United States
Environmental Protection
Agency
Officao* W.i,e-
Reguiatic-i!.- *--a
Criteria jnr- a^'
Wash.nt": ,- TC
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Jsni.v-y
006200
Water
Ambient
Water Qua I it v
Criteria
for
OHEA
OF
CENTRAL FILE
Arsenic - 1984
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AMBIENT AQUATIC LIFE WATER QUALITY CRITERIA FOR
ARSENIC
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL RESEARCH LABORATORIES
DULUTH, MINNESOTA
NARRAGANSETT, RHODE ISLAND
000001 JB\
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;a \ ป.ซi-. . -'.rt-.-oi by che Criceria and Standards Division,
c. '*ci:-ns and Standirds, U.S. Environmental Proceccion
-:/ ! fcr ouSlicition. Mention oฃ crade names or commercial
''ot constitute endorsement or recommendation for use.
AVAILABILITY NOTICE
This document is available to the public through the National Technical
Information Service (NTIS) , 5285 Port Royal Road, Springfield, VA 22161.
/2. - P6 8S
000001 C
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FOREWORD
Section 304(a)(l) of the Clean Water Ace of 1977 (P.L. 95-217) requires
che Administrator of the Environmental Protection Agency to publish criteria
for water quality accurately reflecting the latest scientific knowledge on
the kind and extent of all identifiable effects on health and welfare which
may be expected from the presence of pollutants in any body of water,
including ground water. This document is a revision of proposed criteria
based upon a consideration of comments received from other Federal agencies,
State agencies, special interest groups, and individual scientists. The
criteria contained in this document replace any previously published EPA
aquatic life criteria.
The terra "water quality criteria" is used in two sections of the Clean
Water Act, section 304(a)(l) and section 303(c)(2). The term has a different
program impact in each section. In section 304, the term represents a
non-regulatory, scientific assessment of ecological effects. The criteria
presented in this publication are such scientific assessments. Such water
quality criteria associated with specific stream uses when adopted as State
water quality standards under section 303 become enforceable maximum
acceptable levels of a pollutant in ambient waters. The water quality
criteria adopted in the State water quality standards could have the same
numerical limits as-the criteria developed under section 304. However, in
many situations States may want to adjust water quality criteria developed
under section 304 to reflect local environmental conditions and human
exposure patterns before incorporation into water quality standards. If is
not until their adoption as part of the State water quality standards that
the criteria become regulatory.
Guidelines to assist che States Ln che modification of criteria
presented in this document, in the development of water quality standards,
and in other water-related programs of chis Agency, have been developed by
EPA.
Edwin L. Johnson
Director
Office of Wacer Regulacions and Standards
111
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ACKNOWLEDGMENTS
.'pci.-r
: duchor)
Research Laboracory
..jluch, Minnesoca
John H. Gencile
(aalcwacer auchor)
EnvironmencaL Research Laboracory
Narraganaecc, Rhode Island
Charles E. Scephan
(documenc coordinacor)
Environraencal Research Laboracory
Ouluch, Minnesota
David J. Hflnsen
(salcwacaf coordinacor)
Environmental Research Laboracory
Narraganaซt:c, Rhode Island
Clerical Supporc: Terry L. Highland
IV
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CONTENTS
Foreword ............ . ..................
Acknowledgments ........ . .................. iv
Tables ................................ vi
Introduction ............................. i
Acute Toxicity to Aquatic Animals .................. 5
Chronic Toxicity to Aquatic Animals ........ ......... 7
Toxicity to Aquatic Plants ....................... 8
Bioaccumulcition ........................... 10
Other Data .............................. 10
Unused Data .............................. 12
Summary .......................... ..... 14
National Criteria .......................... 15
References .............................. 4j
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TABLES
1.
2.
3.
4.
5.
6.
Acuce Toxicicy of Arsenic co Aquacic Animals . . . .
Chronic Toxicicy of Arsenic co Aquacic Animals
Ranked Genus Mean Acuce Values wich Species Mean Acuce-Chronic
Rac ion
Toxicicy of Arsenic co Aquacic Planes
Bioaccumulacion of Arsenic by Aquacic Organisms . . .
