                          nauplii)
                         Ostrea edulis
                          (oyster larvae)
"fish"

Hacrocystis      CB,LS
  pyri f ers
 (marine Kelp)


"phytoplankton"  LS & FS
 (estuarine)
                             Bimeria           CB.LS
                              franciscana
                              (hydroid)

                             Cnlamydomonas sp.  SB,LS
                              (marine
                              plankton)

                             Skeletonema
                              costatum
                              (marine
                              plankton)
   0.5

   1.0


 2.5-5.0

 3.0-6.0

0.11-0.13

   1.0

  5-10
                              4.5
                              1.15

                             20.0

                            0.40-0.65

                              2.0
10 min exposure, "little effect."

"Significant decrease" in survival
after 10 min exposure.
10 min exposure, "little harm" at
temperatures as high as 30°C.
12 & 20 min exposures, "little
effect;" = 19 C.
Lethal.

No effect on photosynthesis, 5
days.
50% reduction of photosynthesis, 4
days.

Concentration not measured; 50-91%
reduction of photosynthesis after
passing through power plant believed
due to chlorine.

No effect after 3 hr exposure.
                 Time-lag in growth, 5-10 min exposure

                 Growth affected, recovered in 9 days.
                 Adverse effect on growth, 5 min
                 exposure.
                 No growth 30 days after treatment.


                            (Continued)

-------
TABLE 13.  (Continued)
Chlorine



Sodi urn
hypochlorite
(chlorox)
Sodium
pentachloro-
phenate
Sodi um
pentachloro
„, phenate
en

Sodium
pentachloro-
phenate









"marine FS
organisms"


Kuhlia LS
sandvicensis

Kuhlia LS
sandvicensis

Crassostrea gigas LS
(oyster)



Mylilus LS
edulis
(bay mussel)









0.5



10.0
2.0

20.0


0.027


0.069
0.11
0.20


0.20

0.30

0.30

0.4

0.4
Continuous chlorination controls
marine organisms ; 5-6 ppm used during
shut-down. (Methods appliec are des-
cribed)
Violent reactive response.
Violent reactive response (L min
exposure).
Medium reaction, 2 min exposure


4.3% abnormal embryos in 48 hr.
x

72.4% abnormal embryos in 48 hr.
100% abnormal embryos in 48 hr.
12% abnormal embryos, 28 ppt
salinity

21% abnormal embryos, 24 ppt
salinity
17.6% abnormal embryos, 28 ppt
salinity
33.6% abnormal embryos, 24 ppt
salinity
22.1% abnormal embryos, 28 ppt
salinity
69.1% abnormal embryos, 24 ppt
                                            salinity
                                                              (Continued)

-------
                             TABLE 13,  (Continued)
en
i
Pentachlorophenol Macrocystls LS
pyritera
Sodium
pentachloro-
phenate
(Sanobrite)
Sodium
pentachloro-
phenate
(Santobrite)
Bromine
(kelp)
Macrocystis CB.LS
pyri tera
(kelp)
"mussel, anemones, SB, IS
barnacles"
CB.LS
Kuhlia LS
sandvicensis

2,66
1.0
0,3
0.1
1.0
10.0
1.0
1.0
10.0
Eliminated all photosynehesis in 4
days.
Eliminated photosynthesis in 2 days.
50% inactivation of photosynthesis
in 4 days
Ineffective.
Killed all organisms, 3 days.
Killed all anemones, tunicates, and
bryozos in 1 day; all barnacles in
3 days, all mussels in 5 days.
Killed all tunicates and bryozoa in
1 day; all anemones, mussels and
barnacles in 4 days.
No irritant response, (2 min exposure)
Violent irritant response.

