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

-------
                                    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.
                                       11

-------

-------
                                   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
                                     iii

-------
                                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

-------
                                    CONTENTS








                                                                         Page




Foreword	  i i i



Acknowl edgments	   i v




Tables	   vi








Introduction	    1



Acute Toxicity to Aquatic Animals	    4



Chronic Toxicity to Aquatic Animals	    5



Toxicity to Aquatic Plants	    6



Bioaccumulati on	    7



Other Data	    7



Unused Data	    8




Summary	    9



National Criteria	   10



Implementation	   11








References	   28

-------
                                    TABLES
                                                                         Page




1.   Acute Toxicity of Antimony( 111)  to Aquatic Animals	   16




2.   Chronic Toxicity of Antimony( 111)  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(lII)  by Aquatic Organisms	   25




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

-------
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 -t-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

                                                              't
wel1-oxygenated waters.  The possible effect of dissolved oxyge'h 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 biomethy1 ation is  also an
                                                    $

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



(SbHg)  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 (SbgOg) or



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

-------
antimony levels in natural  waters,  and can influence  the  results  of  toxicity
                                                      , n
tests.   Antimony(III)  does  not occur as a free  ion,  Sb   .   In solution,

antimony(111)  will occur as the cation antimony oxide (SbO*)  or  as  antimony


oxychloride  (SbOCl) (Burns  et al.  1981),  with the  former  predominating.

Soluble antimony will  be the total  antimony occurring in  solution in either  of


these forms.   Antimony oxychloride  transforms to antimony trioxide  (SbgOg)

which precipitates, becoming less  available to  aquatic  organisms.   Brooke  et

al.  (1986)  conducted a study of the effect of' chloride  enrichment on

maintaining  dissolved  antimony concentrations in solutions.   When the chloride

concentration was low, dissolved antimony concentrations  in static  exposures

were reduced by as much as  76% in  96 hours.  When solutions were enriched  with


sodium chloride, adjusting  the chloride ion concentration to 1000 mg/L,  the

maximum reduction in dissolved antimony in 96 hours was 13%.

    Working  with antimony trioxide, soluble antimony concentrations do not

reach levels high enough to produce mortalities for most aquatic organisms,

due to the low solubility of antimony trioxide.  The highest dissolved


antimony concentration attained by Brooke  et al. (198&) was 3,300 Mg/L when

antimony trioxide was added to lab water at a nominal concentration of

110,000 ng/L.   When antimony trichloride (SbCl3) is used, higher soluble

antimony levels can be obtained, but this  is limited by the transformation of

antimony oxychloride  (SbOCl) to antimony trioxide (SbgOg).  Ambient

chloride levels will  have a  strong  influence on this precipitation  and in turn


will influence the maximum  soluble antimony  levels which can be maintained.


    Because antimony  trioxide  will not produce  dissolved antimony!111)


concentrations high enough  to  result  in acute mortality, toxicity  tests using


this compound were not used  in derivation  of national freshwater criteria for

-------
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 when antimony(111) 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 LC50s 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

-------
comprehensive literature search for information for this  document  was




conducted in July,  1986; some more recent information was also  included.








Acute Toticitv 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, Pimephales promelas.  the cladocerans



Daphni a magna and Ceriodaphnia dub i a and a hydra,  Hydra oli gacti s .  The minnow



and cladoceran Species Mean Acute Values were 21,800 pg/L,  18,140 Mg/L,



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




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



to I), 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 available, the most  sensitive genus, Hvdra. is at  least 51 times more



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



antimony(111) was  calculated  to  be  175.0 Mg/L,  using the procedure




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




freshwater Species Mean  Acute Value.

-------
    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 Mg/L  for adult sea urchins,  Hvtechi nus




pictus (Bettelle Ocean Sciences 1987)  to > 1,000,000 ng/L for the




mummichog, 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, Mysidoosi s bahi a




(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 Iina caused by the hydrolysis of antimony trichloride to antimony




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




from the acute  value of 21,900 ng/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, Daphni a magna.  In




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




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

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

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

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

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

    An early life-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 ng/L.  No significant reduction in survival or growth was observed at

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

1,616 ng/L and 13.51, respectively.

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

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

beryl 1ina (Hughes and Boothman 1987).  Results from the tests were similar,

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

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

at < 2,230 MgA-  Chronic values for the two tests were 2,874 and
                                                            /
3,016 Mg/L: tne 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 ng/L,  respectively.




Toxicity to Aquatic  Plants

    Data on the effects of  antimony(111) 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 /ug/L (U.S. EPA  1978).   Within  the  obvious

-------
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  mi nor)




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




concentration attainable,  25,200  Mg/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 chlorophylF  a. at 4,200 ng/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.

-------
Other Data



    Additional data concerning the lethal  and sublethal  effects  of



antimony(111)  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 gai rdneri).  goldfish (Carassius auratus).  and a toad (Gastrophvrne



carolinensi s).  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 pg/L, than the rainbow trout and the toad,  which had



ECSOs of 660 and 300 Mg/L, respectively.



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



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



fathead minnow  (Pimephales promelas) and a bluegill (Lepomi s macrochi rus).



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



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




antimony(111) 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(111).








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.,




Woodiwiss and Fretwell  1974) were not adequately described.   Results by  .



Tamulinus (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 „

-------
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; long 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 antimony(III) 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 pg/L, respectively.   Chronic toxicity



of antimony(111) to Daphnia magna and the fathead minnow has been studied.



