United States
Environmental Protection
Agency
               Officao* W.i,e-
               Reguiatic-i!.- *--a
               Criteria jnr- a^'
               Wash.nt": ,- TC
      r>iซv..icn
             Jsni.v-y
006200
Water
Ambient
Water  Qua I it v
Criteria
for
OHEA
                             OF
                      CENTRAL FILE
Arsenic - 1984

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AMBIENT AQUATIC LIFE WATER QUALITY CRITERIA FOR

                   ARSENIC
      U.S.  ENVIRONMENTAL PROTECTION  AGENCY
       OFFICE  OF RESEARCH AND DEVELOPMENT
       ENVIRONMENTAL RESEARCH LABORATORIES
               DULUTH, MINNESOTA
           NARRAGANSETT, RHODE ISLAND
                                                  000001 JB\

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                  ;a  \ ป.ซi-.   . -'.rt-.-oi  by  che  Criceria and Standards Division,
                 c.  '*ci:-ns  and  Standirds,  U.S. Environmental Proceccion
              •-:••/• !  fcr ouSlicition.   Mention oฃ crade names or commercial
              ''ot constitute endorsement or recommendation  for use.
                             AVAILABILITY NOTICE
     This  document  is  available  to  the  public through the National Technical
Information Service  (NTIS) ,  5285  Port Royal Road, Springfield, VA  22161.
                             /2.  - P6 8S
                                                                           000001  C

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                                  FOREWORD

     Section 304(a)(l) of the Clean Water Ace  of 1977 (P.L.  95-217)  requires
che Administrator of the Environmental Protection Agency to  publish  criteria
for water quality accurately reflecting the latest scientific knowledge  on
the kind and extent of all identifiable effects on health and welfare  which
may be expected from the presence of pollutants in any body  of water,
including ground water.  This document is a revision of proposed criteria
based upon a consideration of comments received from other Federal agencies,
State agencies, special interest groups, and individual scientists.  The
criteria contained in this document replace any previously published EPA
aquatic life criteria.

     The terra "water quality criteria" is used in two sections of the  Clean
Water Act, section 304(a)(l) and section 303(c)(2).  The term has a  different
program impact in each section.  In section 304, the term represents a
non-regulatory, scientific assessment of ecological effects.   The criteria
presented in this publication are such scientific assessments.  Such water
quality criteria associated with specific stream uses when adopted as  State
water quality standards under section 303 become enforceable maximum
acceptable levels of a pollutant in ambient waters.  The water quality
criteria adopted in the State water quality standards could  have the same
numerical limits as-the criteria developed under section 304.  However,  in
many situations States may want to adjust water quality criteria developed
under section 304 to reflect local environmental conditions  and human
exposure patterns before incorporation into water quality standards.  If is
not until their adoption as part of the State  water quality  standards  that
the criteria become regulatory.

     Guidelines to assist che States Ln che modification of  criteria
presented in this document, in the development of water quality standards,
and in other water-related programs of chis Agency, have been developed  by
EPA.
                                      Edwin L.  Johnson
                                      Director
                                      Office of Wacer Regulacions  and  Standards
                                     111
                                                                     00000!

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                              ACKNOWLEDGMENTS
          .'pci.-r
          :  duchor)
              Research  Laboracory
..jluch,  Minnesoca
                                          John H. Gencile
                                          (aalcwacer auchor)
                                          EnvironmencaL Research Laboracory
                                          Narraganaecc, Rhode Island
Charles E.  Scephan
(documenc coordinacor)
Environraencal Research  Laboracory
Ouluch, Minnesota
                                          David J. Hflnsen
                                          (salcwacaf coordinacor)
                                          Environmental Research Laboracory
                                          Narraganaซt:c, Rhode Island
Clerical Supporc:   Terry L.  Highland
                                     IV
                                                                          000001

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                                  CONTENTS
 Foreword  ............  .  ..................




 Acknowledgments   ........  .  ..................    iv




 Tables  ................................    vi









 Introduction .............................     i




 Acute Toxicity to Aquatic Animals   ..................     5




 Chronic Toxicity to Aquatic Animals   ........ .........     7




 Toxicity to Aquatic Plants  .......................     8




 Bioaccumulcition  ...........................    10




 Other Data ..............................    10




Unused Data ..............................    12




 Summary  ..........................  .....     14




National Criteria  ..........................     15









References  ..............................     4j
                                                                    00000

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                                  TABLES
1.




2.




3.









4.




5.




6.
Acuce Toxicicy of  Arsenic  co Aquacic Animals .  .  .  .  	




Chronic Toxicicy of Arsenic co Aquacic Animals 	




Ranked Genus  Mean  Acuce Values wich Species Mean Acuce-Chronic
Rac ion
Toxicicy of Arsenic  co  Aquacic Planes  	




Bioaccumulacion of Arsenic by Aquacic Organisms  .  .  .




