Draft
10/30/85
AMBIENT AQUATIC LIFE WATER QUALITY CRITERIA FOR
CHLORPYRIFOS
NOTE: This draft contains only freshwater data. The saltwater data
will be incorporated later. The freshwater CCC is likely
to change when the saltwater data are incorporated.
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL RESEARCH LABORATORIES
DULUTH, MINNESOTA
NARRAGANSETT, RHODE ISLAND
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NOTICES
This document has been reviewed by the Criteria and Standards Division,
Office of Water Regulations and Standards, U.S. Environmental Protection
Agency, and approved for publication.
Mention of trade names or commercial products does not constitute
endorsement or recommendation for use.
This document is available to the public through the National Technical
Information Service (NTIS), 5285 Port Royal Road, Springfield, VA 22161.
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FOREWORD
Section 304(a)(l) of the Clean Water Act of 1977 (P.L. 95-217)
requires the 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 that nay 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 term "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.
If water quality criteria associated with specific stream uses are adopted
by a State as water quality standards under section 303, they become
enforceable maximum acceptable concentrations of a pollutant in ambient waters
within that State. The water quality criteria adopted in the State water
quality standards could have the same numerical values 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. It is not until their adoption as part of
the State water quality standards that the criteria become regulatory.
Guidelines to assist the States in the modification of criteria
presented in this document, in the development of water quality standards.
and in other water-related programs of this Agency, have been developed
by EPA.
Director
Office of Water Regulations and Standards
111
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ACKNOWLEDGMENTS
Loren J. Larson
(freshwater author)
University of Wisconsin-Superior
Superior, Wisconsin
Jeff Hyland
(saltwater author)
Environmental Research Laboratory
Narragansett, Rhode Island
Charles E. Stephan
(document coordinator)
Environmental Research Laboratory
Duluth, Minnesota
David J. Hansen
(saltwater coordinator)
Environmental Research Laboratory
Narragansett, Rhode Island
Clerical Support:
Terry L. Highland
Shelley A. Heintz
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CONTENTS
Page
Foreword iii
Acknowledgments iv
Tables vi
Introduction 1
Acute Toxicity to Aquatic Animals
Chronic Toxicity to Aquatic Animals
Bioaccutnulation
Other Data
Unused Data
Summary
National Criteria
References
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TABLES
1. Acute Toxicity of Chlorpyrifos to Aquatic Animals
2. Chronic Toxicity of Chlorpyrifos To Aquatic Animals
3. Ranked Genus Hean Acute Values with Species Mean Acute-Chronic
Ratios
4. Toxicity of Chlorpyrifos to Aquatic Plants
5. Bioaccumulation of Chlorpyrifos by Aquatic Organisms
6. Other Data on Effects of Chlorpyrifos on Aquatic Organisms ..
VI
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Introduction*
Chlorpyrifos is one of several organophosphorus compounds developed in
the 1960s to replace persistent organochlorine pesticides. It has been
widely used as a broad spectrum insecticide for agricultural and domestic
pests. It is directly applied to aquatic environments in mosquito, midge.
and blackfly abatement projects.
Chlorpyrifos is produced by the Dow Chemical Company (Midland, MI,
USA) under the trade names Dursban® and Lorsban®. Gray (1965) and Marshall
and Roberts (1978) have reviewed its composition and physical and chemical
properties. Its commercial formulations for pesticide application include
emulsifiable concentrates (EC), wettable powders (WP), granules, and
controlled-release polymers. The resulting concentration of Chlorpyrifos
in water and its persistence varies from one formulation to another. In
general, emulsifiable concentrates and wettable powders produce a large
pulse in Chlorpyrifos concentrations immediately after application.
Water concentrations rapidly decline as Chlorpyrifos is taken up by the
several natural sinks (discussed later]. Granules and controlled-release
formulations do not produce as prominent an immediate pulse in water, but low.
yet significant concentrations remain in the environment for a longer
duration.
The percentage of active ingredient in the formulations can vary
considerably, both between formulations and within a single formulation
* An understanding of the "Guidelines for Deriving Numerical National Water
Quality Criteria for the Protection of Aquatic Organisms and Their Uses"
(Stephan et al. 1985). hereafter referred to as the Guidelines, is necessary
in order to understand the following text, tables, and calculations.