Ocher Daca on Effeccs of Arsenic on Aquacic Organisms
Page
19
24
26
29
32
35
VI
oooooi G-
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Introduction*
Arsenic is found in all living organisms, -including chose in aquacic
systems. Lictle is known abouc che mechanisms of arsenic coxicicy co aquacic
organism:;; however, arsenic readily forms stable bonds co sulfur and carbon
in organic compounds. Like mercury, arsenic(III) reacts wich sulfhydryl
groups of proteins; enzyme inhibition by chis mechanism may be che primary
mode of coxicicy. Arsenic(V) does noc react wich sulfhydryl groups as
readily but may uncouple oxidacive phosphorylacion (Fowler, et al. 1977;
Schiller, et al. 1977).
The chemistry of arsenic in water is complex, consisting of chemical,
biochemical, and geochemical reactions which together control the concentra-
tion, oxidation state, and form of arsenic in water (Braman, 1983; Callahan,
et al. 1979; Holm, ec al. 1979; Scudlark and Johnson, 1982). Four arsenic
species common in nacural waters are inorganic arsenic(III) and arsenic(V),
mechaneairsonic acid, and dimechylarsinic acid. In aerobic water, inorganic
arsenicdll) is slowly oxidized co arsenic(V) at neutral pH, but che reaction
proceeds measurably in several clays in strongly alkaline or acidic solutions.
Because i:he chemical and toxicological properties of che forms appear co be
quice different and che coxicici.es of che forms have noc been shown co be
additive,, che data for inorganic arsenicCIII), inorganic arsenic(V) , mono-
sodium mnchanearsonace (MSMA), and other arsenic compounds will be creaced
separately. Methods have been developed for separately measuring these forms
of arsenic in water (Fichlin, 1983; Grabinski, 1981; Irgolic, 1982).
*An understanding of che "Guidelines for Deriving Numerical Nacional Wacer.
Quality Criteria for che Protection of Aquacic Organisms and Their Uses"
(Scephan, et al. 1985), hereafter referred co as the Guidelines, is necessary
in order co understand che following cexc, cables, and calculations.
1
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Because of the variecy of forms of .inorganic arsenic(III) and inorganic
arsenic(V) and lack of definicive information abouc cheir relative
coxicicies, no available analycical measurement is known co be ideal for
expressing aquacic life criteria for arsenic. Previous aquatic life criteria
for arsenic (U.S. EPA, 1980) were expressed in terms of total recoverable
inorganic arsenicCIII), but the total recoverable method cannoc distinguish
between inorganic arsenicC III) and arsenic(V). Acid-soluble arsenic(HI)
(operationally defined as the arsenic(III) that passes through a 0.45 ijm
membrane filter after the sample is acidified to pH - 1.5 to 2.0 with nitric
acid) and acid-soluble arsenic(V) are probably the best measurements at the
present for the following reasons:
1. These measurements are compatible with all available data concerning
toxicity of arsenic to, and bioaccumuiation of arsenic by, aquatic
organisms. No test results were rejected just because it was likely that
they would have been substantially different if they had been reported in
terms of acid-soluble arsenic.
2. On samples of ambient water, measurement of acid-soluble arsenic(lll) and
arsenic(V) should measure all forms of arsenic that are toxic to aquatic
life or can be readily converted co toxic forms under natural conditions.
In addition, these measurements should not measure several forms, such as
' arsenic that is occluded in minerals, clays, and sand or is strongly
sorbed to particulate matter, that are not toxic and are not likely to
become toxic under natural conditions.
3. Although water quality criteria apply to ambient water, the-measurements
used to express criteria are likely to be used co measure arsenic in
aqueous effluents. Measurements of acid-soluble arsenic(III) and
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arsenicCV) should be applicable co effluents. If desired, dilution of
effluent with receiving water before measurement of acid-soluble arsenic
might be used to determine whether the receiving water can decrease the
concentration of acid-soluble arsenic because of sorption. However, the
relationship between what is in an effluent and what will result in the
receiving water should take into account any conversion of one oxidation
state of arsenic to the other.
4. The acid-soluble measurement should be useful for most metals, thus
minimizing the number of samples and procedures that are necessary.
5. The acid-soluble-measurement does not require filtration at the time of
collection, as does.the dissolved measurement.
6. For the measurement of total acid-soluble arsenic the only treatment
required at the time of collection is preservation by acidification to pH
= 1.5 to 2.0, similar to that required for the measurement of total
recoverable arsenic. Durations of 10 minutes to 24 hours between
acidification and filtration probably will not affect the measurement of
total acid-soluble arsenic. However, acidification might not prevent
conversion of inorganic arsenic(III) to arsenic(V) or vice versa.