Chronic values were 3,218 and  1,616 ng/L, respectively.



    The freshwater alga Selenastrum capricornutum had an EC50 of 610 ^g/L




in a 4-day exposure to antimony!111).   There was no effect on a freshwater




vascular plant, Lemna minor, at the highest concentration attainable in

-------
water.   Negligible uptake of antimony( 1 1 1 )  was reported in the bluegill




( Lepomi 3 macrochi rus) .




    Acute toxicity tests have been conducted on ant imony( 1 1 1 )  with eleven




genera of saltwater animals and the acute  values range from 3,780 MgA for




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




Fundulus heterocl i tus.   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,




Meni di a beryl 1 i na . were 2,874 and 3,016 Mg/L; the acute-chronic ratios were




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




affected by 4,200
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  antimony( 1 1 1 )




does not exceed 30 /^g/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! 1 1 1 )
                                       10

-------
does not exceed 500 Mg/L more than once every three  years on the average




and if the one-hour average concentration does not exceed 1,500 ng/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.








Implementat i 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(111) (operationally




defined as the antimony( 111) that passes through a 0.45 p.m membrane filter



after the sample has been acidified to a pH between 1.5 and 2.0 with 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(111) 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(111) that are toxic to
                                       11

-------
          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.


      3.   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(11 I)  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(111) because  of sorption.


      4.   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.


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


          the  time of  collection, as does the dissolved measurement.


      6.   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.


      7.   Durations of 10  minutes to 24 hours between acidification and  filtration


          of most  samples  of ambient water probably  will not substantially affect

*o
'**        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

-------
     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(111) 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

-------
measurement is 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(111)  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 antimonyf111) 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(III) 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(111)  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 wasteload 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

-------
                                IO
                                CO
                                01
                                                                                               to
                                                                                               oo
                                                                                               en
                                                to
                                                oo
                                                en
                «
                U
                e
                0
                                                        oo
                                                        o>
                                             o
                                             o
                                                                                                o
                                                                                                o
                                                            o
                                                            o
 n  »

—   «   a
                                a
                                a
                                to
                                    a
                                    a
                                                                                                                    m
                                                                                                                    CM
        a  o  _i
        in  1*1  •«•.
                                a
                                a
                                m
                                    a
                                    a
a
•w
to

m
a
o
in
a
a
in
                                                                                                a
                                                                                                PS.

                                                                                                m
a


in
            a
            a
            a
            3
            a
.5       «   •»    I     *"
!Z       it   o  —4     ~
^       •    ,  „•"    2
            -1  O
        -o  -.. «J
         k,   01  a
         o   •  o
                        en

                        to
                                 e   o
                                 o  —
                                             o  —
                                             e  -=
                                                 e   o
                                                 o  —
 e   o
 o  —
e   o       co
o  —       o  —
E  we       E  js
                         e   o
                         o  —
                         >•  I-
                         e   o
                         o  —
             e   o
             o   —
             E   -=
 e  o
 o  —
 E  -=
—  o
                                                                                                                                                 o  —
                                                                                                                                                 e  —
                 •

                 u
(/»
3
*»
O
9
4)
.»
V)

U
0
o
_•
o

0
L.


z
^
o
3
- 3
•o o

Ml k.
« -0
e E
e 3


.
.— ^.
o
.«
Q
3
•o
O
C C
O JI
W Q
« 0
o -^
o o

O i.

o u
u.
^m

ao

tl
u
« a
u •—
o e
-o -c
o a
— . o
CJ Gk

— ^ — ^.
u u


^f ^f
CM O4

NX 0
<— ' e
C 0
o E
u
4> 0
O —
o e

o a

<-> 0
tl
o E

« 0

o e
^5 ^S
o a

U 0
3
4)
0
e
E

^_
o
•o
3
4)
a
^3 (rt
O 3
a. k.
— a
JB E
o. E
& "
f 0
— ^ — .
• .M .M
— • in
^ a
— . k. CO —
e to- • — • a>
> <••«• •«
k. O. k.
O V)
— a
>• 0
mmf ^
»— tn
vt a
— o
•o e
•o u
0 >

3 C
o -o
k. k.
O
» <3
O
A O
e E

o o
QC OO
E
• o
O k.
e o
e
— in
E «
~_>
•o o
O -^

-------
                 CO
                 at
                 o
                 o
 o

 0
 a.
ts>
                                                           o   f*»
                                                           0   00
                                                           o  u
                                                          CO  I/I
                                                                        o  ao
                                                                        o  0)
                                                                       O  —

                                                                        0   v>
            o   u
           CO  
                        «  00
                        o  o>
                        O  —


                        «   (n
                        —   0
                        —   O
                        0   e
                        •«-   0
                                                                   oo
                                                                   ^.
                                                                   o>
                                     0   OO
                                     o   O)
                                    o   —


                                     0   ft
                                      .   g)

                                    —•   o
                                     «   CO
                                     o   01
                                    o   —

                                     0   in
                                                                                                        O   —
                                                                                                                                      —  0
                                                                                                                                      —•  u
 u  •>-
 0   3
                                                                                                             a
                                                                                                             a
                                                                                            a
                                                                                            a
                             a
                             a
                                                                                                        a
                                                                                                        CNI


