e _
                                         WO  5  88
                                                     Draft
                                                     8/30/88
  AMBIENT AQUATIC LIFE  WATER  QUALITY CRITERIA FOR

                   ANTIMONY(III)
        U.S.  ENVIRONMENTAL PROTECTION AGENCY
         OFFICE  OF  RESEARCH AND DEVELOPMENT
        ENVIRONMENTAL RESEARCH LABORATORIES
                 DULUTH, MINNESOTA
             NARRAGANSETT, RHODE  ISLAND

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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 products does not constitute endorsement
or recommendation for use.

This document is available to the public through the National Technical
Information Service (NTIS), 5285 Port Royal Road, Springfield, VA  22161.
                                        ii

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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 6. Prothro
                                    Director
                                    Office of Water Regulations and Standards
                                     iii

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                                ACKNOWLEDGMENTS
Loren J.  Larson
(freshwater author)
University of Wisconsin-Superior
Superior, Wisconsin
Robert S.  Carr
(saltwater author)
Battelle Ocean Sciences
Duxbury, Massachusetts
Charles E. Stephan
(document coordinator)
Environmental. Research Laboratory
Duluth, Minnesota
David J. Hansen
(saltwater coordinator)
Environmental Research Laboratory
Narragansett, Rhode Island
                                        IV

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                                   CONTENTS








                                                                         Page




Foreword. . .	  ' i i



Acknowledgments	   iv




Tables	•	•••	   vi








Introduction	    1



Acute Toxicity to Aquatic Animals	    4



Chronic Toxicity to Aquatic Animals	    5




Toxicity to Aquatic Plants	•	    6




Bioac cumulation	;	• •	    7




Other Data	    7




Unused Data	    8



Summary	 . .	   9



National Criteria		  10




Implementation	• •	  11
References,
                                                                           28

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                                    TABLES
                                                                         Page


1.   Acute' Toxicity of Antimony(111) to Aquatic Animals	  16
        •                         *•;

2.   Chronic Toxicity of Antimony( III) to Aquatic Animals	  19


3.   Ranked Genus Mean Acute Values with Species Mean Acute-Chronic


      Ratios	•	  21


4.   Toxicity of Antimony( 111) to Aquatic Plants	  24


5.   Bioaccumulation of Antimony( 111) by Aquatic Organisms	  25


6.   Other Data on Effects of Antimony(111) on Aquatic Organisms	  26
                                        VI

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Introduction

    Antimony occurs naturally in the  environment.   Geologic  formations  and


minerals such as stibnik,  kermesite,  senarmonite,  and jamesonite  are  comprised


in part of antimony.  Water-borne antimony can result from natural  weathering


of these formations or from anthropogenic sources  such as effluents of  mining,


manufacturing and municipal wastes.  Important uses of antimony,  as antimony


oxide,  include  its  incorporation into various materials as a flame  retardant.


There are no known  biological functions for antimony (Wood and Wang 1985).


    Oxidation states of antimony include -3, 0,. +3, and +5.  According to


Callahan et al. (1979), the  +3  state occurs under "moderately oxidizing


conditions," whereas +5 predominates in highly oxidizing  environments.  Field


data  from Andreae  et al.  (1981)  indicated that in natural waters antimony(V)


greatly predominates,  although  their samples appear  to have been taken from


we 11-oxygenated waters.   The possible  effect of dissolved oxygen levels

approaching or  entering anoxia  on  the  ratio  of Sb(111)/Sb(V)  is  unknown.


    Callahan et al.  (1979)  stated  that important  processes  influencing the
                                                            /'
fate  of antimony  in the aquatic environment  include  chemical  speciation

(determined by  ambient oxygen levels),  volatilization, and  sorption  to


sediments.  Andreae et al.  (1981)  indicated  that  biomethylation  is also  an

important  process which may, in addition to  the volatilization of  stibine


(SbH3)  from reducing sediments, act  to remobilize antimony from bed


sediments.   These processes and reactions are similar to those found for


certain other metals and  metalloids  (e.g.,  arsenic,  selenium, mercury) and  are


 important in assessing environmental impacts (Wood and Wang 1985).