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over time as manufacturers' specifications change. This results in a
large percentage of often unspecified ingredients, many used as carriers,
in commercial formulations. These ingredients are considered inert,
although technical grade chlorpyrifos has generally been found to be more
toxic than an equal quantity of active ingredient in formulation (Darwazeh
and Mulla 1974; Jarvinen and Tanner 1982; Siefert et al. 1984). For this
reason, the effect of the inert ingredients can not be discounted. Under
normal application conditions, the commercial formulations are often
combined with petroleum products, such as No. 2 diesel oil or kerosene,
to increase the rate of dispersal. Solvents have been shown to have
significant toxic effects separate from chlorpyrifos (Wallace et al.
1973: Jamnback and Frempong-Boadu 1966).
Numerical water quality criteria are derived herein solely for the
chemical chlorpyrifos. Although some data obtained from studies using
formulations are discussed, only data derived from toxicity tests utilizing
an adequately high-quality chlorpyrifos are used in deriving criteria.
The toxic effect of chlorpyrifos is the result of metabolic conversion
to its oxygen analogue, chlorpyrifos-oxon, and its subsequent inhibitive
interaction with various enzyme systems (e.g., cholinesterases, carboxylases,
acetylcholinesterases, mitochondrial oxidative phosphorylation). Its
activity with acetylcholinesterase (AChE) is generally accepted to be its
most critical toxic effect. AChE inhibition results in accumulation of
the neurotransmitter, acetylcholine, in synapes, disrupting normal neural
transmission. Although in fish even substantial reductions in brain AChE
activity have not always been fatal, the effect of this condition on
normal activity (e.g., feeding, reproduction, predator-prey relationships,
etc.) in nature is not known.
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Although less persistent than organochlorine compounds, chlorpyrifos
is very immobile when applied to most terrestrial environments. Because
of its affinity to organic soils, little to no leaching occurs. In lieu
of direct application to aquatic environments, chlorpyrifos can enter
through spray drift from adjacent agricultural areas or sorbed to entrained
particles resulting from erosion of treated areas.
Once chlorpyrifos enters an aquatic system, it appears to be rapidly
sorbed to suspended organics and sediments, although some is removed by
volatilization and degradation. Its penetration into the sediment appears
to be shallow, most occurring in the upper several milimeters. The
equilibrium between sediment, suspended organics and the water is poorly
understood. Chlorpyrifos residues in natural sediments and water samples
have been reported by Braun and Frank (1980), Rawn et al. (1978), Winterlin
et al. (1968), Nelson et al. (1973). Hughes et al. (1980), Hughes (1977),
Hurlbert et al. (1970), Siefert et al. (1984), and Macalady and Wolfe (1985).
Evans (1977) reported significant chlorpyrifos concentrations, still
toxic to mosquito larvae, one year after application of a slow-release
polymer formulation to a natural pond.
The use of slow-release polymers will probably result in differential
exposure, both in concentration and duration, between benthic and pelagic
organisms. Organisms inhabiting the water-sediment interface have the
potential to receive larger and more sustained concentrations than free-swimming
organisms.
Chlorpyrifos, although highly toxic, is rapidly metabolized by fish,
3,5 .6-trichloro-2-pyridinol being the major product (Marshall and Roberts,
1978). Residues in fishes are generally low for this reason. Several
studies have reported residues of chlorpyrifos in wild fishes (Clark et
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al. 1984, Mulla et al. 1973), and cultured or experimental fishes (Macek
et al. 1972, Winterlin et al. 1968, Siefert et al. 1984).
All concentrations herein are expressed as chlorpyrifos, not as the
material tested. Whenever adequately justified, a national criterion may
be replaced by a site-specific criterion (U.S. EPA 1983a) , which may
include not only site-specific criterion concentrations (U.S. EPA 1983b).
but also site-specific durations of averaging periods and site-specific
frequencies of allowed exceedences (U.S. EPA 1985). The latest literature
search for information for this document was conducted in February, 1985;
some newer information was also used.
Acute Toxicity to Aquatic Animals
Most of the available data on the acute toxicity of chlorpyrifos to
freshwater animals is from the U.S. Fish and Wildlife Service Laboratory
in Columbia. MO or the U.S. EPA Laboratory in Duluth, MN. The data from
the Fish and Wildlife Service are contained in publications by Johnson
and Finley (1980), Macek et al. (1969), Sanders (1969, 1972) and Sanders
and Cope (1968) and include values for five invertebrates and five fishes.
The data from the EPA were published by Holcombe et al. (1982), Jarvinetr,
and Tanner (1982), Phipps and Holcombe (1985a, b), and Siefert et al.
(1984), and also include values for five invertebrates and five fishes^.
The only other acute value is from a test with a beetle by Federle and"
Collins (1976).
Within arthropods and fishes separately, and within all species combined,
there appears to be an inverse relationship between size and sensitivity;
to chlorpyrifos. The snail, Aplexa hypnorum, is the only species that ik
not either an arthropod or a fish for which an acute value is available:-..