                                                                                                        10
                                                                                                             a
                                                                                                             a
                                                                                            o
                                                                                            a
    in
a  c*
vn  u  •>-.
u
_J   t.   3
     a  —
                             a
                             a
     8-J
 0
 a  _i  O
     en  a
     •  w
10
»
 I
                                                                         •o
                                                                           a
                                                                                         0
                                                                                        •a
                  a   o
                  o  —
 a   o
 o   —
 S   -=
e  o
o  —
8  •«=
e   o
o   —
e  o
o  —
E  J=
                                                                                                 o  •-
                                                                                                 E  x
                                                                                                 •—  o
e  o

E  ^
>>  V.
e   o
o   —
k.
«•«


•
o
e
.S
S
« -w
0 o
.— 0
u -e
0 •-
a o
tSt kte
o
«•
0
E
o
w
a
V)
0
O
.e
0
0
E

CL>








-
_

C7f
0
3
.w
CO
3
U

^
U
o
u
o
E
to

E
o
a
0
~j
0 3
L. •*-
3 O
O —

E ^
— o
~~" >
•o o
._
_• M
0 3
e —
e •—
0 -C
.— o
J= O
u =
L. • —
-< 0


I/I
^
- c
— . — » o
•«- 0 .—
3 V)
-o e
O 0
*— • i_
—
E >

o n
• —
-o 0
e k.
0 0
f! Z
•— o
e -a
0
> V)
3 —
~i V)
~— a
o

._ ._
v) m
*• >
3 a
«i fc o
0 —
•— o
e j>
0
> VI
3 —
•-^ «
- Q
O

.— ._
in in
9* 9
a a
o
• *•
^" S
^* 0
3 V)
•o «
O k.
^.^
O
-0 0
o -e
o. •*•
0 O
v> -w

— -. o
•^ k.
3 O
19
O V)
~^ 3
,^
"O C
O >
O> X
•— o
-= 0
0. «
E -c
•< ce

o.
E
._
«-
(A 0
C
« • 0
^L -"^» *O
.1^ 4)
U — . (rt
-*. .— 3
(rt C —

c > -^
o a c
O •— t 0
(j ,_ , f^
                                                                          17

-------
 0  OO
 o  Ol
o  —


 0   in
—   0
—   u
 0   e
»-   0
 o  rv.

 0  co
                             O  —
                                              E


                                              u
                                              o
 in  »
 o       o
—   0   a
 o  *•
 4)   3
                             o
                             a
                             CO
                             a
                             a
                             a

                             o"
                             a
                             a
                                                                      00
                                                                      O)
                                                                                       o  r«.
                                                                                       0  ao
                                                                                      o  —

                                                                                       0  
                                                                      a
                                                                      a
                 a
                 oo
a
a
a  o  —i
ui  LJ
u
-l   u   3
     a
                                              a
                                              a
                             a
                             a
                             a
^
a
u

8
M
W
» i.
e o
o —
E -=
•Z .—
e u
< ^-


O
•^1
o
^

0
*



3

•






<••!»
^
>»W >• Q >» 0 >» 0 >• t. >k^ >«W
CO G "^ c"9 CT3 CO CO CO
O— O— O— O— O— 0— O —
E .= Ex ex Ex e j= 6 j= 6 j=
.-» w — O — O — O — u —  ^«- ^-^ ^-^ ^-«K ^^*

-
*


3 333 3 3 2

• . • .
(/^  OO OO OO u.





V)

0 —
^ r*
3 
00 _l
k. - 0
0 ~«. a
J= 0
— . in
u — o
• •• c 9
>— 0 e
— > 0
031-
O ~i 0
a. ^_- j=
i.
0
0
- .c
0>
o in
j™ 3
O —
•— 3
i i
3 3
a u.
(0
u
0
0
. ^
OV
o in
J= 3
U ^M
— 3
i =
3 3
a i—
3
0
• a
O 0
c —
e u
•— o
«
•w — » e
000
0 — -O
jr ._ o
« c c
o. 0 —
0 > u
0 3 O
JZ — ^ >
00 ~~ O
tn
3
O
* O
O 0
c —
C l_
— o
E >

•^ • — • c
O 0 O
0 — -o
-C — O
n c c
0. 0 .—
0 > U
030

00 —— <_)


0 0
in —
k. —
0 >

M« --M. 4)
.— 0 -a
v> -~
— 0
-0 C —
c a *o
9 > —
— 3 C
C 	 10
— — 2
0 O
•o c
« —
0 >
9 - ^
_ -~ 0
— 0 .0

• — o
-o c —
c 0 -a
0 > —
— 3 C
C — » 0
— — * a











ii

™j

-C
01

o
u
1
O 0
— ' W

"~ 'i
II 0>
JZ
U. .
— - o —
~ S
o — =
•*» -^ oo
in c
o •=
II 0
V) k.
OO < 1 —
%
o ^
                                                                             18

-------
                                                               10
                                                               o>
               CO
               C7>
                                                            01 O
                                                            9  O
                                                                           E
                                                                          .c