Therefore, measurement of acid-soluble arsenic(III) or acid-soluble
arsenicCV) or both will probably require separation or measurement ac che
time of collection of the sample or special preservation to prevent
conversion of one
oxidation state of arsenic to the other.
The
2.0
8. Differences
the
carbonate system has a much higher buffer
than it does from pH = 4 to 9 (Weber and
in pH within the range of 1.5 to
substantially.
.pacicy from
Stumm, 1963).
2.0 probably
1.5 co
will not affecc
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9. The acid-soluble tneasuretnenc does noc require a digestion seep, as does
che cocal recoverable measurement.
10. After acidificacion and filcracion of che sample co isolace che
acid-soluble arsenic, che analysis can be performed using either atomic
absorption spectroscopy or ICP-emission spectroscopy for either total
acid-soluble arsenic or total .acid-soluble inorganic arsenic (U.S. EPA,
1983a). It might be possible to separately measure acid-soluble
arsenic(III) and acid-soluble arsenic(V) using che methods described by
Grabinski (1981) and Irgolic (1982).
11. It is noc possible co separately measure total recoverable arsenic(III)
and total recoverable arsenic(V).
Thus, expressing aquatic criteria for arsenic in terms of the acid-soluble
measurement has boch coxicological and practical advantages. On che other
hand, because no measurement is known to be ideal for expressing aquatic life
criteria for arsenic or for measuring arsenic in ambient water or aqueous
effluencs, measurement of both tocal acid-soluble arsenic and cocal
recoverable arsenic in ambienc water or effluent or both might be useful.
For example, chere might be cause for concern if total recoverable arsenic is
much above an applicable limit, even chough total acid-soluble arsenic is
below the limit.
Unless otherwise noted, all concentrations reported herein are expecced
co be essencially equivalent to acid-soluble arsenic concencracions. All
concentrations are expressed as arsenic, not as che chemical tested. The
criceria presenced herein supersede previous aquatic life water quality
criceria for arsenic (U.S. EPA, 1976a, 1980) because these new criceria were
derived using improved procedures and additional information. Whenever
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adequacely juscified, a nacionaL cricerion may be replaced by a sice-specific
criterion (U.S. EPA, 1983b), which may include noc only sice-specific
cricerion concencracions (U.S. EPA, 1983c), buc also sice-specific duracions
of averaging periods and sice-specific frequencies of allowed exceedences
(U.S. EPA, 1985). The lacesc liceracure search for informacion for chis
docuraenc was conducced in May, 1984; some newer informacion was also used.
Acuce Toxicicy co Aquacic Animals
Inglis and Davis (1972) found chac hardness did noc affecc che coxicicy
of inorganic arsenic(III) co che bluegill. The. fachead minnow was much less
sensicive co arsenic crisulfide (Table 6) chan co sodium arsenice (Table 1).
Genus Mean Acuce Values (Table 3) were calculated as geomecric means of che
sixceen available Species Mean Acuce Values (Table 1). Acuce values are
available for cwo species in each of cwo genera and che range of Species Mean
Acuce Values wichin each genus is less chan a faccor of 3.3. Four cruscacean
genera are much more sensicive chan che ocher cesced invercebrace and fish
genera. Boch che raosc resiscanc genus, Tanycarsus, and che raosc sensicive
genus, Ganmarus, are invercebraces, buc Gammarus is 110 cimes more sensicive
chan Tanycarsus. A freshwacer Final Acuce Value of 718.2 pg/L for inorganic
arsenic(lll) was calculaced from che Genus Mean Acuce Values (Table 3) using
che calculacion procedure described in che Guidelines.
Acut:e cescs have been conducced on inorganic arsenic(V) wich six species
in five genera and che Species Mean Acuce Values ranged from 850 rig/L for a
cladoceran co 49,000 ,jg/L for che raosquicofish (Table 1). Inorganic
arsenic(V) was slighcly more coxic chan arsenic(III) co rainbow crouc, buc
arsenic(III) was nearly cwice as coxic co che fachead minnow and Daphnia
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The acuce sensicivicies of eighc species exposed co MSMA range from
1,921 jg/L for the bluegill co 1,403,000 ug/L for che channel cacfish (Table
1). The fachead minnow was approximacely 12 cimes more sensicive co MSMA
chan co sodium arsenace and che goldfish, fachead minnow, and bluegill were
approximacely 5 co 22 cimes more sensicive co MSMA chan co sodium arsenice.