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The Species Mean Acute Values (Table 1) were used to calculate Genus
Mean Acute Values (Table 3). Although values are available for 13 genera,
none is a planktonic crustacean. The most sensitive genus, Gammarus. is
more than 4,300 times more sensitive than the most resistant genera.
Aplexa, Carassius, and Ictalurus, but the four most sensitive genera are
within a factor of 4. and all are invertebrates. Mean acute values are
available for more than one species in each of two genera, and the range
of Species Mean Acute Values within each genus is less than a factor of
3. The freshwater Final Acute Value of 0.1669 pg/L was calculated from
the Genus Mean Acute Values (Table 3) using the procedure described in
the Guidelines. Criterion Maximum Concentration is 0.08345 wg/L, which is
below the normal detection limits.
Chronic Toxicity to Aquatic Animals
Available data on the chronic toxicity of chlorpyrifos contains
information on a single test species, the fathead minnow. Chronic values
for technical grade and encapsulated material were 2.26 ;jg/L and 3.25
iJg/L, respectively, in early life stage tests (Jarvinen and Tanner, 1982).
Growth over the 32-day tesp was the most sensitive parameter using
technical grade chlorpyrifos whereas with the encapsulated formulation,
growth and survival were equally sensitive. In a life cycle test with
the same species (Jarvinen et al. 1983) unacceptable effects occurred at
0.41 »Jg/L in the first generation and at 0.12 ^ig/L in the second generation,
showing rather poor agreement between the early life-stage test and the
life-cycle test. Based on these results the acute-chronic ratio for
chlorpyrifos is greater than 1,417 with the fathead minnow. Jarvinen et
al. (1983) also estimated the chronic effect of chlorpyrifos on the
viable biomass recruitment of a natural population of the fathead minnow.
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Requirements for an adequate data set for the calculation of Final Chronic
Value as prescribed in the Guidelines are not met.
Toxicity to Aquatic Plants
Several field studies have examined the effects of chlorpyrifos on
phytoplankton under more or less natural conditions (Brown et al. 1976;
Butcher et al. 1975, 1977: Hughes et al. 1980: Hurlbert 1969: Hurlbert et
al . 1972; Papst and Boyer 1980). All used an emulsifiable concentrate
formulation of chlorpyrifos which makes them inappropriate for inclusion
in Table 4, but the general trends identified are germaine to a discussion
of the effects of chlorpyrifos under natural conditions. With the
exception of Brown et al. (1976), all observed increased phytoplankton
numbers after pesticide application. This change is generally accepted
not to be a direct effect of chlorpyrifos, but rather a result of changes
in the herbivore-algal relationship caused by large reductions in
zooplankton populations. Reduced macrozooplankton numbers releases phytoplankton
community from herbivory. Papst and Boyer (1980) attempted to substantiate
this hypothesis experimentally by following concentrations of pheopigments,
the major chlorophyll a degradation product of herbivory.. after chlorpyrifos
application. Although this study did identify reductions in pheopigments,
the effect was delayed. They observed rapid increases in microzooplankton
(e.g., rotifers) numbers immediately after chlorpyrifos application,
presumably due to reduced competition with macrozooplankton. Other studies
have also observed an increase in microzooplankton after chlorpyrifos
treatment (Hughes 1977; Hurlbert et al. 1970, 1972; Siefert et al. 1984).
Although increased phytoplankton numbers can be explained by release from
herbivory, another possible factor may be increased phosphate concentration
directly from the decomposition of chlorpyrifos and from the decomposition
of intoxified organisms (Butcher et al. 1977).
6
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Bioaccumulation
Although chlorpyrifos is hydrophobia, which would suggest its
accumulation in tissues, this is offset by its rapid metabolism (Kenaga
and Goring 1980; Marshall and Roberts 1978), In the fathead minnow, an
average BAF at 60 days is 1673 (Jarvinen et al. 1983). Although this
study used an encapsulated formulation, chlorpyrifos test concentrations
were orepared separate from the test chamber. In a review, Kenaga and
Goring (1980) cite results of an unpublished study reporting a bioconcentration
factor in an unnamed fish of 450.
No U.S. FDA Action Level has been set for chlorpyrifos, therefore no
Final Residue Value could be derived.