                                                                          "o
«   3
                                                           10


                                                           O
«
o
— *
^
5,
•
s
e
<
0


*™
u

M
O
u
2
o
^
-tf

^


-^

01
^
H"


a
u .•
'• *• 1H
0 .- •**
1. • a

vO
«v
1
a
i/>
u
u
u
a.
(/»
ac
u
>—
vf

in in 1

0 PO _«
« -1 0
k at o
X i °
^E
l_
C71
^
• U
e o
o —
S -=
•^ o
^— *^
C5 U
« -~


_ •
a
fO
CM
1
a
fO
—






u
a
CM
CM



*
"9
• mf
>• U
e o
o —
B -=
tmf o
^— •••
e i.
< -^



a
CD
a
^»
i
a
1/1
i*j
c^
UJ
o»
VI
^»
UJ
h-
s
h-
.J
^
i/k
CM
(M






•«
a
»*>




9
^>
.^
>• U
e o
o —
fi J=

^B .^
e ..
•< +-



a
"i
a
^
i
a
in
a
CM






^
a
>o




0
•o
•^
^ k.
e o
o —
S -=
— u
^— •«•
e u.
•*. •»-











0
o>
o
in
i
0


>-
h.
o
*

It

t/»
—I
UJ

. _
«
u
1
«
.-











^
c
o
E

e
o
o

V.
c
o

( -
a
u

e
a
o
o
•o

a
in 0
0 U
— o
u -o
0 0
a —
(^ C.9
O
0
» e
o| o u
i .i ^
1 -i s
o
.»
e

a
0
&..
•o o
0 -C
0 a

— E
0 —
u. a.
                                                            in  —
                                                            u  —
 o  •—
—.  c
 e  0
                                                                       0   o
                                                                      "9   e
                                                                                          o

                                                                                          0
                                      0      —
                                      in       o
                                      o
                                                                                                 in      E
                                                                                                 ••-     oo
                                                                                                         o
                                                                                                        U.      CO
                                                                 19

-------
                                               at
                                               in
                                                   
-------
m
o
      O  I  —

     —  90
      «  3
      a.  o
      a  «
      v  a
     —  «  a
      0—3
      O  * •—
      a.  u
                                   a
                                   a
a
a
a
a
a
a
a
o
a. "*
"> —
2 "
*• a.
'• "»
!••»
v> 5
« Lt
3 5
— s
o 5
» 5
a £
^» Hfc
a tn *••


2
VI
3
k.
• _
f
U
O
k.
U
o
- e

u « — in
« .- — —
u o» S
e 0 00
a a 3 o
V k^l — 0
a oo _i
o
0
4)
.••
k.
O
^
VI
3
—

•o u

^ k.
« J3
e E
e 3
* J
3
O
e
E
• *
~v
O
•^J
3
*
Q
•

0 3

— 9
t. i
E o
«K 0


«
O
«_
4)
...
Ob - t-
M *^ 9
9
. ^
>. .f
.« o
^_ VI
M a
— o
•o e
•o u
o >
^^ ^^
a e
o -o
t» w
^. ...
a
• 9
O
.a o
e E
o o
QC (A
- e
» 0
o u
e Q
e
•~ VI
s «

•o o
O ^1
« a
j= «
— E
0 •-
i~ a.

o
._
^
3
^9
O
C
- a
a o
o 6

0 0

O e
•o js
o a
— 0
<-> Q

O
e c
a .c
k. a
0 Q

> o a
• o k.


-------
    o
 «  —
 a  •
 0  o
a  u u
    .•  e
 vi  u  —,
 0   i   —
—  0  O
 o  —  ac
                                                                                                        o>
                                                                                                        l/l
                                                                                                        lO
                                  a
                                  a
                                                                                 a
                                                                                 
oe
UJ
t-
«
»
^
«
VI

VI
3
»•
_
U
O
u
0
0
- .C
Ol
o in
.e 3
u —
— 3
i i
3 3
a u.

VI
3
e
o
u
.a
e
VI
3
• •«
•o e
o >
0. X
— o
.e a
a. 0
S -=
« oc

•
g
0

o
u
V)
0
u

- o
•o 0
O JZ
Q. -~
o o
VI •«
.« o
u —
f 0
in e
0 0
a. -o
._
U VI
«• 3
VI —
o
c -o
o e
O 0
u 0.
j=
i/i
0
i.
• .^
e >
u
O VI
» —
-0 0
e u
0 0
 ae
o

VI
.«
VI
a
- o
•& •«
VI VI
>• >
a a
O
V*
- o
9 0
T3 C

(rt — "
U —
9 »
» i.
— a>
.- J3
V>
O
TJ .—
e T3
o •—
— e
e a>
— - a
• o
o 9
e •—
— o
6 >

•o e
0 0
9 •O
.C O
w e
a. •-
9 U
9 0
^1 >
(/) u
trt
0
o
«
Ol trt
— 0
u c
U 0)
9 i.
J= 0
.£
i>
.— 0
Wm <9
— a
a 3
0 —
a- u
VI
3
O
.—
U
o
t_
- >
•o o
.0.
^ (rt
9 3
e —
e •—
a -c
.— a
.c o
 >
IS* _J
a
o
 0   u

-------
—  .-   o
                                                                              CO

                                                                              o>
                                                                                                                       a.
                                                                                                                       ^
 (rt   «
 o   u   «
.0   «   I-
 

                                                                                                       O
                                                                                               o

                                                                                               3
                                                                                                       E

                                                                                                       x
                                                                                                       o
                                                                                                               o      —
                                                                                                                i        e
                                      «
                     —•      —•       o
                                                      o       •*•
                     6
                     O
                     u.      u.      o
                                                                        23

-------
                                                       CO

                                                       C71
                 0
                 u
                 4)