LEGEND:
SB =
CB =
LS =
FS =
Static bioassay
Constant-flow bioassay
Lab study
Field study



-------
     In his discussion of the toxicity of chlorine on aquatic  life,Brung (30)
     cited a laboratory study with synthetic seawater.   This study demonstrated
     that phytoplankton (Cyclofella nana), when exposed to residual  chlorine
     concentrations of 0.150 mg/1  for more than 10 to 20 minutes, showed in-
     hibited growth patterns.  With residual concentrations of chlorine great-
     er than 0,45 mg/1 for 6 seconds exposure time, similar growth inhibition
     patterns occured.
     In recent studies conducted by Goldman et.al. (31) it was found that the
     metabolic activity of larval  zooplankton was seriously affected at chlor-
     ine residual levels below the level  of detectablHty (< 0.01 mg/1).   This
     was found as a result of exposing the larvas to chloramine in concentra-
     tions < 0.01 mg/1 for 30 minutes under controlled conditions.
     Another recent study by Erickson and Freeman (32) evaluated the effect
     of various chlorinated and brominated compounds on four species of marine
     phytoplankton.  They studied the toxic effect of chloroform and bromo-
     form on the phytoplankton and found  no noticeable impact occurred at
     concentration of 32 mg/1 for either  compound.  However they discovered
     that monochloramlne inhibits cell division at concentration as low as
     0.125 mg/1 utilizing seawater under  laboratory  controlled  conditions.
     Given the above information and data presented in the earlier portion
of this document, it is expected that various organo-bromides  analogous to
the organo-chlorides discussed in Section 3.0 (Characterization of Chlori-
nated Seawater) will be formed.  The toxicity of these brominated species
on aquatic organisms have not been clearly established.  However, since tox-
icity 1s a function of concentration and  time, and since bromamines are more
labile as a group than chloramines and are more readily reduced to their con-
stituents (Johnson (11) ^one could make the supposition that brominated spe-
cies may not be as toxic as the chlorinated analogs.   Assuming that both
species are present in equivalent concentrations, and that both have com-
parable toxicitles, the brominated species will  decay more quickly and con-
sequently its toxic effect will be dissipated more rapidly.
     Actual toxicity information on the various species formed in chlori-
nated seawater is scarce.  Currently, Battelle Pacific Northwest and the
University of Maryland are conducting independent studies to evaluate the

                                     5-17

-------
toxicity of compounds formed by chlorinating seawater.  The Battelle study
Involves the comparative assessment of toxicity between chloroform and bromo-
form on aquatic organisms.  Four marine water organisms (Quahaug, East Coast
Oyster, White Shrimp and Atlantic Menhaden), are being evaluated for bromo-
form toxicity.  Concurrently four freshwater species of fish (Blue Gill,
Small Mouth Bass, Channel Catfish and Rainbow Trout) are studied for their
reactions towards chloroform.  Both of these are in-situ,continuous flow
through studies.  Although preliminary data have been compiled, actual find-
Ings or conclusions are not currently available for inclusion in this report.
The University of Maryland was conducting similar biological studies except
their effort was directed preimarily at evaluating the "net toxic effects"
of chlorinated seawaters from power plants.  The completed report of their
studies have not been published at this time.  Preliminary communications
with the author revealed that: (1) bromoform may not be the most toxic con-
stituent from seawater chlorination because of its high volatility; further
studies are needed to characterize other brominated species; (2) Blue Crabs
are most tolerant to chlorination or products of chlorination; (3) oysters
and their larvae, being the most sensitive species to chlorination, are more
susceptible to chlorine toxicity at lower than at higher concentrations.
This 1s due primarily to oysters' inability to detect low chlorine dosages
and their ability to biosynthesize anaerobically under stress or at high
chlorine dosages.
Comparison of Toxic Levels with Levels Expected from Power Plant Discharges
     In his discussion of continuous chlorination as applied to power plant
cooling circuits, White (20) stated that, to achieve adequate biofouling pro-
tection, the concentration levels of free chlorine residual  at the condenser
tailpipes should be maintained at 0.25 to 0.50 mg/1 (ppm).  As previously
noted, at these levels, chlorine has toxic effects on certain marine organ-
Isms.  These levels are within the cooling circuit, and the  typical  power
plant cooling circuit is designed to retain the cooling water from 5 to 10
minutes.  Because of chlorine demand and/or decay, the majority of the free
chlorine residual will combine with other seawater components and form new
chlorinated organic species.
                                     5-18