Other Data
Data in Table 6 include investigations utilizing technical grade
chlorpyrifos. unless noted otherwise. Many were inadequate in duration
or tested associated effects of chlorpyrifos toxicity. Because of its
use as a biological control agent in mosquito abatement programs, the
mosquitofish has been widely studied to determine the effects of chlorpyrifos
applications on its survival and effectiveness as a mosquito larvae
predator. Ransen et al. (1972) reported an LC50 of 4000 >jg/L for this
fish at 24 hr. At 36 hr. LC50 of 215-230 pg/L was reported (Ferguson et
al. 1966), and at 72 hr. the LC50 was 0.19-0.22 >jg/L (Ahmed and Washino
1977). After * 24 hr. exposure to 5.0 *Jg/L, Johnson (1978a) observed a
decreased thermal tolerance in mosquitofish. Hansen et al. (1972) reported
an avoidance of chlorpyrifos when mosquitofish were given a choice between
clean water and a dosage of 100 ,jg/L in laboratory experiments. The
authors noted that this result did not prove that avoidance of chlorpyrifos
occurs in nature. The green sunfish was reported to have a 36-hr LC50
7
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of 22.5-37.5ug/L (Ferguson et al. 1966). At the same exposure duration,
the LC50 for the golden shiner was 35.0-45.0 pg/L. For rainbow trout,
the 96 hr. LC50s at 1.6*, 7.2", and 12.7° C were 51., 15., and 7.1 yg/L,
respectively (Macek et al. 1969). Increased toxicity of chlorpyrifos
with increased temperature was thought to be the result of increased
metabolism producing lower DO levels and higher metabolic wastes, or
increased enzyme activity converting chlorpyrifos to its more toxic form,
chlorpyrifos-oxon. In a 24-hr, exposure to 100 ug/L, atlantic salmon had
a 4* C lower temperature preference (Peterson 1976). Whether the preference
for a lower, presumibly less toxic temperature regimen was of any survival
benefit in nature is not known.
Because of the widespread use of chlorpyrifos as a mosquito larvicide,
many toxicity studies have used various species of mosquito larvae as
test organisms. Unfortunately, many studies have followed guidelines set
forth by the World Health Organization on testing of pesticides. These
guidelines prescribe a 24-hr duration, making result unusable for
derivation of numerical water quality criteria.
As would be expected, chlorpyrifos is highly toxic to mosquitos.
Rettich (1977) reportd 24 hr. LCSO's of 0.5 to 3.5 ;jg/L for 4th instars
of 6 species of the genus Aedes. For A. aegypti, a species not tested by
Rettich, Saleh et al. (1981) cited 24 hr. LCSOs of 0.0011 and 0.0014
;jg/L, for 2nd and 4th instars, respectively. Minimum lethal time (MLT)
for this species at 10 Mg/L is 18 hrs. (Verma and Rahman 1984). Reports
of 24 hr. LC50s for 4.th instars of various Culex species range from 0.41
pg/L to 2.0 pg/L (Ahmed 1.977; Kelson et al. 1979; Rettich 1977). For £.
pipiens, Saleh et al. (1981) found a 24-hr. LC50 of 0.0052 ,Jg/L.
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Use of chlorpyrifos as & pesticide in controlling noxious midge
populations has been documented (Ali and Mulla 1978a. 1980; Mulla and
Khasawinah 1969; Mulla et al. 1971; Thompson et al. 1970). LCSOs at 24
hr. for various midges generally range from 0.5 Mg/L to 40 Mg/L (Ali and
Mulla 1978a. 1980; Mulla and Khasawineh 1969) although a value of 1,470
pg/L was reported for Cricotopus decorus (Ali and Mulla 1980) .
Ahmed (1977) determined 24 hr. LCSOs in 6 species of aquatic coleopteran
and observed a range of 4.6 (jg/L to 52.0 Mg/L? he also cited for the same
test duration an LC50 of 15 ,jg/L for Belostoma sp. Levy and Miller (1978)
observed the delayed effects of a 24-hr, exposure to 1.0 and 4.0 ^jg/L on
a planarian, Dugesia dorotocephala over 108 hrs. They reported no
significant effects at either concentration. Siefert et al. (1984) cited
LCSOs for various durations with Chaoborus. Daphnia. a pigmy backswimmer,
an amphipod and a mayfly.
Several studies have provided interesting information of the effects
of chlorpyrifos, although are not suited for inclusion in data used to
derive numerical water quality criteria. Winner et al. (1978) used a
single chlorpyrifos concentration (E.G.) in an experiment on the effects
in a merraithid nematode parasite of mosquito larvae. They examined
toxicity to infectious, parasitic, post-parasitic, and embryo stages of
the nematode. Rawn et al- (1978) investigated the effect of various
sediments on the toxicity of chlorpyrifos to larvae of a mosquito in
artificial ponds. They found lower toxicity and lower water residues in
sod-lined ponds compared to sand-lined ponds at equal application rates.