                 0)
 o
 o
             o
             u
                                      a

                                      to
a
a
a
a
a.

 o
                                           o
                                           u
                                           o
                                                                                         a.
                                                                                         o
                                                       o
                                                       in
                         u
                         UJ
                         a.
                         (SI
                 u
                 Ul
                 a.
             o —
             —   (/I
         M  tt    I
         n  o —^
         «       tr
         e  _i  o
        ^ ~».  cj
         U  Ol   O
         ecu
a
lO
                                                                                                      n>
 =   o
 o   —•
 E   -=
                                                                                     o  —
                                                                                     E  x
                                                                                     —  o
                                       O   3

                                       C71  U
                                       i_   1)
                                      O  
                                -   o


                               O   9
                                                                                                      O

                                                                                                      e
                                                                                                      o
                                                                                         24

-------
                                 a
                                 co
                                 o»
                                      e
                                      o
                                  «-   e

                              n  o  "3
                              —  o   a
                              «  —   a

                              e  —   u
                              •o
                              o
                                                         o


                                                         o
                               a

                               o
at

O
 o

 •
 e


 o
            «•  u
            a  «
            a  *•
            u  a
                                                         in
                                                         o
         M   M    I
         n   a  —4
         «       M
         «  _J  O
        •o  -». o
         u   01  a
                                o  —
                                S   x
                               —   o
                                                   o
                                                   o

                                                   e
                                                   o
                                                           c
                                                           o
                                                           O   3
                                                           L.   I/I
                                                          •~   in
                                                           c  —
                                                           o  —
                                                           o
                                                           o  -o
                                                                               25

-------
                                               a
                                               CO
                                               en
                                                                     CO
                                                                     en
                                      <£>
                                      CO
                                      en
                                       E

                                       x
                                               «
                                               en
                                                                              o
                                                                              o
                                                       o

                                                      CO
                                                       a
                      a
                      a
                      a
                  a
                  a
o
at
u
O
                     a
                     CO


                     en
                                      a
                                      a
                              a
                              «•>
                              u
          —  o
       a  a •_
       m  a  «
       o -o ^

                                                             •«•  o
                                                             0  —
                              a
                              \n
                                                                                                         a
                                                                                                         Ul
                                                                                                         o
 o

 n
                                       10
                                       en
                                                  in
                                                  o
           in

           o
              I



              o
           IA  0>

           O  Vt
           •^  *•
              o
                                      iO
                                      en
O     MM)
—     M  • —4
o     0     n

-     -s• «
e  -a
o  —
•  X     S -C    S
._  o    — u    •—

e  u     e u.    e
e  o
o —
e  o
o —
                                                           c o
                                                           o —
                                                           E -=
                                                          — a
                                                                      o —
                                                                      S  x
                                                                     •—  O
                                       o —
                                       E x
                                      — o
                                       o —
                                       E  x
                                      —  o
o  —
E  x
—  o
o —
£ -=
U 0 M
j: — o
-«*» tn

o
e
- o
e o
o E
u
» 0
o •—
o c
-o .c
o a
— o
<_> a
-~ 0 «
a > e
OUT)
u o w

~«. 0
BOO
o »
-a t. o
e -a E
- 6 -
0 41 0
CC ~— VI
>. -^
k. 0
-O U
E a
« 0

M
A 3
« —
— V)
— 
^H
«
- E
» 0
o w
c a
c
•— (rt
s ±

•o o
o -=
« a
.= «
— E
0 —
i— a.
>- n
U 0
1,^ MB
^_ a,
E
* o
o >.
e a
e
— trt
E «

"O 0
o .e
« a
-= 

•w o
o .c
« a
-C 4)
— E
0 —
u. a.
in
a
_
«
- E
* — 0
o e> u
e > a
e u
— on
E — «

•o o o
0 >- J=
4> U o
-C -Q «
•» E E
0 « —
l_ — Q.
W
O
_M
4)
E
B O
0 U
<= a
c

g  D
•^ 3 =
O 	 1 •-
U. 	 Q-
                                                          26

-------
            «

            •
            •
                  o
                  u
                  
«J
^
O
O
^
4}
<•
.^
3
O
t
*
O
i.
L.
0

(A
e
e
-H
O
b.
* o
— * o
o
> 0
u. c
o >

o a
» o
U L.
•d ^K
E vi
a> o
• — • o
                                             a
                                             o
                                             e
                                             o
                                             e
                                             «
                                             o
                                                             27

-------
                                  REFERENCES








Amiard,  J.C.  1976.  Experimental  study of the toxicity of salts of  cobalt,




antimony,  strontium and silver with some crustaceans and their larvae and some




teleosts.  Rev.  Intern.  Oceanogr.  Med. 43:79-95








Anderson,  B.C.  1948.  The apparent thresholds of toxicity to Daphni a magna for




chlorides  of  various  metals when added to Lake Erie water.  Trans.  Am. Fish.




Soc.  78:96-113.








Andreae, M.O.,  J.F. Asmode, P. Foster and L. Vantdack. Determination of




antimony(111),  antimony(V), and methylantimony species in natural waters by




atomic absorption spectrometry with hydride generation. Anal. Chem.




53:1766-1771.









Barrows, M.E.,  S.R. Petrocelli and K.J. Macek. 1980.  Bioconcentration and




elimination of selected water pollutants by bluegill  sunfish  (Leoomi s




macrochi rus)  In: Dynamics, exposure  and hazard assessment of  toxic  chemicals.