Channel cacfish and amphipods, however, were much less sensicive co MSMA chan
sodium arsenice.
Noc enough acuce values are available for calculacion of freshwacer
Final Acuce Values for inorganic arsenic(V) or MSMA.
Daca are available on che acuce coxicicy of inorganic arsenic(III) co
salcwacer species in chree fish and eighc invercebrace genera (Tables 1 and
3). The fish species cesced were che mosc resiscanc wich a range of LCSOs
from 12,700 jjg/L for che sheepshead minnow co 16,030 ^g/L for che Aclancic.
silverside. Among che inverrabraces, che lowesc acuce value, 232 Mg/L. was
obcained wich zoeae of che Dungeness crab whereas che highesc value, 10,120
jg/L, was from a cesc wich che polychaece worm, Neanches arenaceodencaca.
Incerescingly, che acuce value for che Pacific oyscer is almosc as low as
chac for che Dungeness crab, buc chac for che eascern oyscer is almosc as
high as chac for che polychaece worm. In addicion, Alderdice and Brecc
(1957) obcained a 48-hr LC50 of 8,300 ;Jg/L wich arsenic crioxide co chum
salmon (Table 6). Holland, ec al. (1960) decermined a 10-day LC54 of 3,787
,ag/L for che pink salmon, whereas Curcis, ec al. (1979) reporced a 96-hr LC50
of 24,700 ug/L for arsenic crisulfide in cescs wich juvenile whice shrimp
(Table 6). Of che eleven Genus Mean Acuce Values in Table 3, all eighc for
invercebraces are lower chan che chree for fish. The mosc sensicive genus,
Cancer, is 69 cimes more sensicive chan .che mosc resiscanc, Menidia. The
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salcwacer Final Acuce Value for inorganic arsenic(III) is 137.1 pg/L, which
ia about one-half che lowesc Species Mean Acuce Value.
Daca are available for inorganic arsenic(V) wich cwo salcwacer species.
The coxicicy of arsenic(V) co a mysid, Mysidopsis bahia, (LC50 - 2,319 ;jg/L)
is similar co chac of arsenic(III) (LC50 - 1,740 Mg/L). Arsenic(V) is more
coxic chart arsenic(III) co che atnphipod, Ampelisca abdica, whose Species Mean
Acuce Values are 4,610 pg/L for arsenic(V) and 8,227 pg/L for arsenicCIII).
Noc enough daca are available co calculace a salcwacer Final Acuce Value for
inorganic arsenic(V).
Chronic Toxicicy co Aquacic Animals
Three chronic cescs have been conducced on inorganic arsenic(III) wich
freshwacer species (Table 2). A life-cycle cesc wich Daphnia magna (Call, ec
al. 1983; Lima, ec al. 1984) resulced in a chronic value of 914.1 pg/L based
on chronic liraics of 633.0 and 1,320 -Jg/L. The 96-hr LC50 for chis species
in che same scudy was 4,340 Jg/L, resulcing in an acuce-chronic racio of
4.748. The chronic values for che fachead minnow and flagfish exposed co
arsenic(lll) were approximacely che same. The 96-hr LC50 values for che cwo
species were also similar and che acuce-chronic racios were 4.660 and 4.862,
respecciveily.
Daca on che chronic coxicicy of arsenic co salcwacer species are
available for only one species, Mysidoosis bahia (Table 2). In a 35-day
life-cycle cesc on arsenic(III), no adverse effeccs were scaciscically
significanc ac 631 ng/L, whereas 1,270 ;Jg/L affecced reproduccion and
significancly reduced survival. These resulcs provide a chronic value of
895.2 .Jg/L and an acuce-chronic racio of 1.944.
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The four acute-chronic ratios available for inorganic arsenic(III) are
i.748, 4.560, 4.362, and 1.944 and che geometric mean of 3.803 is che Final
Acuce-Chronic Racio. Division of che freshwacer and saltwater Final Acuce
Values by chis ratio results in freshwater and saltwater Final Chronic Values
of 188.9 and 36.05 ,jg/L, respectively (Table 3).