     Precipitation of antimony, primarily as antimony trioxide (Sb203) or


 antimony oxychloride (SbOCl) can be an important factor  in limiting soluble

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antimony levels in natural waters,  and can influence the  results  of  toxicity



tests.  Antima
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antimony(III).   Results from studies on freshwater organisms  in which  antimony

trioxide was used were placed in Table 6,  if otherwise  acceptable.   In all

cases, toxicity tests utilizing antimony trioxide produced "greater than"

values.  Only acute toxicity tests utilizing antimony trichloride were

included in the freshwater section of Table 1 and used  to derive freshwater

criteria.  Data from acceptable tests on both antimony  trichloride and

antimony trioxide were used in the derivation of the saltwater criterion.

    Unless otherwise noted, all concentrations of antimony(111) in water

reported herein from toxicity and bioconcentration tests are  expected to be

essentially equivalent, to acid-soluble antimony(111) concentrations.  All

concentrations are expressed as antimony, not as  the chemical tested.

Although antimony(V)  is expected to be the predominant oxidation state at

chemical equilibrium  in oxygenated alkaline water (Andreae et al.  1981), it

was assumed that whin  antimony(III) was introduced into  stock or test

solutions,  it would persist as  the predominate state throughout the test,  eVen

if no  analyses specific for the antimony(111) oxidation  state were  performed.

    A  comprehension 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

understand  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 round-off error in subsequent

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

presented herein supersede the  aquatic life information in the  previous  .

criteria  document  for antimony  (U.S.  EPA  1980a)  because these  criteria were
                                                                              ^
derived using  improved procedures and additional information.   The latest

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comprehensive literature search for information for this document  was


conducted in July, 1986; some more recent information was also included.
Acute Toxicitv to Aquatic Animals


    Acceptable data on the acute toxicity of antimony(111)  to freshwater


organisms are available for seven species (Table 1).  Five  of those species,


an annelid, amphipod, caddisfly, the rainbow trout, and the bluegill,  have


reported LCSOs greater than the highest soluble antimony(111) levels


attained.  These values were greater than about 26,000 ng/L (Brooke et al.


1986; Spehar 1987).


    Finite LCSOs were reported  by Brooke et'al. (1986), Kimball (Manuscript),


and Spehar (1987) for the fathead minnow, Pimeohales  promelaa. the cladocerans


Daphnia magna and Ceriodaohnia  dubia and a  hydra,  Hvdra oligactis.  The minnow

                                       $'•
and cladoceran Species Mean Acute Values* were  21,800  ng/L,  18,140  /jg/L,


and 3,470 Hg/L,  respectively.   The  hydra was  considerably  more  sensitive  to


antimony(III) with  a  96-hr LC50 of  500  ng/L.   Antimony(111)  was more  toxic


to fi. magna  in tests  in  which  the  organisms were  fed.  The 48-hr  EC50 was 33%


lower when the cladoceran was  fed.


     Freshwater Species  Mean  Acute  Values  (Table 1) were calculated as
                             \

geometric  means  of  the  available acute  values, and then Genus Mean Acute


Values  (Table  3) were calculated as geometric means of the available  Species


Mean Acute Values.   Of  the nine freshwater genera for which mean acute values


are  availably  the most sensitive genus,  Hvdra. is at least 51 times  more


 sensitive  than the most resistant genus.   The freshwater Final Acute  Value for


 antimony(lll)  was calculated to be 175.0 ng/L, using the procedure


 described in the Guidelines.  The Final Acute Value  is lower than the  lowest


 freshwater Species Mean Acute Value.

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    The acute toxicity of antimony(111)  to saltwater animals has  been




determined with seven invertebrate and  four fish species (Table 1).   The  range




of acute values extends from 3,780 pg/L for adult sea urchins,  Hvtechinus




nictus (Bettelle Ocean Sciences 1987)  to > 1,000,000 jig/L for the




muramichog, Fundulus heteroclitus (Dorfman 1977).,  Acute values were similar



from tests with antimony trichloride and antimony trioxide with the sheepshead



minnow, Cvprinodon variegatus. and possibly with the mysid, Mvsidopsis bahia



(Battelle Ocean Sciences 1987; Heitmuller et al. 1981; U.S. EPA 1978).  Hughes



and Boothman (1987) reported unstable antimony  in flow-through tests with




Menidia beryl 1ina caused by the hydrolysis of antimony trichloride to antimony




oxychloride.   The acute  value of 7,830 /ig/L from their test differed  little




from the  acute value  of  21,900 pg/L from  a static test with the  same




species (Battelle Ocean  Sciences  1987), probably because most  of the  mortality




in both tests  occurred during the first 24 hours of  the  96-hr  tests.