Hague, R.  (Ed.). Ann Arbor Science,  Ann Arbor, MI.  pp. 379-390.








Battelle Ocean Sciences. 1987. Acute toxicity of antimony(111)  to  saltwater




organisms. Report to U.S.  EPA, Criteria and Standards  Division, Washington,




DC.








Birge, W.J. 1978. Aquatic  toxicology of trace elements  of  coal  and fly  ash.




In: Energy and environmental  stress  in  aquatic systems. Thorp,  J.H.  and J.




Gibbons (Eds.).  CONF-771114.  National Technical  Information Service,




Springfield,  VA. pp. 219-240.




                                       28

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



pollutants using fish and amphibian eggs as bioassay organisms. In: Animals as



monitors of environmental pollutants. Nielson, S.W., G. Migaki and D.G.



Scarrelli (Eds.). National Academy of Sciences, Washington. DC. pp. 108-118.








Birge, W.J.,  J.A. Black, A.G. Westerman and J.E.  Hudson. 1980. Aquatic



toxicity tests on inorganic elements occurring in oil shale. In: Oil shale



symposium: Sampling, analysis and quality assurance. Gale, C.  (Ed.). EPA-



600/9-80-022 or PB80-221435. National Technical  Information Service,



Springfield.  VA. pp. 519-534.








Brezina, E.R. and M.V. Arnold.  1977. Levels of heavy metals  in fishes  from




selected Pennsylvania waters. Publication No.  50. Pennsylvania Department of



Environmental Resources, Bureau of Water Quality Management, Harrisburg,  PA.








Brooke, L.T., D.J. Call, C.A. Lindberg and T.P.  Markee.  1986.  Acute toxicity



of antimony(III) to several  species of freshwater organisms. Center for  Lake




Superior Environmental Studies, University of  Wisconsin-Superior,  WI.








Buccafusco, R.J., S.J. Ells  and G.A. LeBlanc.  1981.  Acute  toxicity of  priority



pollutants to bluegill (Lepomis macrochi rus).  Bull.  Environ. Contain. Toxicol.



26:446-452.








Burns, D.T.,  A. Townshend and A.H. Carter. 1981. Inorganic  reaction chemistry.



Vol.  2. Reactions of the elements and their compounds.  Part  A. Alkali  metals




to nitrogen.  Ellis Horwood  Ltd., Chichester,  U.K.
                                       29

-------
Callahan,-M.A.,  M.W.  Slimak,  N.W.  Gabel,  I.P.  May,  C.F.  Fowler,  J.R.  Freed,  P.




Jennings,  R.L.  Durfee,  F.C.  Whitmore,  B.  Maestri,  W.R.  Mabey,  B.R.  Holt and C.



Gould.  1979.  Water-related environmental  fate  of 129 priority  pollutants.  Vol.



I.  EPA-440/4-79-029a.  pp. 5-1 to 5-8.








Chassard-Bouchard,  C.  and G.  Balvay.  1978.  Application of electron probe x-ray



microanalysis to the detection of metal pollutants in freshwater zooplankton.



Microsc.  Acta (Suppl.)  2:185-192.








Chattopadhyay,  A.,  K.M. Ellis and K.  Desilva.  1979. Determination of trace



elements in fisheries samples by instrumental  neutron and photon activation



analysis.  Nucl.  Act.  Tech. Life Sci.  Proc.  Int. Symp. pp. 667-683.








Cherry, D.S., R.K.  Guthrie,  F.F. Sherberger and S.R. Larrick.  1979. The



influence of coal ash and thermal discharges upon  the distribution and



bioaccumulation of aquatic organisms. Hydrobiologia 62:257-267.








Cherry, D.S., J.H.  Rodgers,  Jr., R.L. Graney and J. Cairns, Jr.  1980.  Dynamics



and control of the asiatic clam in the New River,  Virginia. Bulletin No.  123.



Virginia Water Resources  Research Center, Blacksburg, VA.








Crecelius, E.A., M.H.  Bothner and R. Carpenter. 1975. Geochemistries of



arsenic, antimony, mercury,  and related  elements  in  sediments of  Puget  Sound.




Environ. Sci. Technol.  9:325-333.








Curtis, M.W. and C.H.  Ward.   1981. Aquatic toxicity of forty industrial




chemicals: Testing in  support of hazardous substance spill prevention



regulation. J. Hydrol.  (Amst.) 51:359-367.




                                       30

-------
DeGoey,  J.J.M., V.P.  Guinn,  D.R. Young and A.J.  Mearns.  1974. Neutron
activation analysis trace-element studies of Dover sole liver and marine
sediments. Nucl. Sci.  Abstr. 29:189-200.


Dorfman, D. 1977. Tolerance of Fundulus heteroclitus to different metals in
salt waters.  Bull.  N.  J. Acad. Sci.  22:21-23.


Friant,  S.L.  and H. Koerner. 1981. Use of an in-situ artificial substrate for
biological accumulation and monitoring of aqueous trace metals. A preliminary
field investigation.  Water Res. 15:161-167.