Ocher Daca on Effeccs of Arsenic on Aquacic Organisms
Page




 19




 24








 26




 29




 32




 35
                                     VI
                                                                          oooooi  G-

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Introduction*

     Arsenic is found in all living organisms, -including chose in aquacic

systems.  Lictle is known abouc che mechanisms of arsenic coxicicy co aquacic

organism:;; however, arsenic readily forms stable bonds co sulfur and carbon

in organic compounds.  Like mercury, arsenic(III) reacts wich sulfhydryl

groups of proteins; enzyme inhibition by chis mechanism may be che primary

mode of coxicicy.  Arsenic(V) does noc react wich sulfhydryl groups as

readily but may uncouple oxidacive phosphorylacion (Fowler, et al. 1977;

Schiller, et al. 1977).

     The chemistry of arsenic in water is complex, consisting of chemical,

biochemical, and geochemical reactions which together control the concentra-

tion, oxidation state, and form of arsenic in water (Braman, 1983; Callahan,

et al. 1979; Holm, ec al. 1979; Scudlark and Johnson, 1982).  Four arsenic

species common in nacural waters are inorganic arsenic(III) and arsenic(V),

mechaneairsonic acid, and dimechylarsinic acid.  In aerobic water, inorganic

arsenicdll) is slowly oxidized co arsenic(V) at neutral pH, but che reaction

proceeds measurably in several clays in strongly alkaline or acidic solutions.

Because i:he chemical and toxicological properties of che forms appear co be

quice different and che coxicici.es of che forms have noc been shown co be

additive,, che data for inorganic arsenicCIII), inorganic arsenic(V) , mono-

sodium mnchanearsonace (MSMA), and other arsenic compounds will be creaced

separately.  Methods have been developed for separately measuring these  forms

of arsenic in water (Fichlin, 1983; Grabinski, 1981; Irgolic, 1982).
*An understanding of che "Guidelines  for Deriving Numerical Nacional Wacer.
Quality Criteria for che Protection of Aquacic  Organisms  and  Their Uses"
(Scephan, et al. 1985), hereafter  referred  co as the Guidelines,  is necessary
in order co understand che  following  cexc,  cables,  and  calculations.

                                       1

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      Because of the variecy of  forms of .inorganic  arsenic(III)  and  inorganic




arsenic(V) and lack of definicive  information  abouc  cheir  relative




coxicicies, no available analycical measurement  is known co  be  ideal  for




expressing aquacic life criteria for arsenic.  Previous aquatic  life  criteria




for arsenic (U.S. EPA, 1980) were  expressed  in terms of total recoverable




inorganic arsenicCIII), but the total recoverable method cannoc  distinguish




between inorganic arsenicC III)  and arsenic(V).   Acid-soluble arsenic(HI)




(operationally defined as the arsenic(III) that  passes through  a 0.45 ijm




membrane filter after the sample is acidified  to pH - 1.5  to 2.0 with nitric




acid) and acid-soluble arsenic(V)  are probably the best measurements  at the




present for the following reasons:




1.  These measurements are compatible with all available data concerning




    toxicity of arsenic to, and bioaccumuiation  of arsenic by,  aquatic




    organisms.   No test results were rejected  just because it was likely that




    they would  have been substantially different if they had been reported in




    terms of acid-soluble arsenic.




2.  On samples  of ambient water, measurement of  acid-soluble arsenic(lll) and




    arsenic(V)  should measure all  forms of arsenic that are  toxic to  aquatic




    life or can be readily converted co toxic  forms under natural conditions.




    In addition,  these measurements should not measure several  forms, such as




  '  arsenic that  is occluded in minerals, clays, and sand or is  strongly




    sorbed  to  particulate matter, that are not toxic and are not likely to




    become  toxic  under natural conditions.




3.  Although water quality criteria apply to ambient water,  the-measurements




    used to express criteria are likely to be  used co measure arsenic in




    aqueous effluents.  Measurements of acid-soluble arsenic(III) and

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    arsenicCV)  should be  applicable  co  effluents.   If desired,  dilution of




    effluent  with  receiving  water  before measurement of  acid-soluble  arsenic




    might  be  used  to determine whether  the  receiving water  can decrease  the




    concentration  of acid-soluble  arsenic because  of sorption.   However,  the




    relationship between  what is in  an  effluent  and what will result  in  the




    receiving water should take into account  any conversion of one oxidation




    state of  arsenic to the other.



4.  The acid-soluble measurement should be  useful  for  most  metals, thus




    minimizing the number of samples and procedures that are necessary.




5.  The acid-soluble-measurement does not require filtration at the time of




    collection, as does.the dissolved measurement.