An early life-stage test with the fathead minnow (DeFoe, 1982) exposed
co arsenic(V) resulted in chronic limits of 530 and 1,500 Mg/L and a chronic
value of 891.6 ug/L. The 96-hr LC50 for this species in the same study was
25,600 ug/L producing an acute-chronic ratio of 28.71 (Table 2). A
life-cycle test with.Daphnia magna (Biesinger and Christensen, 1972) (Table
6) exposed to arsenic(V) was not used in the calculation of a chronic value
because the test concentrations were not measured as specified in the
Guidelines. However, the chronic limits in this test were 520 and 1,400 ug/L
and che comparable acute value was 7,400 Jg/L, resulting in an estimated
acuce-chronic ratio of 8.7.
The fathead minnow was approximately 3 times more sensitive on a chronic
basis co arsenic(V) than to arsenic(III), but Daphnia magna appeared to be
equally sensitive to both forms of inorganic arsenic. No chronic tests have
been conducted on MSMA or any other organic arsenic compound.
Toxicity to Aquatic Planes
Adverse effects were observed at concentrations of arsenic(III) ranging
from 2,320 ug/L for three species of algae and one submerged plant co over
59,000 ug/L for che alga, Selenascrum capricornucum (Table 4). Except for S_.
capricornucum. values reported for aquatic plants exposed to arsenic(III) are
comparable co the acute values for some of che more sensitive invertebrate
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species (Table 1) and to che chronic values reported for che fachead minnow
and flatfish (Table 2).
Concentrations of inorganic arsenic(V) chat caused adverse effects on
six species of freshwater algae ranged from 48 to 202,000 ug/L (Table 4). A
14-day EC50 value of 48 tJg/L obtained for the most sensitive alga,
Scenedesmus obliquus, was 18 times lower than the lowest acute value and
approximately 19 times lower than the only chronic value available for
inorganic arsenic(V). Data on the sensitivity of j>_. capricornutum to boch
oxidation states of inorganic arsenic cover a wide range and appear to depend
on the kind of toxicity test used (Richter, 1982).
Data on the toxicity of arsenic(III) to saltwater plants are available
for four species of microalgae and two species of macroalgae (Table 4).
Growth of the saltwater diatoms, Skeletonema costacum and Thalassiosira
aestivalis, was affected at 20 ug/L and 22 rig/L, respectively, and photosyn-
thesis of J3_. costatum was reduced at 19 ;Jg/L. These values are less than che
Final Chronic Value for arsenic(III) but the ecological implications of
reduced growth on these species is uncertain. Boney, et al. (1959) showed
that arsenic(III) inhibited the development of sporelings of the red
macroalsja, Plumana elegans. at 577 ug/L. In addition, formation of manure
cystocairps by another red macroalgae, Champia parvula, was prevented ac 95
gg/L and growth of female plants was reduced at 145 ug/L.
Daca on the toxicity of arsenic(V) to saltwater plants are available for
four species of microalgae and one species of macroalgae (Table 4). Based
upon these data, there is no significant difference between the toxicicy of
arsenic(HI) and arsenic(V) to the plant species tested. Thursby and Sceele
(1984) found that phosphate decreased the toxicity of arsenic(V) to Champia
parvula,, but did not affect the coxicity of arsenic( III) .
9
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Bioac cumulation
Bioconcencracion ce3cs have been conducted on arsenic( III) , arsenic(V),
and a number of organic arsenic compounds with a variety of freshwater fish
and invertebrates (TabLe 5). The highest bioconcencracion factor (BCF) was
17, which was obtained for inorganic arsenic(III) with a snail (Spehar, et
al. 1980). An early life-stage test on arsenic(V) wich the fathead minnow
(DeFoe, 1982) showed that the BCF decreased with increased exposure
concentrations in the water. BCFs were slightly lower (down to 1.2) in
exposure concentrations that caused significant adverse effects than in those
chat did not (Table 5).
A study by Oladimeji, ec al. (1982) showed chat the pretreatment of
rainbow trout to arsenic(III) enhanced the elimination of a subsequent dose
of arsenic. Additional results indicated that fish retained less arsenic
after 4 weeks of exposure than after 2 weeks.