    Acute values for  the seven most sensitive species,  four  invertebrate



species from three phyla,  and three fish  species, differed by  only a  factor of




3.4:   The saltwater Final  Acute Value  is  2,934  Mg/L,  which is  lower  than




the lowest  saltwater  Species  Mean Acute Value.   The  saltwater  Final  Acute



Value  is  much  higher  than  the  freshwater  Final  Acute Value,  probably because




chloride  reduces the  toxicity of  antimony(111).
 Chronic Toxicity  to  Aquatic  Animals



     The available data  that  are  usable  according to  the  Guidelines  concerning




 the  chronic  toxicity of antimony(111)  are summarized in  Table 2.   Kimball



 (Manuscript)  conducted  a life-cycle  test with a cladoceran,  Daohnia magna.   In




 relatively hard water (220 mg/L  as  CaC03),  survival  of the cladoceran was




 reduced.to 40% at a  concentration of 4,160 ng/L, although reproduction of

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the survivors was equal or better than that of the controls.   Survival  of

cladocerans exposed to 2,490 pg/L was equal to that of the controls.   The

chronic value for this test was 3,218 pg/L and the acute-chronic ratio was

5.633.  The 28-day LC50 was 4,510 pg/L.

    An early Ilife-stage chronic exposure with the fathead minnow (Pimephales

promelas) was also conducted by Kimball (Manuscript).  Growth of juveniles was

the most sensitive effect, and was reduced at a concentration of

2,310 psg/L.  No significant reduction  in survival or growth was observed at

1,130 pg/L.  The resulting chronic value and  acute-chronic ratio were

1,616 ng/L and 13.51,  respectively.

    The chronic toiicity  of antimony(111)  has been determined in two early

life-stage tests with  a saltwater  fish, the  inland silverside,  Menidia

bervllina  (Hughes and  Boothman 1987).   Results  from  the  testa were similar,

with  concentrations  >  8,770 ng/L  reducing  survival,  and  concentrations

>  4,030 ng/L reducing  weights  of  surviving fish.   No effects  were  detected

at <  2,230 ng/L.  Chronic values  for the  two tests were  2,874 and
                                                             /
3,016 /ig/L;  the  acute.-chronic  ratios were  2.724 and  2.596,  respectively.

    The available Species Mean Acute-Chronic Ratios  are  5.633,  13.51,  and

2.659 (Table 3).  The  geometric  mean of these three  values  is 5.871,  which  is

the Final  Acute-Chronic  Ratio.   Division of the freshwater  and  saltwater  Final

Acute Values by  5.871  results  in freshwater and saltwater Final Chronic Values

of 29.81  and 499.7  pg/L,  respectively.
 Toxicitv to Aquatic Plants

     Data on the effects of antimony(III) on aquatic plants are summarized in

 Table 4.  In a 4-day exposure with the green alga Selenastrum capricornutum.

 the EC50 (chlorophyll a.) was 610 jig/L.(U.S. EPA 1978).  Within the obvious

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limitations of this  restricted data set,  this  might  indicate  a  high  relative



toxicity of antimony(111)  to freshwater algae  compared to  other freshwater



organisms.   Brooke et  al.  (1986)  reported the  EC50 for duckweed (Lemna  minor)




to be greater than solubility.  No effects were observed at the highest




concentration attainable,  25,200 ng/L.



    Information on the toxicity of antimony(111) to saltwater plants is




limited to one 96-hr test with the diatom, Skeletonema costatum (U.S.  EPA




1978).  No effect was observed on chlorophyll A at 4,200 -fig/L.



