S  88  092
                                                   Draft
                                                   8/31/88
AMBIENT AQUATIC LIFE  WATER  QUALITY CRITERIA FOR

               HEXACHLOROBENZENE
     U.S. ENVIRONMENTAL PROTECTION AGENCY
      OFFICE OF RESEARCH AND DEVELOPMENT
      ENVIRONMENTAL RESEARCH LABORATORY
               DULUTH, MINNESOTA

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                                    NOTICES
This document has been reviewed by the Criteria and Standards Division, Office
of Water Regulations and Standards, U.S. Environmental Protection Agency, and
approved for publication.
Mention of trade names or commercial
or recommendation for use.
products does not constitute endorsement
This document is available to the .public through the National Technical
Information Service (NTIS), 5285 Port Royal Road, Springfield, VA  22161
                                      1i

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                                   FOREWORD


      Section 304(a)(l) of the Clean Water Act requires the Administrator of
the Environmental Protection Agency to publish water quality criteria that
accurately reflect the latest scientific knowledge on the kind and extent of
all identifiable effects on health and welfare that might be expected from the
presence of pollutants in any body of water.  Pursuant to that end, this
document proposes water quality criteria for the protection of aquatic life.
These criteria do not involve consideration of effects on human health.

      This document is a draft, distributed for public review and comment.
After considering all public comments and making any needed changes, EPA will
issue the criteria in final form, at which time they will replace any
previously published EPA aquatic life criteria for the same pollutant.

      The term "water quality criteria" is used in two sections of the Clean
Water Act, section 304(a)(l) and section 303(c)(2).  In section 304, the term
represents a non-regulatory, scientific assessment of effects.  Criteria
presented in this document are such scientific assessments.  If water quality
.criteria associated with specific stream uses are adopted by a State as water
quality standards under section 303, then they become maximum acceptable
pollutant concentrations that can be used to derive enforceable permit limits
for discharges to such waters.

      Water quality criteria adopted in State water quality standards could
have the same numerical values as criteria developed under section 304.
However, in many situations States might want to adjust water quality criteria
developed under section 304 to reflect local environmental conditions before
incorporation into water quality standards.  Guidance is available from EPA to
assist States in the modification of section 304(a)(l) criteria,,and in the
development of water quality standards.  It is not until their adoption as
part of State water quality standards that the criteria become regulatory.
                                    Martha G. Prothro
                                    Director
                                    Office of Water Regulations and Standards

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                                ACKNOWLEDGMENTS
Daniel J. Call
(freshwater author)
University of Wisconsin-Superior
Superior, Wisconsin
Charles E. Stephan
(document coordinator)
Environmental Research Laboratory
Duluth, Minnesota

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                                    CONTENTS
                                                                          Page
 Notices	 ^	   i i
 Foreword.	 ~.. . . .	  i i i
 Acknowledgments. . ,	„	   iv
 Tables	   vi

 Introduction.	    1
 Acute Toxieity to  Aquatic Animals-.-	    2
 Chronic Toxieity to Aquatic Animals..	    3
 Toxieity to Aquatic Plants	    3
 Bioaccunmlation.	    4
 Other Data.	    6
 Unused Data.	    7
 Summary.	 1	    8
 National Criteria	;	'-.	    9
 Implementation	    g

References.	   21

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                                     TABLES
                                                                         Page



1.  Acute Toxicity of Hexachlorobenzene to Aquatic Animals...	n




2.  Chronic Toxicity of Hexachlorobenzene to Aquatic Animals	 14



3.  Toxicity of Hexachlorobenzene to Aquatic Plants...................... 15



4.  Bioaccumulation of Hexachlorobenzene by Aquatic Organisms.	 16



5.  Other Data on Effects of Hexachlorobenzene to Aquatic Organisms...... 19
                                      VI

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 Introduction




     Hexachlorobenzene (HCB)  has been detected  in environmental  samples from



 around the world in recent years,  and is  recognized  as  a  global  pollutant




 (Ballschmiter and Zell  1980;  Brevik .1981;  Brunn and  Manz  1982;  Chovelon et



 al.  1984;  Galassi et'al.  1981;  Jan and Malnersic 1980;  Johnson  et  al.  1974;'