Friant,  S.L.  and J.W.  Sherman. 1980. The use of algae as biological
accumulators  for monitoring aquatic pollutants.  In: 2nd interagency workshop
on in-situ water quality sensing: Biological sensing. National Marine
Pollution Program Office, National Oceanic and Atmospheric Administration,
Rockville, MD.  pp.  185-206.
                                                            /

Goldberg, E.D.  (Ed.).  1972.  Baseline studies of pollutants in the marine
environment and research recommendations. NSF-1DOE-74-26. pp. 231-273.


Greig,  R.A. and J.  Jones. 1976. Nondestructive neutron activation analysis of
marine  organisms collected from ocean dump sites of the middle eastern  United
States.  Arch.  Environ. Contain. Toxicol. 4:420-434.


Hall, R.A., E.G. Zook and O.M. Meaberm. 1978. National Marine Fisheries

Service  survey of trace elements  in the fisheries  resource.  NOAA Technical

Report  NMFS SSRF-721.
                                       31

-------
Heit,  M.  and C.S.  Klusek.  1985.  Trace element concentrations in the dorsal




muscle of white suckers and brown bullheads from two acidic Adirondack lakes.



Water Air Soil Pollut.  25:87-96.








Heitmuller, P.T.,  T.A.  Hollister and P.R.  Parrish.  1981.  Acute toxicity of  54



industrial chemicals to sheepshead minnow (Cyprinodon variegatus).  Bull.



Environ.  Contam.  Toxicol.  27:596-604.








Hildebrand, S.G.  and J.A.  Carter. 1976. The potential toxicity and



bioaccumulation in aquatic systems of trace elements present in aqueous coal



conversion effluents. In:  Trace substances in environmental health - X.



Hemphill, D.D. (Ed.). University of Missouri, Columbia, MO. pp. 305-312.








Hollibaugh, J.T.,  D.L.  Seibert and W.H. Thomas. I960. A comparison of  the acute



toxicities of ten heavy metals to phytoplankton from Saanich  Inlet, B.C.,



Canada. Estuarine Coastal Sci. 10:93-105.








Hughes, M.M.  and W.S. Boothman.  1987. SAI  Corp., Narragansett, RI. (Memorandum



to D.J. Hansen, U.S. EPA, Narragansett, RI. April 28.)








Jay, F.B. and R.J. Muncy. 1979. Toxicity to channel  catfish of wastewater  from




an Iowa coal  beneficiation plant. Iowa State J. Res. 54:45-50.








Juhnke, I. and D.  Ludemann.  1978. Results  of the investigation of  200  chemical




compounds for acute  fish  toxicity with the golden orfe test.  Z. Wasser Abwasser



Forsch. 11:161-164.
                                        32

-------
Kimball,  G.  Manuscript. The effects of lesser known metals and one organic to

fathead minnows (Pimephales promelas) and Daphnia magna... Available from:

Charles E. Stephan, U.S. EPA, Duluth, MN.



Knie, J., A. Halke, I. Juhnke and W. Schiller. 1983. Results of studies of

chemical substances using four biotests. Dtsch. Gewasserkd. Mitt. 27:77-79.



Korda, R.J., I.E.  Henzler, P.A. Helmke, M.M. Jimenez. L.A. Haskin and E.M.

Larsen. 1977. Trace elements in samples of fish, sediment  and taconite  from

Lake Superior. J.  Great Lakes Res. 3:148-154.



LeBlanc,  G.A. 1980. Acute toxicity of priority pollutants  to water flea

(Daphnia magna).  Bull. Environ. Contam. Toxicol. 24:684-691.



LeBlanc,  G.A. and J.W. Dean. 1984. Antimony  and thallium toxicity to embryos

and  larvae of fathead minnows (Pimephales promelas). Bull. Environ. Contam.

Toxicol.  32:565-569.



Lucas, H.F., Jr.,  D.N. Edgington and P.J. Colby. 1970.  Concentrations of  trace

elements in Great Lakes fishes. J. Fish. Res. Board Can. 27:677-684.



Moller, H.,  R. Schneider and C. Schnier. 1983. Trace metal and PCB content of

mussels (Mytilus edulis) from the southwestern Baltic Sea.  Int.  Revue ges.

Hydrobiol. 68:633-647.




Parrish,  P.R., K.S. Buxton and J.R. Gibson.  1976. Oysters  (Crassostrea
                                                                              H
vi rginica) exposed to a complex industrial waste survival  growth  and uptake  cu

antimony compounds. Proc. Natl. Shellfish Assoc. pp.  104.

                                        33

-------
Payer,  H.D.  and K.H.  Runkel.  1978.  Environmental  pollutants in freshwater algae



from open-air mass cultures.  Arch.  Hydrobiol.  11:184-198.








Payer,  H.D., K.H. Runkel, P.  Schramel,  E.  Stengel,  A.  Bhumiratana  and C.J.



Soeder. 1976. Environmental influences  on the  accumulation of lead,  cadmium,



mercury, antimony, arsenic, selenium, bromine  and tin in unicellular algae



cultivated  in Thailand and in Germany.  Chemosphere 5:413-418.








Seelye. J.G., R.J. Hesselberg and M.J.  Mac. 1982. Accumulation by fish of



contaminants released from dredge and sediments.  Environ.  Sci. Technol.




16:459-464.








Shuman, M.S., L.A. Smock and C.L. Haynie.  1977. Metals in the water, sediments



and biota of the Haw and New Hope Rivers,  North Carolina.  UNC-WRRI-77-124.



Water Resources  Institute, University of North Carolina, Chapel Hill, NC.