6.  For the measurement of total acid-soluble arsenic  the only treatment




    required  at the time of collection is preservation by acidification to pH




    = 1.5 to 2.0,  similar to  that required for the measurement of total




    recoverable arsenic.   Durations of 10 minutes to 24 hours between




    acidification and  filtration  probably will not affect  the measurement of




    total acid-soluble arsenic.   However, acidification might not prevent




    conversion of  inorganic  arsenic(III) to  arsenic(V)  or  vice  versa.




    Therefore, measurement  of acid-soluble arsenic(III) or  acid-soluble




    arsenicCV) or both will  probably require separation or measurement  ac che




    time  of  collection of  the sample or  special preservation to  prevent
     conversion  of  one
              oxidation state of arsenic to the other.
     The
     2.0
 8.   Differences
     the
carbonate system has a much higher buffer




than it does from pH = 4 to 9 (Weber and




        in pH within the range of 1.5 to




       substantially.
   .pacicy from




Stumm, 1963).




2.0 probably
                                                                      1.5 co
                                                               will not affecc

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9.  The acid-soluble tneasuretnenc does noc require a digestion seep, as does




    che cocal recoverable measurement.




10. After acidificacion and filcracion of che sample co isolace che




    acid-soluble arsenic, che analysis can be performed using either atomic




    absorption spectroscopy or ICP-emission spectroscopy for either total




    acid-soluble arsenic or total .acid-soluble inorganic arsenic (U.S. EPA,




    1983a).   It might be possible to separately measure acid-soluble




    arsenic(III) and acid-soluble arsenic(V) using che methods described by




    Grabinski (1981) and Irgolic (1982).




11. It is noc possible co separately measure total recoverable arsenic(III)




    and total recoverable arsenic(V).




Thus, expressing aquatic criteria for arsenic in terms of the acid-soluble




measurement  has boch coxicological and practical advantages.  On che other




hand, because no measurement is known to be ideal for expressing aquatic life




criteria for arsenic or for measuring arsenic in ambient water or  aqueous




effluencs, measurement of both tocal acid-soluble arsenic and cocal




recoverable arsenic in ambienc water or effluent or both might be  useful.




For example, chere might be cause for concern if total recoverable arsenic is




much above an applicable limit, even chough total acid-soluble arsenic is




below the limit.




     Unless otherwise noted, all concentrations reported herein are expecced




co be essencially equivalent to acid-soluble arsenic concencracions.  All




concentrations are expressed as arsenic, not as che chemical tested.  The




criceria presenced herein supersede  previous aquatic life water quality




criceria  for arsenic (U.S. EPA, 1976a,  1980) because these  new criceria  were




derived using improved procedures and additional information.  Whenever

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adequacely juscified, a nacionaL cricerion may be replaced by a sice-specific




criterion (U.S. EPA, 1983b), which may include noc only sice-specific




cricerion concencracions (U.S. EPA, 1983c), buc also sice-specific duracions




of averaging periods and sice-specific frequencies of allowed exceedences




(U.S. EPA, 1985).  The lacesc liceracure search for informacion for chis




docuraenc was conducced in May, 1984; some newer informacion was also used.









Acuce Toxicicy co Aquacic Animals




     Inglis and Davis (1972)  found  chac hardness did noc  affecc che coxicicy




of inorganic arsenic(III) co  che bluegill.  The. fachead minnow was much less




sensicive co arsenic crisulfide (Table 6)  chan  co sodium  arsenice  (Table  1).




Genus Mean Acuce Values  (Table  3) were calculated as geomecric means of che




sixceen available Species Mean Acuce Values (Table  1).  Acuce values are




available for  cwo species in  each of cwo genera and che range of  Species  Mean




Acuce Values wichin  each genus  is  less chan a faccor of 3.3.  Four cruscacean




genera are much more sensicive  chan che ocher cesced invercebrace  and  fish




genera.  Boch  che raosc  resiscanc  genus, Tanycarsus, and che  raosc  sensicive




genus, Ganmarus, are invercebraces, buc Gammarus  is 110 cimes more sensicive




chan Tanycarsus.  A freshwacer  Final Acuce Value  of 718.2 pg/L  for inorganic




arsenic(lll) was calculaced from  che Genus Mean Acuce  Values (Table  3) using




che  calculacion procedure  described in che Guidelines.




     Acut:e  cescs have  been  conducced on  inorganic arsenic(V) wich six  species




in five  genera and  che Species  Mean Acuce Values ranged  from 850 rig/L  for a




cladoceran  co  49,000 ,jg/L for che raosquicofish (Table  1).  Inorganic




 arsenic(V)  was slighcly more coxic chan arsenic(III)  co  rainbow crouc, buc




 arsenic(III) was nearly cwice as coxic co che  fachead  minnow and Daphnia

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     The acuce sensicivicies of eighc species exposed co MSMA range  from




1,921 jg/L for the bluegill co 1,403,000 ug/L for che channel cacfish (Table




1).  The fachead minnow was approximacely 12 cimes more sensicive co MSMA




chan co sodium arsenace and che goldfish, fachead minnow, and bluegill were




approximacely 5 co 22 cimes more sensicive co MSMA chan co sodium arsenice.