 Kaiser 1977; Kuehl  et al.  1983,1984;  Laska et  al.  1976; Niimi  1979;




 Paasivirta et al. 1981;  Sackmauerova et al.  1977;  Schmitt et  al.  1985;



 Skaftason and Johannesson 1982; Tsui  and  McCart 1981; Veith et  al.. 19795).




 Contamination of Lake Ontario with hexachlorobenzene and  other  chlorobenzenes



 has  occurred since  1915,  but  at a  much greater rate  in  the past three  decades



 (Oliver and Nicol 1982).   HCB is soluble  in water to about 6  jug/L




 (Abernethy et al. 1986;  Metcalf et al.  1973),  and its concentrations  in




; rivers and lakes are generally reported in terms of  ng/L  (Niimi  and Cho




 1981).   It has an octanol/water partition coefficient of  6.18 (Neeiy  et al.




 1974).   The common  occurrence of HCB in tissues of aquatic organisms  can  be



 attributed to its high  affinity for lipids and its persistence  in  the




 environment (Callahan et  al.  1979).   Connor (1984) estimated  that  HCB




 contributed little  to increased risk of cancer associated with  consumption of



 freshwater fish from contaminated  water.




     HCB is used as  a seed  grain fungicide,  a peptizing  agent  in the




 production of nitroso and  styrene  rubber  for tires,  a wood preservative,  a




 porosity controller in  the manufacture  of  graphite electrodes,  a fluxing




 agent  in aluminum smelting, and in pyrotechnics manufacture (Courtney  1979;




Quinlivan  et  al.  1975/1977; U.S. EPA  1980;  Young et  al. 1980).   HCB wastes




also originate  from the production of  certain  pesticides  (Cleveland et al.




 1982),  chlorinated  solvents,  vinyl  chloride  monomers, and chlorine or  sodium




chlorate when produced electrolytically (Quinlivan et al.  1975/77).   Some of




the  commercial  formulations of  HCB contain toxic impurities,  including




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   pentachlorobenxene, polychlorinated dibenzo-p-dioxins, and polychlorodi-
     •
   benzofurans  (Villanueva et al.  1974-).

      This document does not contain information concerning the effects of HCB

   on saltwater species  and their  uses because adequate data and resources were

   not available.  An understanding of the "Guidelines for Deriving Numerical

   National Water Quality Criteria for the Protection of Aquatic Organisms and

   Their Uses"  (Stephan  et al. 1985), hereinafter, referred to as the Guidelines,

   and the response to public comment (U.S. EPA 1985a), is necessary in order to

   evaluate the  following text, tables, and calculations.  Results of such

   intermediate  calculations as recalculated LCSOs and Species Mean Acute Values

   are given to  four significant figures to prevent roundoff error in subsequent

   calculations, not to  reflect the precision of the value.  The criteria

   presented herein supersede previous information on HCB (U.S. EPA 1980)

,   because these criteria were derived using additional information.  The latest

   comprehensive literature search for information for this document was

   conducted in February, 1986.  Some more recent information was also

   included.   Data in the files of the U.S. EPA's Office of Pesticide Programs

  concerning the effects of hexachlorobenzene on aquatic organisms and their

  uses  have not been evaluated for possible use in the derivation of aquatic

   life  criteria.
  AcuteToxicity to Aquatic Animals

      Data that may be used, according to the Guidelines, in the derivation of

  a freshwater Final Acute Value for HCB are presented in Table 1.  The only

  experimentally determined .acute values were at concentrations that are at

  least 1000 times the solubility limit.  Although the .quantitative value of

  these measurements might be suspect, they do indicate that.concentrations

  near solubility should not cause acute toxicity.  Some acute exposures were

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           for longer than 96 hr with no resultant mortalities.  For example,



 adult crayfish, Procambarus clarki .  were unaffected over a period of 20 days




 at a mean HCB concentration of 27.3 ng/L,  and largemouth bass, -Micropterns



 salmoides. were unaffected over 10 days at 25.8 /zg/L (Laseter et al. 1976;