Macek et al. (1972) conducted a field study which included analysis of
fish brain AChE activity, fish stomach contents, residues in fish and
water, numbers of larval insects, and numbers of emerging insects.
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Siefert et al. (1984) conducted an extensive survey of changes within a
natural pond after chlorpyrifos was applied using standard methods employed
by pest control authorities. Their study included analysis of water
quality, fish and invertebrate populations, and associated laboratory
studies.
Schaeffer and Dupros (1970) examined the effect of polluted waters
on the stability of chlorpyrifos in the field. As part of a laboratory
study, El-Refai et al. (1976) tested the effectiveness of a simulated
water treatment facility in lowering toxicity of Nile River water spiked
with chlorpyrifos. They found a 332 decrease in toxicity with alum
treatment, and no significant change with sand filtration.
Jamnback and Frempang-Boadu (1966), Mohsen and Mulla (1981). and
Muirhead-Thomson (1978, 1979) observed delayed effects after short exposures.
Unused Data
Some data on the effects of chlorpyrifos on aquatic organisms were
not used because the studies were conducted with species that are not
resident in North America (e.g.. Moorthy et al. 1982). Results of tests
reported by Ali (1981). Ferguson et al. (1966); Naqvi (1973): and Nelson and
Evans (1973) were not used because the test organisms probably had been
previously exposed to pesticides or other pollutants. Ramke (1969) only
presented data that have been published elsewhere.
Data were not used if the test was on a commercial formulation (e.g.,
At allah and Ishak 1971; Birmingham and Colman 1977: Chang and Lange 1967;
Hurlbert et al. 1970: Ledieu 1978; Mulla et al. 1973: Roberts and Miller
1971; Scirocchi and D'Erme 1980: Siefert et al. 1984; Smith et al. 1966)
or if the source of the chlorpyrifos was not adequately described (e g.,
Ali and Mulla 1976, 1977: Boike and Rathburn 1969; Gillies et al. 1974;
10
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Johnson 1977b, 1978b; Kenaga et al. 1965; Micks and Rougeau 1977; Muirhead-
Thomson and Merryweather 1969; Ruber and Kocor 1976; Thayer and Ruber
1976; Wilder and Schaefer 1969; Zboray and Gutierrz 1979). Data were not
used if Che organisms were exposed to chlorpyrifos by injection or gavage
or in food (e.g., Wilton et al. 1973) or if chlorpyrifos was a component
of a mixture (Meyer 1981), or were fed during exposure in short term
tests (Karnak and Collins 1974). The concentration of solvent was too
high in the tests of Davey et al. (1976) and Al-Khatib (1985). Barton
(1970) conducted a static chronic test with mosquito larvae. Because
polyethylene sorbs chlorpyrifos (Brown et al. 1976; Hughes 1977; Hughes
et al. 1980), toxicity tests conducted in polyethylene were not used
(e.g., Brown and Chow 1975; Darwazeh and Mulla 1974; Dixon and Brust
1971; Hughes 1977; Miller et al. 1973; Roberts et al. 1973a, b). Results
of some laboratory tests were not used because the tests were conducted
in distilled or deionized water without addition of appropriate salts
(e.g., Jones et al. 1976: Nelson and Evans 1973; Rongsreyam et al. 1968;
Steelman et al. 1969). High control mortalities occurred in tests reported
by Khudairi and Ruber (1974), Test procedures were inadequately described
by Ruber and Baskar (1969). Roberts and Miller (1970) tested only one
concentration of chlorpyrifos. BCFs obtained from microcosm or model
ecosystem studies were not used if the concentration of chlorpyrifos in
water decreased with time or if the exposure was too short (e.g., Metcalf
1974). Results of field tests were not used if the concentrations of
chlorpyrifos were not measured (e.g., Ali and Mulla 1976, 1977, 1978a, b
Axtell et al. 1979; Best. 1969: Carter and Graves 1972; Chang and Lange
1967; Chatterji et al. 1979; Cooney and Pickard 1974; Evans et al. 1975;
Frank and Sjogren 1978; Hazeleur 1971; Hoy et al. 1972: Jamnback 1969;
11
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Lembright 1968; Linn 1968; McNeill et al. 1968; Moore and Breeland 1967;
Mulla and Khasawinah 1969: Mulla et al. 1971; Nelson et al. 1976a, b;
Polls et al. 1975: Roberts et al. 1984; Steelman et al. 1969; Stewart
1977: Tawfik and Gooding 1970: Taylor and Schoof 1971; Thompson et al.