In the one acceptable bioconcentration test on arsenic with a saltwater
species, a BCF of 350 was obtained with the oyster, Crassostrea virgini^.
after 112 days of exposure (Zaroogian and Hoffman, 1982). In a test that
only lasted 4 days, Nelson, et al. (1976) obtained a BCF of 15 with the bay
scalloo (Table 6) .
No Final Residue Value could be determined because no maximum permissi-
ble tissue concentration is available for arsenic.
Other Data
Comparison of data for fish in Tables 1 and 6 indicates that in almost
all cases, arsenic toxicity increased with increased duration of exposure.
One value for che bluegill (Hughes and Davis, 1967) was an exception
10
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resultins; in a low 48-hr LC50 of 290 ug/L. A special pellecized form of
sodium arsenice was used, which may have accounted for che low LC50. The
invertebrate data were too variable to indicate a trend in toxicicy in regard
to duration of exposure.
Spehar, et al. (1980) compared che toxicities of different forms of
arsenic in the same water. In 28-day tests, inorganic arsenic(lll) was more
toxic to the araphipod, Gammarus pseudolimnaeus, than inorganic arsenic(V),
sodium dimethyl arsenate, or disodiura methyl arsenate. Survival of
stoneflieis, snails, and rainbow trout was not adversely affected by any of
the compounds at the concentrations tested.
Two studies on the effects of environmental factors on the toxicity of
arsenic to freshwater organisms have been reported. Sorenson (1976c) showed
that increased water temperature decreased the median lethal time of green
sunfish during exposure to two concentrations of arsenic(V) (Table 6). Lima,
et al. (1984) found that the toxicity of inorganic arsenic(III) to Daphnia
magna was decreased by about a factor of 3 when food was added in 48-hr cescs
compared to exposures in which food was not added. Additional exposures
showed that arsenic(III) did not affect additional unfed animals from 48 co
96 hours, indicating that the lack of food in these tests was noc too stress-
ful. Ars^enicdll) increased albinism in channel catfish (Westerman and
Birge, 1978).
Exposures of embryos and larvae of rainbow trout and goldfish to
inorganic: arsenic(III) resulted in values that were several cimes lower chan.
those for older juvenile stages of these species (Tables 1 and 6), and chese
values were lower than the chronic values in Table 2. The lowest value
obtained in any test on arsenic, however, was 40 ,jg/L from a 7-day exposure
11
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of embryos and Larvae of che coad, Gascrophryne carolinensis, co inorganic
arsenic(III) (Birge, 1978). This value is abouc a faccor of 4.5 lower chan
che freshwacer Final Chronic Value for inorganic arsenic(III).
Bryan (1976) exposed che salcwacer polychaece worm, Nereis diversicolor,
co arsenic(III) and escimaced che 192-hr LC50 co be greacer chan 14,500 yg/L
(Table 6). Arsenic(III) caused ocher effeccs, such as depressed oxygen
consumpcion race and behavioral changes, in mud snails exposed co concencra-
cions greacer chan 2,000 ug/L for 72 hours (Maclnnes and Thurberg, 1973).
Unused Daca
Some daca on che effeccs of arsenic on aquacic organisms were noc used
because che scudies were conducced wich species chac are noc residenc in
Norch America. Daca were noc used if arsenic was a coraponenc of a mixcure
(Thomas, ec ai. 1980; Wong, ec al. 1982). Reviews by Chapman, ec al. (1968),
Eisler (1981), Eisler, ec al. (1979), Kaiser (1980), Phillips and Russo
(1978), Taylor (1981), Thompson, ec al. (1972), and U.S. EPA (1975, 1976b)
only concain daca chac had been published elsewhere.
Daca in Dabrowski (1976), Paladino (1976), and Paladino and Spocila
(1978) and one value in Mounc and Norberg (1984) were noc used because
concrol survival was coo low. Scudies by Eipper (1959), Grindley (1946),
Irgolic, ec al. (1977), and Spocila and Paladino (1979) were noc used because
insufficienc decail was reporced abouc such iceras as use of concrols and
concrol survival or because mechodology problems occurred during che cescs
which made che resulcs quescionable. Bringmann and Kuhn (1982) culcured
Daphnia Tiagna in one wacer buc conducced cescs in anocher wacer. Tescs by
Comparecco, ec al. (1982), Jones (1940, 1941), Schaefer and Pipes (1973),
12
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Scary and Kraczer (1982), and Weir and Hine (1970) were noc included because
che medium or dilution water was unacceptable.