    A Final Plant Value, as defined by the Guidelines, cannot be obtained




because no test has been conducted with a sensitive aquatic plant species in




which the concentration of  antimony(111) was measured.
Bioaccumulation



    Barrows et al. (1980) studied uptake of antimony(111)  in bluegills  (Table



5).   In a 28-day  exposure, no antimony  residues  significantly  greater than



those of the  controls were found.   Antimony is known  to  occur  in  the tissues



of  saltwater  organisms  (Hall et  al.  1978;  Goldberg  1972;  Chattopadhyay  et al.



1979; Greig and Jones 1976).  No data  are  available on the magnitude of



bioconcentration  of  antimony(111)  in salt  water.  Antimony is  one of several



elements known to form  methyl-metal compounds  in environmental exposures which




readily bioaccumulate  (Wood  and Wang 1985).



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




tissue,  as  defined in the Guidelines,  is available  for antimony(111),  and,




therefore,  no Final  Residue  Value can be calculated.

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Other Data



    Additional data concerning the lethal and sublethal  effects of




antimony(III) on aquatic species are presented in Table  6.   Birge (1978)  and



Birge et al.  (1979,1980) conducted studies on the mortality and teratogenic



effects of antimony trichloride on embryo-larval  stages  of  rainbow trout



(Salmo gairdneri). goldfish (Carassius auratus).  and a toad (Gastrophvrne



carolinensis).  ECSOs (death and deformity) were calculated at 4 days



post-hatch.  The goldfish was significantly more resistant  to antimony(111),



with an EC50 of 11,300 Mg/L, than the rainbow trout and the toad, which had




ECSOs of 660 and 300 (ig/L, respectively.



    Also included  in Table 6 are results of toxicity tests on antimony



triozide (SboOo).  Results are available for a cladoceran  (Daphnia magna).



fathead minnow (Pimeohales promelas) and a bluegill (Lepomis macrochirus).




Presumably due to  the low solubility of  this salt, all results were  reported



as "greater than"  values.  Independent of nominal concentrations, soluble




antimony(III) levels in all these tests  were probably about 4,000 ng/L



(Brooke et al. 1986), which is below the known acute sensitivity  of  most




freshwater fish and invertebrates to antimony(III).
Unused Data



    Some data on the effects of antimony  on  aquatic organisms were  not used



because the studies were conducted with species  that are not  resident  in North



America (e.g., Juhnke and Ludemann 1978).  Results were not used  when  the  test



procedures (e.g., Amiard 1976; Knie  et al. 1983)  or test material  (e.g.,



Tfoodiwiss and, Fretweli  1974) were not adequately described.   Results by  .



Taraulinus (1979) were not used because the dilution water  was  renewed  only



once a week.  Data were not  used when antimony  was a component  of. an effluent.

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mixture,  or sediment (e.g.,  Hildebrand and Carter 1976;  Jay and Muncy 1979;
Payer and Runkel 1978;  Seeleye et al.  1982;  Thomas et al.  1980b).   Tests
conducted with too few test organisms (e.g., Tarzwell and Henderson 1960) were
not used.  Results of tests conducted on antimony(V) were not used (e.g.,
Hollibaugh et al. 1980; Thomas et al. 1980a).
    Reports of the concentrations of antimony in wild aquatic organisms.(e.g.,
Brezina and Arnold 1977; Chassard-Bouchard  and Balvay 1978; Chattopadhyay et
al. 1979; Cherry et al. 1979,1980; DeGoey et al.   1974; Friant and Koerner
1981; Friant and Sherman 1980; Goldberg  1972; Greig  and Jones 1976; Hall et
al. 1978; Hert and Klusek 1985;  Korda et  al. 1977;  Lucas et al. 1970; Moller
et al. 1983; Payer et  al. 1976;  Shuman et al. 1977;  Smock  1983a,b; Telitchenko
et al. 1970; Tong et al. 1974; Uthe and  Bligh 1971)  were not used to  calculate
bioaccumulation  factors when  the number  of  measurements of the  concentration
in water was too small.
 Summary
     Acute  toxicity  of  antiraony(IIl)  to  several  freshwater species  did not
 occur  below the  limits of  solubility of antimony salts.   These species
 included an annelid,  an amphipod,  a  caddisfly,  and rainbow trout.   Four
 species  were reported to be acutely  sensitive to antimony(111).   Mean acute
 values for the fathead minnow,  Daphnia  magna. Ceriodaphnia dubia.  and a hydra
 were 21,800, 18,140,  3,470, and 500  /ig/L,  respectively.   Chronic toxicity
 of antimony(III) to Daphnia magna and the fathead minnow has been studied.
 Chronic values were 3,218 and 1,616 pg/L,  respectively.
     The freshwater alga Selenastrum capricornutum had an EC50 of 610 Mg/L
 in a 4-day exposure to antimony(III).  There was no effect on a freshwater
 vascular plant,  Lemna minor, at the highest  concentration attainable  in

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water.  Negligible uptake of antimony(111)  was reported in the bluegill



(Lepomi s macrochi rus).