-------
     In papers presented by Sugam (8) and Johnson (11), the decay of chlorine
by oxidation-reduction reactions with various halides and ami no-nitrogen com-
pounds present in seawater was discussed.  Both concluded that chlorine is
short-lived in seawater and that the major components in chlorinated seawater
would be oxidants of chlorine and bromine as well as organic and inorganic
halogenated amines.  Thus, the "free chlorine residual" would be converted
to "combined residual chlorines".  Other studies conducted by Carpenter et.
al. (9) and Hostgaard-Jensen et.al.  (33) resulted in similar findings.
Carpenter's work supported much of Johnson's findings regarding the presence
of a large amount of bromlnated species in chlorinated seawaters.
     Hostgaard-Jensen et.al.  (33) also concluded that chlorine decay could
occur as a result of reactions with organic material and other chemical spe-
cies present in seawater; thus, the chlorine could be reduced to organic ion-
ic and/or chlorides.  They then studied the decay of chlorine residuals in
cooling water upon discharge into water bodies.  In these studies they found
that laboratory experiments predicted chlorine residual concentrations approx-
imately twice as high as those actually measured in field tests.  In field
tests they found that the discharge water contained 1.0 mg/1 residual chlor-
ine and within 100 meters of the outfall the residual chlorine concentration
was between 0.05 to 0.10 mg/1.
     In his study of five California power plants Hergott et al. (12) found
that if a free chlorine residual concentration of 0.50 mg/1 (ppm) was main-
tained at the condenser tailpipes, the maximum total oxidant residual at the
outfall would be 0.16 mg C^/l which would decrease to approximately 0.09
mg C12/1 within 50 feet (15.3 m).
     The reduction in chlorine concentration from the cooling water outfall
to some distance away from the outfall is due to two factors:  chlorine decay
by chemical reactions and effluent dilution.  Both of these factors are of
Importance in analyzing the toxicity of chlorinated cooling water effluent.
     By comparing the chlorine residual concentrations in the outfall of the
power plant cooling systems discussed above with the toxicity information pre-
sent 1n the Toxic Level Section, it can be seen that the chlorine levels in
                                    5-19

-------
cooling water discharges can be toxic to certain marine organisms.   The de-
gree of toxicity is, however, dependent upon the organism exposed and the
exposure time.  The reaction of soft organisms,  slime and  sponges, to chlorine
is in some respects quite different than that of hard-shelled organisms, such
as mussels and barnacles.  Some organisms, which are identified in Tables 12
and 13, show great tolerances to high levels of chlorine for short exposure
times while they are quite intolerant to low level concentrations for long
exposure times.  Other organisms adapt readily to low level  concentrations
and long exposure times but respond violently to high levels for short  ex-
posure time.  It 1s for this reason that blofouling control  techniques  in-
corporate continuous low level chlorlnatlon 1n conjunction with intermittent
high level chlorination.
Qualitative Analysis of the Toxicity and Measurement of Pollutants  Formed
In Chlorinated Seawater
     This section will  discuss the information previously presented  and points
out areas where data gaps exist.   A discussion of the amperometric  titration
method and how well it can be used to measure oxidants from chlorination is
also Included.
     As pointed out by Johnson (11) the major problem that confronts the re-
search in determining the toxicity of compounds  found in chlorinated seawater
1s the Identification of chemical  species that are actually  present.  Accord-
Ing to Johnson the major species  of concern are:  bromine,  chloramines,  and
bromamines; each of these components have a high probability of causing toxic
effects to marine life.  Sugam (8) in his discussion of the  various  species
of chlorine produced oxidants supported Johnson's position.   They both  con-
cluded that chlorine was short-lived in seawater, and that in the absence of
amino-nitrogens in seawater (pH8)  the majority of the species measured  as
"residual chlorine" would be bromine.   When ami no-nitrogen is present the
formation of organic and inorganic halo-amines competes with the formation
of bromine.  The formation of halo-amines is favored kinetically by  high pH,
low salinity, high ami no-nitrogen  levels and high ami no-nitrogen to  chlorine
ratios.  Carpenter et.al. (9) in  their study of  halogen chemistry concluded,
as did Sugam and Johnson, that chlorine reacts with bromide  to form  bromine
                                    5-20