1970: Wallace et al. 1973; Washino et al. 1968, 1972a, b; Wilkinson et
al. 1971; Winterlin et al. 1968: Yap and Ho 1977) or if the concentration
in water was not uniform enough (e.g., Macek et al. 1972).
The acute values for eighteen species in fifteen genera range from
greater than 806 yg/L for two fishes and a snail to 0.11 iJg/L for an
amphipod. The bluegill is the most acutely sensitive fish species with
an acute value of 10 (Jg/L, but seven invertebrate genera are more sensitive
Larger organisms seem to be less sensitive.
Chronic toxicity data are available for one species, the fathead
minnow. Unacceptable effects occurred to second generation larvae at
0.12 Mg/L, which was the lowest concentration tested. The resulting
acute-chronic ratio was greater than 1.400.
Little information is available on the toxicity of chlorpyrifos to
aquatic plants, although a consistent observation of increased algal
blooms is frequently reported associated with chlorpyrifos application.
The only available bioconcentration test on chlorpyrifos with freshwater
species was with the fathead minnow and resulted in a BCF of 1,673.
Ktatipnal 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
12
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should not be affected unacceptably if the four-day average concentration
of chlorpyrifos does not exceed AAA jJg/L more than once every three years
on the average or if the one-hour average concentration does not exceed
0.083 Mg/L more than once every three years on the average.
The procedures described in the "Guidelines for Deriving Numerical
National Hater 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 chlorpyrifos does not exceed pig/L more than once every three years on
the average and if the one-hour average concentration does not exceed yyy
»jg/L more than once every three years on the average.
The allowed excursion frequency of three years is based on the
Agency's best scientific judgment of the average amount of time it will
take an aquatic ecosystem to recover from a pollution event in which
exposure to chlorpyrifos exceeds the criterion. 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
selection of an appropriate wasteload allocation model. Dynamic models
are preferred for the application of these criteria. Limited data or other
factors nay make their use impractical, in which case one must rely on a
steady-state model. The Agency recommends interim use of 1Q10 for
Criterion Maximum Concentration (CMC) design flow and 7Q10 for the
Criterion Continuous Concentration (CCC) design flow in steady-state
models. These matters are discussed in more detail in the Technical
Support Document for Water Quality-Based Toxics Control (U.S. EPA 1985)
and the Design Flow Manual (U.S. EPA 1986).
13
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Tab)* 1. Acute Toxlclty of Ct>IorpyrIfo» to Aquatic Animals
CC90 Species Mean
or EC50 Acute Value
Species Method* Cham leal (pg/L) (»g/L> Reference
Snail (adult),
Aplexa hypnorum
Amphlpod,
Gammarus fasctatus
Amphlpod (2 no. old),
Gammarus lacustrls
Amphlpod,
Gammarus pseudol Imnaeus
Crayfish ( 1 .8 g) ,
Orconectes Immunls
Stonefly (naiad),
Pteronarcel la bad la
Stonefly (naiad),
Pteronarcys callfornlca
Stonefly (naiad),
Claassenta sabulosa
Trlchopteran,
Leptocerldae sp.
Pyqmy backs wlmmer,
Neoplea strlola
Pygmy backswlmmer ,
Neoplea strlola
Crawling water beetle
(adult).
Pel tody tes sp.