    Acute toxicity tests have been conducted on antimony(111)  with eleven



genera of saltwater animals and the acute values range from 3,780 ng/L for



the sea urchin, Lvtechinus pictus. to > 1,000,000 ng/L for the mummichog,



Fundulus heteroclitus.   The values for the seven most sensitive genera,



including representatives of four phyla,  differed by only a factor of 3.4.



The chronic values from two early life-stage-tests with the inland silverside,



Menidia bervllina. were 2,874 and 3,016 ng/L; the acute-chronic ratios were



2.724 and 2.596, respectively.  The diatom, Skeletonema costatum. was not




affected by 4,200 fig/L.








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 unaoceptably  if the four-day average concentration of antimony(111)



does not exceed 30 pg/L more than once every three years  on the average



and if the one-hour average concentration does not exceed 88 ng/L more




than once every three years on the average.



    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, saltwater aquatic  organisms and their  uses  should  not be



affected unacceptably  if the four-day  average concentration of antimony(111)
                                       10

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does not exceed 500 ng/L more than once every three  years  on the  average
and if the one-hour average concentration does not exceed  1,500  /ug/L more
than once every three years on the average.   Because sensitive saltwater
animals appear to have a narrow range.in susceptibilities  to antimony(111),
this criterion will probably be as protective as intended  only when the
magnitudes and/or duration of excursions are appropriately small.

Implementati on
    Because of the variety of forms of antimony!111) in ambient  water and the
lack of definitive information about  their  relative toxicities to aquatic.
species,  no available analytical  measurement  is known to  be  ideal for
expressing aquatic life  criteria  for  antimony(III).  Previous aquatic life
criteria  for  metals  and  metalloids  (U.S.  EPA 1980b) were  expressed  in terms  of
the total  recoverable measurement (U.S.  EPA 1983a), but newer criteria for
metals and metalloids have been  expressed in terms  of  the acid-soluble
measurement  (U.S.  EPA  1985b).   Acid-soluble antimony!Ill) (operationally
 defined as the antimqny(111) that passes through a 0.45 urn membrane filter
 after the sample has been acidified to a pH between 1.5  and 2.0 wi.th nitric
 acid)  is probably the best measurement at the present for the following
 reasons:
  1.  This measurement is compatible with nearly all available data concerning
      toxicity of antimony(III) to, and bioaccumulation of antimony(III)  by,
      aquatic organisms.   It is expected that the results of tests  used in the
      derivation of the  criteria  would not  have been substantially  different if
      they had been reported in terms  of acid-soluble antimony(111).
  2.  On  samples of ambient water, measurement of acid-soluble antimony(111)
      will probably measure  all forms  of antimony(III) that  are  toxic to
                                        11

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aquatic life or can be readily converted to toxic forms under natural
conditions.  In addition, this measurement probably will not measure
several forms, such as antimony(111) 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.
Although water quality criteria apply to ambient water, the measurement
used to express criteria is  likely to be used to measure antimony(111)  in
aqueous effluents.  Measurement of acid-soluble  antimony(111) is expected
to be "applicable  to effluents.   If desired,  dilution of effluent with
receiving  water before measurement of acid-soluble  antimony(111) might  be
used to determine whether the  receiving water can  decrease the
concentration of  acid-soluble  antimony(III)  because of  sorption.
The acid-soluble  measurement is expected to  be  useful for  most  metals  and
metalloids,  thus  minimizing the number  of  samples  and procedures  that  are
necessary.
The acid-soluble  measurement does not require  filtration of the sample at
the time  of collection,  as does the dissolved  measurement.
For the  measurement of total acid-soluble antimony, the only treatment
 required at the time of collection is preservation by acidification to a
pH between 1.5 and 2.0,  similar to that required for the total
 recoverable measurement.
 Durations of 10 minutes to 24 hours between acidification and filtration
 of most samples of ambient water probably will not  substantially affect
 the result of the measurement of total acid-soluble  antimony.  However,
 acidification might not  prevent oxidation or reduction of  antimony(111)
 and antimony(V).  Therefore, measurement of acid-soluble  antimony(111)
                                   12