Channel cacfish and amphipods, however, were much less sensicive co MSMA chan




sodium arsenice.




     Noc enough acuce values are available for calculacion of freshwacer




Final Acuce Values for inorganic arsenic(V) or MSMA.




     Daca are available on che acuce coxicicy of inorganic arsenic(III) co




salcwacer species in chree fish and eighc invercebrace genera (Tables 1 and




3).  The fish species cesced were che mosc resiscanc wich a range of LCSOs




from 12,700 jjg/L for che sheepshead minnow co 16,030 ^g/L for che Aclancic.




silverside.  Among che inverrabraces, che lowesc acuce value, 232 Mg/L. was




obcained wich zoeae of che Dungeness crab whereas che highesc value, 10,120




jg/L, was from a cesc wich che polychaece worm, Neanches arenaceodencaca.




Incerescingly, che acuce value for che Pacific oyscer is almosc as  low as




chac for che Dungeness crab, buc chac for che eascern oyscer  is almosc as




high as chac for che polychaece worm.  In addicion, Alderdice and Brecc




(1957) obcained a 48-hr LC50 of 8,300 ;Jg/L wich arsenic crioxide co chum




salmon (Table 6).  Holland, ec al. (1960) decermined a  10-day LC54  of 3,787




,ag/L for che pink salmon, whereas Curcis, ec al. (1979) reporced a  96-hr LC50




of 24,700 ug/L  for arsenic  crisulfide in cescs wich juvenile  whice  shrimp




(Table 6).  Of  che eleven Genus Mean Acuce Values  in Table 3, all eighc  for




invercebraces  are  lower  chan  che  chree  for  fish.   The mosc sensicive genus,




Cancer,  is  69  cimes  more sensicive chan .che  mosc  resiscanc, Menidia.  The

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salcwacer Final Acuce Value for inorganic arsenic(III) is 137.1 pg/L, which




ia about one-half che lowesc Species Mean Acuce Value.




     Daca are available for inorganic arsenic(V) wich cwo salcwacer species.




The coxicicy of arsenic(V) co a mysid, Mysidopsis bahia, (LC50 - 2,319 ;jg/L)




is similar co chac of arsenic(III) (LC50 - 1,740 Mg/L).  Arsenic(V) is more




coxic chart arsenic(III) co che atnphipod, Ampelisca abdica, whose Species Mean




Acuce Values are 4,610 pg/L for arsenic(V) and 8,227 pg/L for arsenicCIII).




Noc enough daca are available co calculace a salcwacer Final Acuce Value for




inorganic arsenic(V).
Chronic Toxicicy co Aquacic Animals




     Three chronic cescs have been conducced on inorganic arsenic(III) wich




freshwacer species (Table 2).  A life-cycle cesc wich Daphnia magna (Call, ec




al. 1983; Lima, ec al. 1984) resulced in a chronic value of 914.1 pg/L based




on chronic liraics of 633.0 and 1,320 -Jg/L.  The 96-hr LC50 for  chis species




in che same scudy was 4,340  Jg/L, resulcing in an acuce-chronic  racio of




4.748.  The chronic values for che fachead minnow and flagfish  exposed co




arsenic(lll) were approximacely che same.  The 96-hr LC50 values for che  cwo




species were also similar and che acuce-chronic racios were 4.660 and 4.862,




respecciveily.




     Daca on che chronic coxicicy of arsenic co salcwacer species are




available for only one species, Mysidoosis bahia (Table  2).   In a 35-day




life-cycle cesc on arsenic(III), no adverse effeccs were scaciscically




significanc ac 631 ng/L, whereas 1,270  ;Jg/L affecced reproduccion and




significancly reduced survival.  These  resulcs provide  a chronic value  of




895.2  .Jg/L and an acuce-chronic racio of  1.944.

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      The  four  acute-chronic  ratios  available for  inorganic arsenic(III)  are




 •i.748,  4.560,  4.362,  and 1.944  and  che  geometric  mean  of 3.803 is  che  Final




 Acuce-Chronic  Racio.   Division  of  che  freshwacer  and saltwater Final Acuce




 Values  by  chis ratio  results  in freshwater  and  saltwater Final Chronic Values




 of  188.9  and 36.05  ,jg/L,  respectively  (Table 3).