Papers by Baker, ec al. (1983), Belding (1927), Brunskill, ec al.
(1980), Budd and Craig (1981), Chriscensen (1971), Chriscensen and Tucker
(1976), Chriscensen and Zielski (1980), Conway (1978), Devi Prasad and
Chowdary (1981), Hilcibran (1967), Jennecc, ec al. (1982), Lawrence (1958),
Maeda, ec al. (1983), McLarcy (1960), Morris, ec al. (1984), Nissen and
Benson (1982), Oladimeji, ec al. (1979, 1982, 1984b), Oncario Wacer Resources
Commission (1959), Penrose (1975), Planas and Lamarche (1983), Surber (1943),
and Wescerraan and Birge (1978) were noc used because che species names were
noc given, che concencracions causing effeccs or che effecc endpoincs were
noc clearly reported or defined, or no cesc effeccs were given. Johnson
(1978) was noc used because che fish were noc acclimaced co che cesc wacer
for a sufficienc amount of citne afcer colleccion from che field. A scudy by
Passino and Kramer (1980) on che effeccs of arsenic on Lake Superior cisco
fry was noc used because fry were obcained from egปs and sperm of cwo
different species.
Several papers dealing wich che accuraulacion of arsenic in aquaeic
organisms, including chose by Brooks, ec al. (1982), Bryan, ec al. (1983),
Copeland, ec al. (1973), Dupree (1960), Ellis (1937), Ellis, ec al. (1941),
Foley, ec al. (1978), Gibbs, ec al. (1983), Harden (1976), Huncer, ec al.
(1981), La louche and Mix (1982), Maher (1983), Marcin, ec al. (1984), May
and McKinney (1981), Mehrle, ec al. (1982), Penningcon, ec al. (1982), Reay
(1972), Sandhu (1977), Sohacki (1968), Sorenson, ec al. (1979, 1980), Scary,
ec al. (1982), Tsui and McCarc (1981), Wagemann, ec al. (1978), Whyce and
Englar (1983), and Wiebe, ec al. (1931), were noc used because che cescs were
13
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conducted in distilled wacer, were not Long enough, or were not flow-through,
or because che concentration of arsenic in the test solution during che test
/aried unacceptably or was unknown. BCFs calculated by Anderson., et al.
(1979), Isensee, et al. (1973), Klumpp and Peterson (1981), Schuth, ec al.
(1974), and Woolson, et al. (1976) were not used because they were calculated
from microcosm or model ecosystem studies in which water concentrations
decreased with time or were obtained after short exposures before
sceady-state was reached.
Summary
The chemistry of arsenic in water is complex and the form present in
solution is dependent on such environmental conditions as Eh, pH, organic
concent, suspended solids, and sediment. The relative toxicities of the
various forms of arsenic apparently vary from species to species. For
inorganic arsenic(III) acute values for sixteen freshwater animal species
ranged from 312 ug/L for a cladoceran to 97,000 ^g/L for a midge, but the
three acute-chronic ratios only ranged from 4.660 to 4.862. The five acute
values for inorganic arsenic(V) covered about the same range, but the single
acute-chronic ratio was 28.71. The six acute values for MSMA ranged from
3,243 to 1,403,000
-------
che alga, Selenascrum capricornutum, was 45 times more sensitive co
arsenic(V) than to arsenic(III), although other data present conflicting
information on the sensitivity of this alga to arsenic(V). Many plant values
for inorganic arsenic(lll) were in the same range as the available chronic
values for freshwater animals; several plant values for arsenic(V) were lower
than the one available chronic value.
The other toxicological data revealed a wide range of toxicity based on
tests wich a variety of freshwater species and endpoints. Tests with early
life stages appeared to be the most sensitive indicator of arsenic toxicity.
Values obtained from this type of test with inorganic arsenic(lll) were lower
than chronic values contained in Table 2. For example, an effect concentra-
tion of 40 ug/L was obtained in a test on inorganic arsenic(III) with embryos
and larva.e of a toad.