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     and/or antimony(V) might  require separation or measurement at the time of




     collection  of the  sample  or  special preservation to prevent conversion of




     one  oxidation state  of  antimony to  the other.



 8.   Ambient  waters  have  much  higher buffer intensities at  a pH between  1.5




     and  2.0  than they  do at a pH between  4 and 9  (Stumm and Morgan  1981).




 9.   Differences in  pH  within  the range  of 1.5 to  2.0 probably will  not  affect




     the  result  substantially.



10.   The  acid-soluble measurement does  not require a  digestion  step,  as  does




     the  total  recoverable measurement.



11.   After acidification  and filtration of the  sample  to  isolate  the




     acid-soluble antimony,  the analysis for  total acid-soluble  antimony can




     be performed using either atomic  absorption  spectrophotometric  or




     ICP-atomic  emission  spectrometric  analysis  (U.S.  EPA  1983a),  as with the




     total recoverable  measurement.   It might be  possible  to separately



     measure  acid-soluble antimony(111) and acid-soluble  antimony(V) using the




     methods  described  by Andreae et al. (1981).



Expressing aquatic life criteria for antimony(III) in terms of the acid-



soluble measurement  has both  toxicological and practical  advantages.  The U.S.



EPA is considering development and approval of just such a method.



    Metals and metalloids might  be measured using the total recoverable method



(U.S. EPA 1983a).  This would have two major impacts because this method



includes a digestion procedure.  First, certain species of some metals  and



metalloids cannot be measured because the total recoverable method  cannot




distinguish between  individual oxidation  states.   Second,   in some cases these




criteria would  be overly  protective when  based on the total recoverable method




because  the digestion  procedure  might dissolve antimony that  is not  toxic and




cannot be converted  to a  toxic form under natural conditions.  Because  no
                                       13

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measurement 1st known to be ideal for expressing aquatic life criteria for
antimony(III) or for measuring antimony(111)  in ambient water or aqueous
effluents, measurement of acid-soluble antimony(111),  acid-soluble antimony,
and total recoverable antimony in ambient water or  effluent or both might be
useful.  For example, there might be cause  for concern when total recoverable
antimony is much above an applicable limit,  even though acid-soluble
antimony(III) is below the limit.
    In addition, metals and metalloids might be measured using the dissolved
method, but this would also have several impacts.   First, whatever analytical
method is specified  for measuring antimony(111) in ambient  surface water will
probably also be used to monitor effluents.  If effluents are monitored  by
measuring only  the dissolved  metals  and  metalloids, the  effluents  might
contain some  antimony(111) that would  not be measured  but might  dissolve, due
to dilution  or  change  in  pH or  both, when the  effluent is mixed  with receiving
water.  Second,  measurement of  dissolved antimony(111) requires  filtration of
the sample at the  time  of  collection.   Third,  the  dissolved measurement  is
especially  inappropriate  for  use  with  such metals  as  aluminum that can exist
as hydroxide and carbonate precipitates in  toxicity  tests  and in effluents.
Use of different methods for  different metals  and  metalloids would be
unnecessarily complicated.  For these  reasons, it  is  recommended that aquatic
 life  criteria, for antimony(III) not be expressed  as  dissolved antimony(111).
    As discussed in the Water Quality Standards Regulation (U.S. EPA 1983b)
 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.
                                        14

-------
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

1983c,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 1983c), but also site-specific, and possibly

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

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

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

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  1985c).  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 fwasteload  allocation
                                                          *'
model.  Although dynamic models are preferred for the application of these

criteria  (U.S.  EPA 1985c), 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 1985c,1987),
                                        15

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Birge,  W.J.,  J.A.  Black and A.G.  Westerman.  1979.  Evaluation of aquatic


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                                         32

-------
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