-------
species and chloride ions.  They further concluded that the halo-organics
formed by chlorinating seawater are likely to be brominated species.
     Currently, studies by the University of Washington, the University of
North Carolina, and Battelle Pacific Northwest are being conducted to iden-
tigy the various species formed by the chlorination of seawater.  Prelimi-
nary findings indicate that the chemistry involved is quite complex and that
the species formed are highly dependent upon the characteristics of the in-
take water (including water quality and salinity, season of the year, and
residence time in the cooling circuit).
     The results of these studies and toxicity testing of the various spe-
cies formed will be necessary in order to formulate any meaningful data on
the toxic effects to marine life.  If, however, assuming that the informa-
tion supplied by Sugam, Johnson, and Carpenter is indicative of the chemical
species found in chlorinated seawater and comparing this information with
current testing techniques, a number of interesting anomalies occur.  Sugam
(25), in more recent studies, found that these brominated species plus others
cause interferences in amperometric titration readings, and that bromamines
cannot be clearly separated from free chlorine or bromine.  Because the am-
perometric method measures bromine and iodine residuals in addition to chlor-
ine residuals, Hergott et al, (1) referred to the results of amperometric ti-
tration tests conducted on chlorinated seawater as "oxidant residuals" rather
than "chlorine residuals".
     The amperometric titration testing method was discussed in detail in
Section 4,0.  It is found that the amperometric titration method appears to
be adequate in any determinations involving toxic oxidants that may be pro-
duced by the chlorination of seawater.  Although the measurement of indivi-
dual species from chlorination may not be possible, a relatively accurate
determination of the total oxidants can be made.  As suggested by Johnson
(11) and discussed by Goldman et al.  (31) and Ericson et al.  (32), compounds
such as bromamines, chloramines and various other brominated species which
cause interferences to the method may have toxicities equal to or greater
than the chlorine itself.  If these compounds are perceived as total oxi-
dant residual rather than free chlorine residual, then the amperometric
titration method may be applicable.
                                    5-21

-------
     If it becomes necessary to monitor individual components in the cooling
water discharge stream, then more advanced analytical methods will  have to
be developed.  Concurrent with analytical method development, studies of the
toxicity of individual as well as combined components must be undertaken.
     Mattice and Zittel (28) developed a graph to show the toxicity of "resi-
dual chlorine" to marine organisms.  The graph summarzied data from various
other research studies.  Figure 7 presents a slightly modified version of
that graph.  This graph contains estimates of both acute and chronic toxicity
thresholds.  The implication of the graph 1s that 1f a dose-time combination
1s lower than the chronic toxicity threshold or to the left of the  acute tox-
icity threshold no mortality is likely to occur as a result of chlorinatlon,
Mattice and Zittel developed the "threshold line" using data which  were, for
the most part, 50 percent effect levels on either mortality or sublethal phy-
siological rates, and then adjusting the line to zero mortality levels.   As
shown on the graph, concentrations below 0.02 mg/1 have no lethal effect re-
gardless of an increase in exposure time.
     Comparing "free residual chlorine" levels developed by current practices
1n power plant cooling circuits with the toxicity threshold shown in Figure 7
1t can be seen that the target levels (0.25 -  1.0 mg/1)  developed within the
 cooling  circuit will  produce  "acute  toxic  effects" on marine life for exposure
                                                                     /
times greater than 2 1/2 minutes (at lower concentration limits), and less
than one minute (at the upper concentration limit).                   !
     As has already been discussed,if rather than measuring "chlorine resi-
dual" the amperometric titration method measure "oxidant residual"  and  if  the
effluent stream is shown to be toxic then current standards should  be revised
to place a limit on the "oxidant residual" rather than "chlorine residual"
1n the effluent stream.
                                     5-22

-------
en
i
no
OJ
                        10.
                   I   1  —
10



I
                    at
                    c
                    i-
                    o
                      0,01-
                      0.001
                            10
                              -1
                                      I  I
                          II    I~T pi    • i I   i     ill   |    ii

                        n          • 1          * 9         • 1
                      10°         101          ID*1         lO3


                                      Duration of Exposure (min)




                        Figure 7.  Toxicity of chlorine to marine organisms (22)
                                                                                                       10'

-------
                                  REFERENCES
 1.   Hergott, S.,  et.al.,  Power Plant  Cooling  Water Chlorination in Northern
      California, University of California,  Berkeley, UCB/SERL No. 77-3,
      August 1977.
 2.   Yu, H.H.S., et.al.,  Alternatives  to  Chlorination for Control of Condenser
      Tube B1o-Fouling,  Monsanto Research  Corp.,  EPA-600/7-77-030, March 1977.
 3.   Federal  Register,  Vol.  39, No.  196,  Oct.  8,  1974.