      An early  life-stage test with  the  fathead  minnow  (DeFoe,  1982) exposed




 co  arsenic(V)  resulted  in chronic  limits  of  530 and  1,500 Mg/L and a chronic




 value of 891.6 ug/L.   The 96-hr LC50 for  this species  in the same  study  was




 25,600  ug/L producing  an acute-chronic  ratio of 28.71  (Table 2).   A




 life-cycle test with.Daphnia magna  (Biesinger and Christensen,  1972) (Table




 6)  exposed to  arsenic(V)  was not used  in  the calculation of a  chronic  value




 because the test concentrations  were not  measured  as specified  in  the




 Guidelines.  However,  the chronic limits  in  this  test  were 520  and  1,400 ug/L




 and che comparable acute  value  was  7,400  Jg/L,  resulting  in an  estimated




 acuce-chronic  ratio of 8.7.




     The fathead minnow  was approximately 3  times  more sensitive on a  chronic




basis co arsenic(V) than  to arsenic(III), but Daphnia  magna appeared to  be




equally sensitive to both  forms of  inorganic arsenic.  No  chronic  tests  have




been conducted on MSMA or  any other organic  arsenic compound.
Toxicity to Aquatic Planes




     Adverse effects were observed at concentrations of arsenic(III) ranging




from 2,320 ug/L for three species of algae and one submerged plant co over




59,000 ug/L for che alga, Selenascrum capricornucum (Table 4).  Except for S_.




capricornucum. values reported for aquatic plants exposed to arsenic(III) are




comparable co the acute values for some of che more sensitive invertebrate

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 species (Table 1)  and to che chronic  values  reported for che fachead  minnow




 and flatfish (Table 2).




      Concentrations of inorganic arsenic(V)  chat  caused adverse effects on




 six species  of freshwater algae ranged from 48 to 202,000 ug/L (Table 4).   A




 14-day EC50  value  of 48  tJg/L obtained for the most sensitive alga,




 Scenedesmus  obliquus,  was 18 times  lower  than the lowest acute value  and




 approximately 19 times lower than the only chronic value available  for




 inorganic  arsenic(V).  Data on the  sensitivity of j>_. capricornutum  to boch




 oxidation  states of inorganic arsenic cover  a wide range and appear to depend




 on  the  kind  of toxicity  test used (Richter,  1982).




      Data  on the toxicity of arsenic(III)  to saltwater plants are available




 for  four species of microalgae and  two species of macroalgae (Table 4).




 Growth  of  the  saltwater  diatoms,  Skeletonema costacum and Thalassiosira




 aestivalis,  was affected  at  20 ug/L and 22 rig/L,  respectively,  and  photosyn-




 thesis  of J3_.  costatum  was reduced at  19 ;Jg/L.   These values are less  than  che




 Final Chronic  Value  for  arsenic(III)  but  the ecological implications  of




 reduced growth  on  these  species is  uncertain.   Boney,  et al.  (1959) showed




 that arsenic(III)  inhibited  the development  of sporelings of the  red




macroalsja, Plumana  elegans.  at  577  ug/L.   In addition,  formation  of manure




 cystocairps by  another  red macroalgae,  Champia  parvula,  was  prevented  ac  95




 gg/L and growth of  female plants  was  reduced at 145  ug/L.




     Daca on  the toxicity of arsenic(V) to saltwater plants are available  for




 four species  of microalgae  and  one  species of  macroalgae (Table 4).   Based




 upon these data, there is no significant difference  between the toxicicy of




 arsenic(HI)  and arsenic(V)  to  the  plant  species  tested.   Thursby and Sceele




 (1984)  found  that phosphate  decreased  the  toxicity of  arsenic(V)  to Champia




 parvula,, but  did not affect  the coxicity of  arsenic( III) .




                                       9

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  Bioac cumulation
       Bioconcencracion ce3cs  have been conducted on arsenic( III) ,  arsenic(V),
  and  a number  of organic  arsenic  compounds  with a variety of  freshwater  fish
  and  invertebrates  (TabLe 5).   The highest  bioconcencracion factor (BCF)  was
  17,  which  was  obtained for inorganic  arsenic(III)  with  a snail  (Spehar,  et
  al.  1980).  An  early  life-stage  test  on  arsenic(V) wich the  fathead  minnow
  (DeFoe, 1982)  showed  that the  BCF decreased with increased exposure
 concentrations  in the water.    BCFs were  slightly lower  (down  to 1.2) in
 exposure concentrations that  caused significant adverse  effects than in  those
 chat  did not (Table 5).
      A study by Oladimeji, ec al. (1982) showed chat the pretreatment of
 rainbow trout  to arsenic(III) enhanced the elimination of a subsequent  dose
 of arsenic.  Additional results indicated that fish retained less  arsenic
 after 4 weeks  of exposure than  after  2 weeks.
      In the one acceptable bioconcentration test on arsenic with  a saltwater
 species, a  BCF  of 350  was  obtained with the oyster,  Crassostrea virgini^.
 after 112 days  of exposure (Zaroogian  and Hoffman,  1982).  In  a  test  that
 only  lasted 4 days, Nelson, et  al. (1976) obtained  a  BCF of 15 with the bay
 scalloo  (Table  6) .
     No  Final Residue Value could  be determined  because  no  maximum permissi-
ble tissue concentration  is available  for arsenic.
Other Data
     Comparison of data for fish in Tables 1 and 6 indicates that in almost
all cases, arsenic toxicity increased with increased duration of exposure.
One value for che bluegill (Hughes and Davis, 1967) was an exception
                                     10