Twelve species of saltwater animals have acute values for inorganic
arsenic(III) from 232 to 16,030 ;jg/L and the single acute-chronic ratio is
1.945. The only values available for inorganic arsenic(V) are for two
invertebrates and are between 2,000 and 3,000 Mg/L- Arsenic(HI) and
arsenic(V) are equally toxic to various species of saltwater algae, buc che
sensitivities of the species range from 19 ng/L to more chan 1,000 ^ag/L. In
a test with an oyster, a BCF of 350 was obtained for inorganic arsenicCIII).
National Criteria
The procedures described in the "Guidelines for Deriving Numerical
National Water Quality Criteria for the Protection of Aquatic Organisms arid
Their Uses" indicate that, except possibly where a locally important species
is very sensitive, freshwater aquatic organisms and cheir uses should not be
affected unacceptably if the four-day average concentration of arsenicCIII)
15
-------
does not exceed 190 ug/L more chan once every chree years on the average and
if che one-hour average concencracion does noc exceed 360 ug/L more chan once
every chree years on che average.
The procedures described in che "Guidelines for Deriving Numerical
National Wacer Qualicy Criceria for che Proceccion of Aquacic Organisms and
Their Uses" indicace chac, except possibly where a locally iraporcanc species
is very sensicive, salcwacer aquacic organisms and cheir uses should noc be
affecced unaccepcably if che four-day average concencracion of arsenic(III)
does noc exceed 36 -jg/L more chan once every chree years on che average and
if che one-hour average concencracion does noc exceed 69 ปjg/L more chan once
every chree years on che average. This criterion might be coo high wherever
Skeleconema coscacum or Thalassiosira aescivalis are ecologically important.
Noc enough daca are available co allow derivation of numerical national
wacer qualicy criceria for freshwater aquacic life for inorganic arsenic(V)
or any organic arsenic compound. Inorganic arsenic(V) is acucely coxic co
freshwacer aquacic animals ac concentrations as low as 850 jg/L and an
acuce-chronic racio of 28 was obtained with the fathead minnow. Arsenic(V)
affecced freshwacer aquacic plants ac concencracions aa low as 48 ug/L.
Monosodium mechanearsenace (MSMA) is acucely coxic co aquacic animals ac
concencracions as low as 1,900 ,jg/L, buc no daca are available concerning
chronic coxicicy co animals or coxicicy co planes.
Very few data are available concerning che coxicicy of any form of
arsenic ocher chan inorganic arsenic(HI) co salcwacer aquacic life. The
available daca do show chac inorganic arsenic(V) is acucely coxic co sale- '
wacer animals ac concencracions as low as-2,319 pg/L and affecced some
saltwater planes ac 13 co 56 yg/L. No daca are available concerning che
16
-------
chronic coxicicy of any form of arsenic other than inorganic arsenic(III) co
salcwacer aquatic life.
EPA believes chat a measurement such as "acid-soluble" would provide a
more scientifically correct basis upon which to establish criteria for
metals. The criteria were developed on this basis. However, at chis time,
no EPA approved methods for such a measurement are available to implement the
criteria through the regulatory programs of the Agency and the States. The
Agency is considering development and approval of methods for a measurement
such as "aicid-soluble". Until available, however, EPA recommends applying
the criteria using the total recoverable method. This has two impacts: (1)
certain species of some metals cannot be analyzed directly because the total
recoverable method does not distinguish between individual oxidation states,
and (2) these criteria may be overly protective when based on the total
recoverable method.
The recommended exceedence frequency of three years is the Agency's besc
scientific judgment of the average amount of time it will take an unstressed
system to recover from a pollution event in which exposure to arsenic(III)
exceeds the criterion. Stressed systems, for example, one in which several
outfalls occur in a limited area, would be expected to require more time for
recovery. The resilience of ecosystems and their ability to recover differ
greatly, however, and site-specific criteria may be established if adequate
justification is provided.
The use of criteria in designing waste treatment facilities requires the
selection of an appropriate wasteload allocation model. Dynamic models are
preferred for the application of these criteria. Limited data or other
factors may make their use impractical, in which case one should rely on a
17
-------
sceady-acace model. The Agency recommends che interim use of 1Q5 or 1Q10 for
Cricerion Maximum Concencracion (CMC) design flow and 7Q5 or 7Q10 for che
Cricerion Continuous Concencracion (CCC) design flow in steady-state models
for unstressed and stressed systems respectively. These matters are
discussed in more detail in che Technical Support Document for Water
Qualicy-Based Toxics Control (U.S. EPA, 1985).
18
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