 4.   Todd, O.K., editor,  The Water  Encyclopedia,  Water  Information Center,
      1970.
 5.   Smith, F.G.W.,  editor, Handbook of Marine Science, Vol. 1, CRC Press,
      1974.
 6.   Strickland &  Parsons, A Practical  Handbook  of Sea  Water Analysis,
      Fisheries Research Board of Canada,  Bulletin No. 167,  2nd. ed., 1972.
 7.   Liptak,  B.C., editor, Environmental  Engineers Handbook, Vol. 1, Water
      Pollution, Chllton Book Company,  1974.

 8.   Sugam, R. and G.R. Helz, Speciation  of Chlorine Produced Oxidants in
      Marine Waters:  Theoretical Aspects.  Chesapeake Science, Vol. 18,
      No. 1, page 113-116.
 9.   Carpenter, J.H.  and  D.L. Macalay,  Chemistry  of Halogens in Seawater.
      Proceedings of the Conference  in  the Environmental Impact of Water
      Chlorination, Oak  Ridge, Tennessee,  October  22-24, 1975.
10.   Johnson, J.D.,  Measurement and Persistance  of Chlorine Residuals in
      Natural  Water.   Proceedings of the Conference in the Environmental
      Impact of Water Chlorination,  Oak  Ridge,  Tennessee, October 22-24,
      1975.
11.   Johnson, J.D.,  Analytical  Problems in  Chlorination of  Saline Water.
      Chesapeake Science,  Vol. 18, No.  1,  page  116-118.
12.   Davis, W.P. and D.P.  Middaugh, A  Review of  the Impact  of Chlorination
      Processes Upon Marine Ecosystems.  Proceedings of  the  Conference on
      The Environmental  Impact of Water  Chlorination.  Oak Ridge, Tennessee,
      October 22-24,  1975.
13.   Jolley,  R.J., G. Jones, W.W. PiH,  and  J.E.  Thompson, Chlorination of
      Organlcs in Cooling  Waters and Process  Effluents.  Proceedings of
      the Conference on  The Environmental  Impact of Water Chlorination,
      Oak Ridge, Tennessee, October  22-24, 1975.
14.   Carpenter, J.H., and  C.A.  Smith,  "Reactions  in Chlorinated Seawater",
      Water Chlorination Environmental  Impact and  Health Effects; Vol.  2,
      editor R.J. Jolley et.al., Ann Arbor Science, 1978.
15.   Kovacic, P.,  M.K.  Lowery,  and  K.W. Field, Chemistry of N-Bromam1nes and
      N-Chloramines.   Chemical Reviews,  1970, Vol. 70, No. 6, pp. 639-665.

                                     6-1

-------
16.  Marks, H.C. and Glass, J.R., "A New Method of Determining  Residual
     Chlorine", JAWWA  Vol. 34, 1942, pp. 1227-1290.

17.  American Public  Health Association, Standard Methods  for  the  Examina-
     tion of Water and Wastewater. 14th ed.,  pp.  322-325, 1975,

18.  American Society for Testing and Materials,  1977  Annual  Book of ASTM
     Standards. pp. 292-298, 1976.

19.  Carpenter, James A., et.al., "Errors in  Determination  of Residual
     Oxldants 1n Chlorinated Sea Water", Environ.  Sen.  and  Tech., 11(10)
     pp. 992-994, Oct. 1972.
20   White, G.C., Handbook of Chlorinatlon, Van Nostrand Reinhold Co., N.Y.
     1972, pp. 264:

21.  Bradbury, J.H. and A.N. Hambly, "An Investigation of Errors in the
     Amperometric and Starch Indicator Methods  for the Titration of Milli-
     normal Solutions of Iodine and Thiosulfate"  Australian J.  Sci. Res.,
     Ser. A, 5 pp. 541-554.

22.  Wong, G.T.F. and P.G. Brewer, "The Marine  Chemistry of Iodine  in Anoxic
     Basing", Geochim. Cosmochim  Acta, 41, pp.  151-159 (1971).

23   Abel, E. and F. Fabian, "Kinetics of the Halogenate-Halide Reaction in
     Heavy Water", Monatsch. 71, pp. 153-175  (1938).