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resultins; in a low 48-hr LC50 of 290 ug/L.  A special pellecized form of




sodium arsenice was used, which may have accounted for che low LC50.  The




invertebrate data were too variable to indicate a trend in toxicicy in regard




to duration of exposure.




     Spehar, et al. (1980) compared che toxicities of different forms of




arsenic in the same water.  In 28-day tests, inorganic arsenic(lll) was more




toxic to the araphipod, Gammarus pseudolimnaeus, than inorganic arsenic(V),




sodium dimethyl arsenate, or disodiura methyl arsenate.  Survival of




stoneflieis, snails, and rainbow trout was not adversely affected by any of




the compounds at the concentrations tested.




     Two studies on the effects of environmental factors on the toxicity  of




arsenic to freshwater organisms have been reported.  Sorenson (1976c) showed




that increased water temperature decreased the median lethal time of green




sunfish during exposure to two concentrations of arsenic(V) (Table 6).  Lima,




et al.  (1984) found that the toxicity of inorganic arsenic(III) to Daphnia




magna was decreased by about a factor of 3 when food was added in 48-hr cescs




compared to exposures in which food was not added.  Additional exposures




showed that arsenic(III) did not affect additional unfed animals from 48  co




96 hours, indicating that the lack of food in these tests was noc too stress-




ful.  Ars^enicdll) increased albinism in channel catfish (Westerman and




Birge, 1978).




     Exposures of embryos and larvae of rainbow trout and goldfish to




inorganic: arsenic(III) resulted in values that were several cimes lower chan.




those  for older juvenile stages of these species (Tables 1 and 6), and  chese




values were  lower than the chronic values in Table 2.  The lowest value




obtained in  any test on arsenic, however, was 40 ,jg/L from a 7-day exposure
                                     11

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of embryos and Larvae of che coad, Gascrophryne carolinensis, co inorganic




arsenic(III)  (Birge, 1978).  This value is abouc a faccor of 4.5 lower chan




che freshwacer Final Chronic Value for inorganic arsenic(III).




     Bryan (1976) exposed che salcwacer polychaece worm, Nereis diversicolor,




co arsenic(III) and escimaced che 192-hr LC50 co be greacer  chan 14,500 yg/L




(Table 6).  Arsenic(III) caused ocher effeccs, such as depressed oxygen




consumpcion race and behavioral changes, in mud snails exposed co concencra-




cions greacer chan 2,000 ug/L for 72 hours (Maclnnes and Thurberg, 1973).









Unused Daca




     Some daca on che effeccs of arsenic on aquacic organisms were noc used




because che scudies were conducced wich species chac are noc residenc in




Norch America.  Daca were noc used if arsenic was a coraponenc of a mixcure




(Thomas, ec ai. 1980; Wong, ec al. 1982).  Reviews by Chapman, ec al. (1968),




Eisler (1981), Eisler, ec al. (1979), Kaiser (1980), Phillips and Russo




(1978), Taylor (1981), Thompson, ec al. (1972), and U.S. EPA (1975, 1976b)




only concain daca chac had been published elsewhere.




     Daca in Dabrowski (1976), Paladino (1976), and Paladino and Spocila




(1978) and one value in Mounc and Norberg (1984) were noc used because




concrol survival was coo low.  Scudies by Eipper (1959), Grindley (1946),




Irgolic, ec al. (1977), and Spocila and Paladino (1979) were noc used because




insufficienc decail was reporced abouc such iceras as use of  concrols and




concrol survival or because mechodology problems occurred during che cescs




which made che resulcs quescionable.  Bringmann and Kuhn (1982) culcured




Daphnia Tiagna in one wacer buc conducced cescs in anocher wacer.  Tescs by




Comparecco, ec al.  (1982), Jones  (1940, 1941), Schaefer and  Pipes (1973),
                                      12

-------
Scary and Kraczer (1982), and Weir and Hine (1970) were noc included because




che medium or dilution water was unacceptable.




     Papers by Baker, ec al. (1983), Belding (1927), Brunskill, ec al.