Smith,  L.L., Jr., D.M. Oseid, G.L.  Kimball and E.M. El-Kandelgy.  1976. Toxicity



of hydrogen  sulfide to various life  history stages of bluegill  (Lepomi s



macrochirus). Trans.  Am. Fish. Soc.  105:442-449.








Smock,  L.A.   1983a. The  influence of  feeding habits on whole  body  metal



concentrations  in aquatic  insects. Freshwater  Biol. 13:301-311.








Smock,  L.A.   1983b. Relationships between metal concentrations  and organism  size



in aquatic  insects. Freshwater Biol. 13:313-321.








Spehar, R.L. 1987. U.S.  EPA,  Duluth, MN.  (Memorandum  to C.  Stephan,  U.S.  EPA,




Duluth, MN.   August 27.)




                                        34

-------
Stephan,  C.E.,  D.I.  Mount, D.J. Hansen, J.H. Gentile, G.A. Chapman and W.A.



Brungs.  1985.  Guidelines for deriving numerical national water quality criteria



for the protection of aquatic organisms and their uses. PB85-227049. National



Technical Information Service, Springfield, VA.








Stumm, W. and J.J. Morgan. 1982. Aquatic chemistry. Wiley, New York, N. Y. pp.




176-177.








Tamulinus, S.H. 1979. The effects of antimony trioxide on channel catfish



Ictalurus punctatus. Ph.D. thesis. Texas A & M University, Bryan, TX.




University Microfilms, Ann Arbor, MI. Order No. 80-12005.
Tarzwcll, C.M. and C. Henderson. 1960. Toxicity of less common metals.  Ind.



Wastes 5:12.
Telitchenko, M.M., G.V. Tsytsarin and Y.L. Shirokova.  1970. Trace  elements and



algal "bloom." Hydrobiol. J. (Engl. Transl. Gidrobiol  Zh.) 6(6):l-6.








Thomas,  W.H., J.T. Hollibaugh and D.L.R. Seibert. 1980a.  Effects of  heavy



metals on the morphology of some marine phytoplankton. Phycologia  19:202-209.








Thomas.  W.H., J.T. Hollibaugh, D.L.R. Seibert and G.T. Wallace, Jr.  1980b.



Toxicity of a mixture of ten metals to phytoplankton.  Mar. Ecol. Prog.  Ser.



2:213-220.








Tong, S.S., W.D. Youngs, W.H. Gutenmann and D.J. Lisk.  1974.  Trace metals  in




Lake Cayuga  lake trout  (Salvelinus namavcush) in relation to  age.  J.  Fish.  Res




Board Can. 31:238-239.



                                        35

-------
U.S.  EPA. '1978.  In-depth studies on health and environmental impacts of

selected water pollutants.  (Table of data available from Charles E.  Stephan,

U.S.  EPA,  Duluth,  MN.)


U.S.  EPA.  1980a. Ambient water quality criteria for antimony.  EPA-440/5-80-020.

National Technical Information Service, Springfield, VA.


U.S.  EPA.  1980b. Water quality criteria documents. Federal Regist.

45:79318-79379.  November 28.


U.S.  EPA.  1983a. Methods for chemical  analysis of water and wastes.

EPA-600/4-79-020 (Revised March  1983). National Technical  Information  Service,

Springfield, VA.


U.S.  EPA.  1983b. Water quality  standards  regulation. Federal  Regist.

48:51400-51413. November 8.
                                                            /

U.S.  EPA.  1983c. Water quality  standards  handbook.  Office  of  Water  Regulations

and Standards,  Washington,  DC.


U.S.  EPA.  1985a. Appendix B - Response to public  comments  on  "Guidelines  for

deriving numerical national water  quality criteria  for  the protection  of

aquatic organisms and their uses."  Federal  Regist.  50:30793-30795.  July 29.


U.S.  EPA.  1985b. Water quality  criteria.  Federal  Regist.  50:30784-30792.  July

29.
                                        36

-------
U.S. EPA. 1985c. Technical support document for water quality-based toxics



control. EPA-440/4-85-032 or PB86-150067. National Technical Information



Service, Springfield. VA.








U.S. EPA. 1988. Chapter I - Stream design flow for steady-state modeling. In:



Book VI - Design conditions. In: Technical guidance manual for performing waste



load allocation. Office of Water, Washington, DC. August.








U.S. EPA. 1987. Permit writer's guide to water quality-based permitting  for



toxic pollutants.  EPA-440/4-87-005. Office of Water, Washington, DC.








Uthe, J.F.  and E.G. Bligh. 1971. Preliminary survey of heavy metal



contamination of Canadian freshwater fish. J. Fish. Res. Board Can. 28:786-788.








Walz, F. 1979. Uptake and elimination of antimony in the mussel, Mvtilus



edulis. Veroff. Inst. Meersforsch. Bremerh.  18:203-215.








Wood, J.M.  and H.K. Wang. 1985. Strategies for microbial resistance to heavy



metals. In:  Chemical processes  in  lakes. Stumm, W.  (Ed.). John Wiley  and Sons



Publishers,  New York. pp. 81-98.








Woodiwiss,  F.S. and G. Fretwell. 1974. The toxicities of sewage effluents,



industrial  discharges and some  chemical  substances  to brown trout  (Salmo



trutta) in the Trent River Authority Area. Water  Pollut. Control 73:396-405.
                                        37

-------