24.  dzecelius, E.A., et.al., "Errors in Determination of  Residual Oxidants
     in Chlorinated Seawater", Battelle Northwest Labs.

25.  Sugam, R., The Chemistry of Chlorine in  Estuarine Waters, Unpub. thesis,
     University of Maryland, College Park, pp.  702 (1977).

26.  Burton, D.T., General Test Conditions and  Procedures for Chlorine
     Toxlclty Tests with Estuarine and Marine Macroinvertebrates and F1sh.
     Chesapeake Science Vol. 18, No. 1, pp. 130-136, March  1977.
27.  Bean, R.M., R.G. Riley and P.W. Ryan, Investigation of Halogenated
     Components Formed from Chiorination of Marine Water, Water Chiorination
     Environmental Impact and Health Effects, Vol.  2,  editor  R. L. Jolley
     et.al., Ann Arbor Science, 1978.

28.  Mattice, J.S., and H.E. Zittel, Site-Specific Evaluation of Power Plant
     Chlorinatlon.  Journal of Water Pollution  Control  Federation, Vol. 48,
     No. 10, pp. 2284-2308, October 1976.

29.  Becker, C.D. and T.O. Thatcher, Toxicity of  Power Plant  Chemicals to
     Aquatic Life.  Battelle Pacific N.W. Laboratories, U.S.  Atomic Energy
     Commission, WASH-1249, June 1978.
30.  Brung, W.A., Effects of Residual Chlorine  on Aquatic Life.  Journal of
     the Water Pollution Control Federation,  Vol.  45,  No. 10, pp. 2180-2193,
     October 1973.
31.  Goldman, J.C., J.M. Coppuzzo and G.T.F.  Wong,  "Biological and Chemical
     Effects of Chlorinatlon at Coastal Power Plants,  Water Chlorination
     Environmental Impact and Health Effects, Vol.  2,  editor  R.L. Jolley
     et.al., Ann Arbor Science, 1978,

                                    6-2

-------
                              BIBLIOGRAPHY
Abel, E. and F. Fabian, "Kinetics of the Halogenate-Hallde Reaction in
     Heavy Water", Monatsch.  71, pp. 153-175 (1938).

American Public Health Association, Standard Methods  for the Examination
     of Water and Wastewater, 14th'ed., pp.  322-325,  1975.

Anerican Society for Testing  and Materials,  1977 Annual  Book of ASTM
     Standards, pp. 292-298,  1976.

Baker, R.J., Types and Significance of Chlorine Residuals.  Journal of
     AWWA.  51 (9), September 1959.

Basch, R.E., and J.6. Truchan, Toxicity of Chlorinated Power Plant
     Condenser Cooling Water  for Fish.  EPA Report No.  600/3-76-009,
     April 1976.

Bean, R.M., R.G. Riley and P.W. Ryan, Investigation of Halogenated
     Components Formed from Chlorination of Marine Water,  Water Chlorination
     Environmental Impact and Health Effects, Vol. 2, editor R.  L.  Jolley
     et al., Ann Arbor Science, 1978.

Becker, C.D. and T.O. Thatcher, Toxicity of Power Plant Chemicals  to
     Aquatic Life.  Ba-telle  Pacific N.W.  Laboratories,  U.S. Atomic Energy
     Commission, WASH-1249, June 1978.

Bellanca, M.A. and D.S. Baily, Effects of Chlorinated Effluent on  the
     Aquatic Ecosystem in the Lower James River, JWPCF,  April  1977.

Bender, M.E., et al, Effects  of Residual Chlorine on  Estuarine Organisms.
     Biofouling Control Proceedings Technology and Ecological  Effects.
     Marcel Dekker, Inc.  1977.

Bongers, L.H. and T.P. O'Connor, Bromine Chloride - an Alternative to
     Chlorine for Fouling Control in Condenser Cooling Systems.  EPA
     Report No. 600/7-77-053, May 1977.

Bongers, L.H., et al., Biotoxicity of Bromide Chloride-  and Chlorine-
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Brung, W.A., Effects of Residual  Chlorine on Aquatic Life.   Journal  of
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Goldman, J.C-, J.M.  Coppuzzo and G.T.F.  Wong,  "Biological  and  Chemical
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