(1980), Budd and Craig (1981), Chriscensen (1971), Chriscensen and Tucker




(1976), Chriscensen and Zielski (1980), Conway (1978), Devi Prasad and




Chowdary (1981), Hilcibran (1967), Jennecc, ec al. (1982), Lawrence (1958),




Maeda, ec al. (1983), McLarcy (1960), Morris, ec al. (1984), Nissen and




Benson (1982), Oladimeji, ec al. (1979, 1982, 1984b), Oncario Wacer Resources




Commission (1959), Penrose (1975), Planas and Lamarche (1983), Surber  (1943),




and Wescerraan and Birge (1978) were noc used because che  species names were




noc given, che concencracions causing effeccs or che effecc endpoincs  were




noc clearly reported or defined, or no cesc effeccs were  given.  Johnson




(1978) was noc used because che fish were noc acclimaced  co che cesc wacer




for a sufficienc amount of citne afcer colleccion from che  field.  A scudy by




Passino and Kramer (1980) on che effeccs of arsenic on Lake Superior cisco




fry was noc used because fry were obcained from egปs and  sperm of cwo




different species.




     Several papers dealing wich  che  accuraulacion  of arsenic  in aquaeic




organisms, including chose by Brooks, ec al.  (1982), Bryan, ec al.  (1983),




Copeland, ec al. (1973), Dupree (1960), Ellis (1937),  Ellis,  ec al. (1941),




Foley, ec al. (1978), Gibbs, ec al.  (1983), Harden (1976),  Huncer,  ec  al.




(1981), La louche  and Mix  (1982), Maher  (1983), Marcin,  ec al. (1984), May




and McKinney  (1981), Mehrle, ec al.  (1982), Penningcon,  ec al. (1982), Reay




(1972),  Sandhu  (1977),  Sohacki  (1968),  Sorenson,  ec al.  (1979, 1980),  Scary,




ec  al.  (1982),  Tsui  and  McCarc  (1981),  Wagemann,  ec al.  (1978), Whyce  and




Englar (1983),  and Wiebe,  ec  al.  (1931), were noc  used because che  cescs  were
                                      13

-------
  conducted  in distilled wacer, were not  Long enough, or  were not  flow-through,




  or because che concentration of arsenic in the  test solution during  che  test




  /aried unacceptably or was unknown.  BCFs calculated by Anderson.,  et  al.




  (1979), Isensee, et al. (1973), Klumpp  and Peterson (1981), Schuth,  ec al.




  (1974), and Woolson, et al. (1976) were not used because they were calculated




  from microcosm or model ecosystem studies in which water concentrations




 decreased with time or were obtained after short exposures before



 sceady-state  was reached.








 Summary




      The  chemistry  of  arsenic  in water is  complex and  the form present in




 solution  is dependent  on  such  environmental  conditions  as  Eh,  pH, organic




 concent,  suspended  solids,  and sediment.  The  relative  toxicities of the




 various forms of  arsenic apparently vary from  species to species.  For




 inorganic arsenic(III)  acute values for  sixteen  freshwater  animal species




 ranged  from 312 ug/L for a  cladoceran  to 97,000  ^g/L for a  midge, but  the




 three acute-chronic ratios  only  ranged  from 4.660 to 4.862.  The  five  acute




values  for inorganic arsenic(V) covered  about  the same range, but the  single




acute-chronic ratio was 28.71.  The six  acute  values for MSMA ranged  from




3,243 to 1,403,000 
-------
 che alga,  Selenascrum capricornutum,  was  45  times  more sensitive co




 arsenic(V) than to arsenic(III),  although other  data present  conflicting




 information on the sensitivity of this alga  to arsenic(V).  Many plant  values




 for inorganic  arsenic(lll)  were  in the same  range  as the  available  chronic




 values  for freshwater animals;  several plant values  for arsenic(V)  were lower




 than  the one available chronic value.




      The other toxicological  data revealed a wide  range of  toxicity based on




 tests wich a variety  of freshwater species and endpoints.   Tests  with early




 life  stages appeared  to be  the most  sensitive indicator of  arsenic  toxicity.




 Values obtained  from  this type of test with  inorganic  arsenic(lll)  were lower




 than  chronic values contained in  Table 2.  For example, an  effect concentra-




 tion of 40  ug/L was obtained  in a test on inorganic  arsenic(III)  with embryos



 and larva.e  of  a toad.