FRESHWATER
f, M Technical
S, U Technical
S, U Technical
F, M Clarke**
F, M Technical
S, U Technical
S, U Technical
S, U Technical
S, M Clarke**
S, M Clarke**
S, M Clarke**
S, U
SPECIES
>806 >806 Phlpps and Hoi combe
1985a,b
0.32 0.52 Sanders 1972
O.I.I 0.11 Sanders 1969; Johnson
and Flnley 1980
0.18 0.18 Slefert et al . 1984
6 6 Phlpps and Ho) combe
1985a,b
0.38 0.38 Sanders and Cope 1968
10 10 Sanders and Cope 1968;
Johnson and Flnley 1980
0.57 0.57 Sanders and Cope 1968;
Johnson and Flnley 1980
0.77 0.77 Slefert et al . 1984
1.22 - Slefert et al. 1984
1.56 1.38 Slefert et al . 1984
0.8 0.8 Federle and Collins
1976
Cutthroat trout (1.4 g),
Satmo clorklI
S, U
Technical
18
18
Johnson and Flnley 1980
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TabU 1. (continued)
Specie* Method* Chemical
Rainbow trout (0.6-1.5 g), S, 0 Technical
Salmo galrdnerl
Rainbow trout (Juvenile), F, M Technical
Salmo qalrdnerl
Rainbow trout (3.0 g) , F, M Technical
Salmo galrdnerl
Lake trout (2.3 g), S, U Technical
Salvellnus namaycush
Goldfish (10.7 9), F, M Technical
Carass Ius auratus
Fathead minnow, S, M Technical
Plmephales promelas^
Fathead minnow (juvenile), F, M Technical
Plmephales j>rpme|as^
Fathead minnow (0.5 g), F, M Technical
Plmephales prometas
Channel catfish (0.8 g), S, U Technical
Ictalurus punctatus
Channel catfish (7.9 g), F, M Technical
I eta I urus punctatus^
Blueglll (0.6 g) , S, U Technical
Lepomls macrochlrus
Blueqlll (0.8 g), F, M Technical
Lepomls macrochlrus
LC50 Spiles Mean
or EC50 Acute Value
7.1
8.0
9
98
>806
170
203
542
280
>806
2.4
10
8.485
98
>806
331.7
806
10
Reference
Macek et at. 1969;
Johnson and Fin ley 1980
Hoi combe et al. 1982
Phlpps and Holconbe
1985a,b
Johnson and Fin ley 1980
Phlpps and MoI combe
1985a,b
Jarvlnen and Tanner
1982
HoIcombe et al. 1982
Phlpps and HoI combe
1985a.b
Johnson and Flnley 1980
Phlpps and HoI combe
1985a,b
Johnson and Flnley 1980
Phtpps and Hoi combe
1985a,b
* S " static; R « renewal; F » flow-through; U » unmeasured; M » measured.
** Clarke » encapsulated technical chlorpyrIfos; doses prepared separate from test chamber.
-------
Table 2. Chronic Toxic Ity of Chlorpyrlfos to Aquatic AnlMl
Species Test*
Fathead minnow, ELS
Plmephales promelas
Fathead minnow, ELS
Plmephales promelas
Fathead minnow, LC
Plmephales promalas
Fathead minnow (second ELS
generation),
Plmephales promelas
Limits Chronic Valu*
Chemical (ugA) (nq/L)
FRESHWATER SPECIES
Technical 1.6-3.2 2.263
Encapsulated 2.2-4.8 3.250
Encapsulated 0.27-0.63 0.4124
Encapsulated <0.12"» <0.12
Reference
Jarvlnen
1982
Jarvlnen
1982
Jarvlnen
Jarv Inen
and Tanner
and Tanner
et al. 1983
et al. 1983
* LC » life-cycle or partial life-cycle; ELS = early life-stage.
** Unacceptable effects occurred at
Specie*
Fathead minnow.
al 1 tested concentrations.
Acute-Chronic Ratio
Acute Valu* Chronic Value
(»gA) (»q/L)
Ratio
170 l,417
Plmephales promelas
-------
Table 3. Ranked Genus Mean Acute Value* with Species Mean Acute-Chronic Ratios
tank*
15
14
13
12
It
10
9
8
7
6
5
4
Genus Mean
Acute Value
806
>806
806
331.7
98
12.36
10
to
6
1.38
0.8
0.77
Species
FRESHWATER SPECIES
Snail,
Aplexa hypnorum
Goldfish,
Car ass 1 us auratus
Channel catfish,
Ictalurus punctatus
Fathead minnow,
Plmephales promelas
Lake trout,
Salvellnus namaycush
Cutthroat trout,
Salmo clarkl
Rainbow trout,
Salmo qalrdnerl
Stonef ly,
Pteronarcys callfornlca
Blueqlll,
Lepomls macrochlrus
Crayfish,
Orconectes Immunls
Pygmy backs w 1 mmer ,
Neoplea strlola
Crawling water beetle,
Pel tody tes sp.
Trlchoptera
Species Mean
Acute Value
(»g/L)M
>806
>806
806
331.7
98
18
8.485
10
10
6
1.38
0.8
0.77
Species Mean
Acute-Chronic
Retlo""
> 1,4 17
Leptocer Idae sp.
-------
Tabla 3. (continued)
Rank"
3
2
1
Genus Maan
Acuta Value
(ng/L) Species
0.57 Stonef ly,
Claasenla sabulosa
0.38 Stonef ly,
P teronarce 1 1 a bad 1 a
0.1850 Amph 1 pod.
Gammarus fasclatus
Amph 1 pod ,
Gammarus lacustrls
Amph I pod ,
Gammarus pseudol Imnaeus
Specie* Maan
Acuta Value
0.57
0.38
0.32
O.It
0.1B
Specie* Maan
Acute-Chronic
Ratio***
-
* Rankad from most resistant to most sensitive based on Genus Mean Acute Value.