 Laska et al. 1978).  Because an acute value is not available for any species




 at or below solubility, a freshwater Final Acute Value cannot be determined.



 If one could be determined,  it would be higher than 6 jug/L,  which was




 reported by Metcalf et al.  (1973) to be the solubility of HCB in water.








 Chronic Toxicitv to Aquatic  Animals




     The available data that  are useable according to the Guidelines




 concerning the  chronic toxicity of HCB are presented in Table 2.  Rainbow




 trout,  Salmo gairdneri .  were exposed to HCB in a 90-day early life-stage test




 (Spehar 1986).   No adverse  effects on hatching,  survival,  or growth were




 observed at  the  highest tested concentration of  3.68 fj.g/1 (Table 2).




 Similarly, fathead minnows,  Pimephales  promelas.  were not affected at




 exposures  up to  4.8 pg/L in  a  32-day early life-stage test (Ahmad et al.



 1984; Carlson and  Kosian 1987).   Survival  at hatch,  survival  at  32 days,  and



 wet weight were  the same  at  all  exposure concentrations  as in the control.




    In  a 7-day  life-cycle test  with  the cladoceran,  Ceriodaphnia dubia.  HCB



 did not  cause any  measurable effect  upon survival  or reproduction at




 concentrations as  high  as 7.0 pg/L (Spehar  1986).  Because a  chronic value




 is not available for any  species,  no  Final  Chronic Value  can  be  calculated.



 If one could be  calculated,  it  would  be higher than  3.68
Toxicity to Aquatic Plants




    Geyer et al. (1985) reported that the green alga, Scenedesmus




subspicatus, was not affected in 4 days by HCB at a concentration of




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 10 ng/L (Table 3).   A 4-day exposure  of  Selenastrum capricornutum to


 30 [ig/L caused a 12% inhibition of  population  growth  (Calaraari et al.


 1983).   A Final  Plant Value,  as defined  in  the Guidelines, cannot be obtained


 because no test  in which the  concentrations of HCB were measured and the


 endpoint was  biologically important has  been conducted with an important


 aquatic plant species.
 Bioaccumulation


     HCB concentrations  in  tissues  of  aquatic organisms appear to equilibrate


 very slowly  with  concentrations  in the water.  Uptake via the food might be
                                 t -

 more important  than  direct uptake  from water for top carnivores, particularly


 in waters where HCB  concentrations are very low (Niimi and Cho  1980).  Oliver


 and  Niimi (1983)  reported  that equilibration had not yet occurred after a


 119-day exposure  of  rainbow trout  to  HCB  at a concentration of


 0.00032 jtxg/L, at  which  time the  bioconcentration factor was 12,000 (Table


 4).   An exposure  to  0.008  jug/L resulted in a bioconcentration factor of


 20,000  with  the trout.  HCB residues  in fathead minnows continually  increased


 in 28-day testa to concentrations  that were from 32,000 to 39,000 times


 greater than the  concentrations  of  HCB in water (Kosian. et al.  1981).


 Following a  rapid uptake during  the first week of exposure, HCB residues in


 fathead minnows gradually  increased through 115 days (Veith et  al. 1979a).


HCB  residues in the minnows were from 16,200 to 45,700 times greater than


concentrations  in water following  exposures of 32 to 115 days.  Carlson and


Kosian  (1987) obtained similar results with f. BCF of 22,000 for fathead


minnows exposed for 32 days.