     Twelve species of  saltwater  animals  have  acute  values  for  inorganic




 arsenic(III) from  232  to 16,030 ;jg/L  and  the  single  acute-chronic ratio is




 1.945.  The only values available  for  inorganic  arsenic(V)  are  for  two




 invertebrates  and  are between 2,000 and 3,000  Mg/L-  Arsenic(HI) and




arsenic(V)   are equally  toxic  to various species  of saltwater  algae,  buc che




sensitivities of the species  range from 19 ng/L  to more chan  1,000  ^ag/L.  In




a test with an oyster, a BCF  of 350 was obtained for inorganic  arsenicCIII).
National Criteria




     The procedures described in the "Guidelines  for Deriving Numerical




National Water Quality Criteria for the Protection of Aquatic Organisms arid




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




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




affected unacceptably if the four-day average concentration of arsenicCIII)




                                     15

-------
 does not exceed 190 ug/L more chan once every chree years on the average and




 if che one-hour average concencracion does noc exceed 360 ug/L more chan once




 every chree years on che average.




      The procedures described in che "Guidelines for Deriving Numerical




 National Wacer Qualicy Criceria for che Proceccion of Aquacic Organisms and




 Their Uses" indicace chac, except possibly where a locally iraporcanc species




 is  very  sensicive, salcwacer aquacic  organisms and cheir uses should noc be




•affecced unaccepcably if che four-day average concencracion of arsenic(III)




does  noc  exceed 36 -jg/L more chan once  every chree years on che average and




if  che one-hour average concencracion does noc exceed  69 ปjg/L more chan once




every chree years  on  che  average.   This  criterion might  be  coo  high wherever




Skeleconema coscacum  or Thalassiosira aescivalis  are ecologically important.




      Noc  enough  daca  are  available  co allow derivation of numerical national




wacer qualicy criceria  for  freshwater aquacic  life  for inorganic  arsenic(V)




or  any organic  arsenic  compound.   Inorganic  arsenic(V) is acucely  coxic  co




freshwacer  aquacic animals  ac concentrations as low as 850  jg/L and an




acuce-chronic racio of  28 was obtained with  the fathead  minnow.  Arsenic(V)




affecced  freshwacer aquacic  plants ac concencracions aa  low as 48 ug/L.




Monosodium mechanearsenace  (MSMA) is  acucely coxic  co aquacic animals ac




concencracions as  low as 1,900 ,jg/L, buc no daca  are available concerning




chronic coxicicy co animals or coxicicy co planes.




     Very few data are  available concerning che coxicicy  of any form of




arsenic ocher chan inorganic arsenic(HI)  co salcwacer aquacic life.  The




available daca do show  chac  inorganic arsenic(V)  is acucely coxic co sale-   '




wacer animals ac concencracions as low as-2,319 pg/L and  affecced some




saltwater planes ac 13  co 56 yg/L.  No daca are available concerning che
                                     16

-------
chronic coxicicy of any form of arsenic other than inorganic arsenic(III) co




salcwacer aquatic life.




     EPA believes chat a measurement such as "acid-soluble" would provide a




more scientifically correct basis upon which to establish criteria  for




metals.  The criteria were developed on this basis.  However, at chis time,




no EPA approved methods for such a measurement are available to implement the




criteria through the regulatory programs of the Agency and the States.  The




Agency is considering development and approval of methods for a measurement




such as "aicid-soluble".  Until available, however, EPA recommends applying




the criteria using the total recoverable method.  This has two impacts: (1)




certain species of some metals cannot be analyzed directly because  the total




recoverable method does not distinguish between individual oxidation states,




and (2) these criteria may be overly protective when based on the total




recoverable method.




     The recommended exceedence frequency of three years is the Agency's besc




scientific judgment of the average amount of time it will take an unstressed




system to recover from a pollution event in which exposure to arsenic(III)




exceeds the criterion.  Stressed systems, for example, one in which several




outfalls occur in a limited area, would be expected to require more time for




recovery.  The resilience of ecosystems and their ability to recover differ




greatly, however, and site-specific criteria may be established if  adequate




justification is provided.




     The use of criteria in designing waste treatment facilities requires the




selection of an appropriate wasteload allocation model.  Dynamic models are




preferred for the application of these criteria.  Limited data or other




factors may make their use impractical, in which case one should rely on a
                                     17

-------
sceady-acace model.  The Agency recommends che interim use of 1Q5 or 1Q10 for




Cricerion Maximum Concencracion (CMC) design flow and 7Q5 or 7Q10 for che




Cricerion Continuous Concencracion (CCC) design flow in steady-state models




for unstressed and stressed systems respectively.   These matters are




discussed in more detail in che Technical Support  Document for Water




Qualicy-Based Toxics Control (U.S. EPA, 1985).
                                     18

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Bringmann, G. and R. Kuhn.  1978b.  Tescing of substances for cheir coxicicy




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                                       50

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                                       of
                                                                     ^
            Conference,  1943.  Washingcon  D c •

                                    g   '  D
                                                        Wildlife Inscicuce 8:
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Phycoplankcon.  Mar. Ecol. Prog
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                               regg
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