*» From Table I.
•»» From Table 2.
Fresh water
Final Acute Value = 0.1669 pg/L
Criterion Maximum Concentration = (O.t669 ug/L) / 2 * 0.08345 i»9/t
-------
Tabla 4. Bloconcantratlofl of CMorpyrlfo* by Aquatic Organ I
Concentration Duration
Spaclaa Cnaalcal* In Watar (pg/D** (days) Tl««ua BCF or BAF*** Rafaranc*
FRESHWATER SPECIES
Fathead minnow, Encapsulated 0.12-2.68 60 Whole 1,673 Jarvlnen at al. 1983
Ptmaphatas promelas body
-------
Table 5. Other Data on Effects of Chlorpyrlfos on Aquatic Organises
Species
Chenlcel
Duration
Effect
Result
(jig/L)* Reference
FRESHWATER SPECIES
Planarla,
Duqesla dorotocepha 1 a
Cladoceran,
Daphnle sp.
Amp hi pod,
Hyalet la azteca
Mayfly.
Ephemeral! a sp.
Pygmy backs wlmmer,
Neoplea strict a
Giant water bug (adult),
Belostoma sp.
Predaceous dlvlnq beetle
(adult),
Hygrotus sp.
Predaceous diving beetle
(adult),
Laccophl lus declplens
Predaceous diving beetle
(adult),
Thermonectus basil larls
Water scavenger beetle
(adult),
Berosus sty lifer us
Mater scavenger beetle
108 hr
Clarke* 4 hr
Clarke* 24 hr
Clarke* 72 hr
Clarke* 144 hr
Technical 24 hr
Technical 24 hr
Technical 24 hr
Technical 24 hr
Technical 24 hr
Technical 24 hr
Delayed effects No effect Levy and M
after 24 hr detected at
exposure 1.0 and 4.0
LC50
LC50
LC50
LC50
LC50
LC50
LC50
LC50
LC50
LC50
0.88 Slefert et
1.28 SUtert et
0.33 Slefert et
0.97 Slefert et
13 Ahmed 1977
40 Ahmed 1977
4.6 Ahmed 1977
6 Ahmed 1977
9 Ahmed 1977
20 Ahmed 1977
(larva),
Hydrophllus trlangularls
-------
Table 9. (continued)
Result
Species
Mater scavenger beetle
(adult).
Hydrophllus trlangularls
Mater scavenger beetle
( larva) ,
Troplsternus lateral Is
Mater scavenger beetle
(adult),
Troplsternus lateral Is
Mosquito (3rd and 4th
Instar) ,
Aedes aegyptl
Mosquito (2nd Instar),
Aedes oeqyptl
Mosquito (4th Instar),
Aedes aegyptl
Mosquito (4th Instar),
Aedes cantans
Mosquito (4th Instar),
Aedes common Is
Mosquito (4th Instar),
Aedes excruclans
Mosquito (4th Instar),
Aedes punctor
Mosquito (4th Instar),
Aedes stlctlcus
Mosquito (4th Instar),
Aedes vexans
Mosquito ( larva) ,
Chemical
Technical
Technical
Technical
Technical
Technical
Technical
Techn leal
Technical
Technical
Techn leal
Technical
Technical
Technical
Duration
24 hr
24 hr
24 hr
18 hr
24 hr
24 hr
24 hr
24 hr
24 hr
24 hr
24 hr
24 hr
24 hr
Effect
LC50
LC50
LC50
LT50
LC50
LC50
LC50
LC50
LC50
LC50
LC50
LC50
LC50
30
52
10
0.0011
1.1
3.5
3.3
2.7
0.5
J.O
3
Reference
Ahmed 1977
Ahmad 1977
Ahmed 1977
Verma and Rahman 1984
Sal eh et al. 1981
0.0014 Sal eh et al. 1981
Rettlch 1977
Rettlch 1977
Rettlch 1977
Rettlch 1977
Rettlch 1977
Rettlch 1977
Ahmed 1977
Anopheles freebornl
-------
Table 5. (continued)
Species
MosqultoHsh,
G ambus la at finis
Guppy,
Poecllla retlculata
Green sunflsh,
Lepomls cyanellus
Chealcal Duration
24 hr
Technical 24 hr
Technical 36 hr
Effect
LC50
LC50
LC50
Result
4,000
220
37.5
22.5
Reference
Hansen et al .
Ronqsrlyam et
Ferguson et al
1972
al. 1968
. 1966
* Clarke » encapsulated technical chlorpyrIfos; doses prepared separate from test chamber.
** Aged II weeks.
-------
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