    Green sunfish, Lepomis  cyanellus. bioconcentrated HCB approximately


22,000 times, whereas fingerling rainbow trout bioconcentrated  HCB


considerably lower at 5,500 times  (Veith et al.  1979a).  In a test with a

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 mixture  of  chlorinated  benzenes,  a  BCF  of  15,660 was obtained for HCB with




 the  guppy,  Poecilia  reticulata  (Konemann and Van Leeuwen 1980).  An apparent




 steady-state  between HCB  residues  in guppy tissue and concentration in the



 water occurred  within 7 days.




     Coho salmon (Oncorhynchus kisufch)  and green sunfish accumulated HCB when




 fed  contaminated food (Leatherland  and  Sonstegard 1982; Sanborn et al.




 1977).   Crayfish (Procambarus clarki) exposed at a contaminated field site to



 a  mean HCB  concentration  of 74.9 /ig/L had a mean whole-body concentration



 factor of 1,464 (Laseter  et al. 1976).  Fox et al. (1983) found a direct




 correlation between  HCB concentrations  in surficial sediments of Lake Ontario




 and  HCB  concentrations  in oligochaetes  that inhabit the sediments.  They also




 reported that HCB accumulation was  greater at the higher trophic levels.




     HCB  and other lipophilic, persistent chlorinated organics are passed from




 parent to offspring  via the yolk and oil of the fish egg.  Survival and




 growth of larvae might  be affected  by this route of uptake in some fish



 species  (Niimi  1983;  Westin et al.  1985).




     Elimination of HCB  from salmonids occurs slowly.  Norheim and Roald



 (1985) determined the half-life of  HCB  in rainbow trout that had been




 injected intraperitpneally and maintained at a water temperature of 7ฐC to be




 81,  146, and 139 days in  Hver, fat, and muscle, respectively.  Niimi and Cho




 (1981) reported  the  biological half-life of HCB to be 224 to 770 days in




 rainbow  trout fed HCB and maintained at a water temperature of 15ฐC.  In a




 subsequent  study (Niimi and Palazzo 1985),  HCB-fed rainbow trout held at 12




and  18ฐC had half-lives of HCB of 173 and 198 days, respectively, whereas




fish held at 4ฐC did not  eliminate  HCB.  Thus, it appears that HCB is highly




persistent  in the tissues of. fish inhabiting cold waters.




    Crayfish that were  exposed to 74.9 fig/L for 10 days under field




conditions eliminated about 15% of  the HCB after three days in clean water.




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 Males eliminated 47% and females 64-% after 25 days  (Laseter et  al.  1976).



 Largemouth bass-eliminated from 73.1 to 91.4% of  the-'whole  body HCB residue



 during 13 days in clean water (Laseter et al.  1976).



     McKim et al.  (1985) studied the uptake efficiency of  HCB and 13 other



 chemicals by rainbow trout gills.   HCB was among  the  chemicals  most



 efficiently removed from water by  gills.   However,  it was not much  more



 efficiently removed than several chlorophenols which,  by  comparison to HCB,



 have a reduced capacity for bioaccumulation.   The high accumulation, levels of



 HCB can be explained by a slow rate of conversion to  water  soluble



 metabolites and subsequent elimination,  combined  with an  efficient  uptake



 from water and food due to its high n-octanol  water partition coefficient  of



 6.18.



     No U.S.  FDA action level  or other maximum acceptable  concentration  in



 tissue for HCB,  as  defined in the  Guidelines,  is  available  for  HCB.



 Therefore,  a Final  Residue Value cannot be calculated.
 Other  Data




    Additional  data  on the  lethal  and sublethal  effects  of  HCB on freshwater



 species are  presented  in  Table  5.   A  green  alga,  Ankistrodesmus falcatus.  was



 unaffected in a 4-hr exposure to 3 jug/L  (Wong  et  al.  1984).   Daphnia  magna



 were unaffected after  24  to  48  hr  at  concentrations  that exceeded the



 solubility of HCB  in water  (Calamari  et  al.  1983;  Sugatt et al.  1984).



 Exposure of  Daphnia  magna to HCB concentrations  in excess of its solubility



 in water for a  period  of  14  days resulted in an EC50  of  16  /ig/L and a



 reduced instantaneous  growth rate  at  23  /ug/L (Calamari et al.  1983).   Due



 to insufficient deaths, LCSOs could not  be  determined for rainbow trout



exposed to 30 f/,g/L for 24 hr (Calamari et al.  1983)  or for  guppies exposed



to 730 /ug/L for 14 days (Konemann  1979,1981).  However,  largemouth bass



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 had liver and kidney  damage  after  10  days  of  exposure  to  3.5 jug/L  (Laseter
                                                                   a


 et al.  1976).







 Unused  Data



     Some  data on  the  effects  of  HCB on  aquatic organisms  and their uses were



 not used  because  the  studies  were  conducted with  species  that are  not



 resident  in  North America  (e.g., Hattori et ai. 1984;  Sugiura et al. 1984).



 Data were not used when  HCB  was  a  component of a  mixture  or wettable powder



 (e.g.,  Gjessing et al. 1984;  Mayer and  Ellersieck 1986; Poels et al. 1980).



 Chiou (1985),  Chiou et al. (1977), Davies  and Dobbs  (1984), Glass  et al.



 (1977), Kaiser et al. (1984),  Klein et  al. (1984), Koch (1982a,b), Matsuo



 (1980,1981),  Oliver (1984a)(  and Sabljic and  Protic  (1982) compiled data from



 other sources.




     Tests were not used  when  only  physiological effects or eniyme  activity



 were  measured (e.g.,  Gluth and Hanke  1984; Hanke  et  al. 1983; Law  and Addison



 1981).  Schmidt-Bleek et al.  (1982) did not adequately describe the methods



 used  for  the  toxicity tests.   Toxicity  data were  not used when the test was



 conducted in  distilled water  (e.g., Abernethy et  al. 1986; Bobra et al.



 1985).




    Studies of HCB residues  in aquatic organisms  were  not used when there



were  insufficient  tissue residue data or accompanying  data on HCB



concentrations in  the water to determine a bioconcentration or



bioaccumulation factor (e.g.,  Atuma and Eigbe 1985;  Clark et al. 1984;



DeVault  1985;  Evans et al.  1982; Giesy et al. 1986;  Glass 1975; Hei.da 1983;



Jaffe and Kites 1986;  Kaiser  1982;  Kaiser and Valdmanis 1978; Keck and



Raffenot  1979; Kuehi  et al. 1980,1981; Niimi  1979; Norstrom et al. 1978;



Paasivirta et  al.   1983a,b;  Pennington et al.   1982; Schmitt et al.  1985;



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 Schuler  et  al.  1985; Swain  1978; Veith et al. 1977,1981; Wierneyer et al.
 1978; Zitko  1971).  Results of studies in which HCB was administered by
 gavage or injection were not used (e.g., Ingebrigtsen and Skaare 1983;  Safe
 et al. 1976).   Studies using radiolabeled HCB in which only radioactivity was
 measured in  the water or in exposed organisms were not used (e.g.,  Freitag
 1987; Freitag et al. 1982,1984,1985; Geyer et al. 1981,1984; Schauerte et al.
 1982).
     Results  of  laboratory bioaccumulation tests were not used when the test
 was not flow-through or renewal (e.g.,  Belluck and Felsot 1981; Korte et al.
 1978; Lu and Metcalf 1975;  MetcalJ et al.  1973;  Zitko and Hutzinger 1976) or
 when the concentration of HCB in the test solution was not adequately
 measured (e.g.,  Isensee 1976;  Isensee et al.  1976).   A study of the
 bioaccuraulation of HCB by organisms inhabiting contaminated sediment was not
 used (Oliver 1984b).
     Results  of bioconcentration tests were  not used  when the duration of
 exposure  was not specified  (e.g.,  Neely et  al.  1974).   Studies on the
 dynamics  and transport  of HCB  at  the sediment-water  interface  were  not  used
 (Baker et al. 1985;  Karickhoff  and  Morris  1985).
Summary
    Hexachlorobenzene  at  a  concentration  of  6  /xg/L  has  been shown not  to
cause acute toxicity to any tested  freshwater  species and  3.68  /ig/L has
been shown not to cause chronic toxicity  to  any  tested  species.   Freshwater
plants were .not affected  at 10 fig/L.   In  a 14-day test,  16 jug/L caused
a 50% reduction in the fertility of Daphnia  magna.   Bioconcentration factors
ranged from 5,1500 to 45,700 in tests with freshwater fish.

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 National Criteria




     The procedures described in the "Guidelines for Deriving Numerical




 National Water Quality Criteria for the Protection of  Aquatic Organisms  and




 Their Uses" indicate that,  except possibly where a locally important  species



 is very sensitive, freshwater aquatic organisms and their  uses should not  be



 affected unacceptably if the four-day average  concentration of hexachloro-



 benzene does not exceed 3.68 ng/L more than once every three years  on the




 average and if the one-hour average concentration does not exceed 6.0 /jg/L



 more than once every three  years on the average.   The  only adverse  effects




 that have been observed in  tests on hexachlorobenzene  include a 50% reduction



 in fertility of Daphnia magna at 16 ;ug/L and organ damage  to largemouth




 bass at 3.5 ng/L.   However,  histopathology data are not used to develop




 criteria and the available  data do not justify establishing criteria



 different from those given  above.








 Implementation




     As  discussed in the Water Quality Standards Regulation (U.S. EPA  1983a)




 and  the  Foreword to this document,  a  water quality criterion for aquatic life




 has  regulatory impact  only  after it has  been adopted in a  state water quality




 standard.   Such a  standard  specifies  a criterion for a pollutant that is




 consistent  with a  particular  designated  use.   With the concurrence  of the



 U.S. EPA, states designate  one  or  more uses  for each body  of  water  or segment




 thereof  and  adopt  criteria  that  are consistent  with the  use(s)  (U.S.  EPA




 1983b,1987).   In each  standard  a state may adopt  the national  criterion, if



one exists,  or,  if  adequately justified, a site-specific criterion.




    Site-specific  criteria may  include not only  site-specific  criterion




concentrations  (U.S. EPA  1983b), but  also  site-specific, and  possibly




pollutant-specific, durations of averaging periods and  frequencies  of allowed



excursions (U.S. EPA 1985b).  The averaging periods of  "one hour" and "four




                                       9

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 days" were  selected by the U.S. EPA on the basis of data concerning how



 rapidly  some aquatic  species react to increases in the concentrations of some



 aquatic  pollutants, and "three years" is the Agency's best scientific



 judgment of the  average amount of time aquatic ecosystems should be provided



 between  excursions (Stephan et al. 1985; U.S. EPA 1985b).  However, various



 species  and ecosystems react, and recover at greatly differing rates..



 Therefore,  if adequate justification is provided, site-specific and/or



 pollutant-specific concentrations, durations, and frequencies may be higher



 or lower than those given in national water quality criteria for aquatic



 life.



    Use  of criteria,  which have been adopted in state water quality



 standards, for developing water quality-based permit limits and for designing



 waste treatment  facilities requires selection of an appropriate wasteload



 allocation model.  Although dynamic models are preferred for the application



of these criteria (U.S. EPA 1985b), limited data or other considerations



might require the use of a steady-state model (U.S. EPA 1986).  Guidance on



mixing zones and the  design of monitoring programs is also available (U.S.



EPA 1985b,1987).
                                       10

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