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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.
11
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FOREWORD
Section 304(a)(l) of the Clean Water Act requires the Administrator of
the Environmental Protection Agency to publish water quality criteria that
accurately reflect the latest scientific knowledge on the kind and extent of
all identifiable effects on health and welfare that might be expected from the
presence of pollutants in any body of water. Pursuant to that end, this
document proposes water quality criteria for the protection of aquatic life.
These criteria do not involve consideration of effects on human health.
This document is a draft, distributed for public review and comment.
After considering all public comments and making any needed changes, EPA will
issue the criteria in final form, at which time they will replace any
previously published EPA aquatic life criteria for the same pollutant.
The term "water quality criteria" is used in two sections of the Clean
Water Act, section 304(a)(l) and section 303(c)(2). In section 304, the term
represents a non-regulatory, scientific assessment of effects. Criteria
presented in this document are such scientific assessments. If water quality
criteria associated with specific stream uses are adopted by a State as water
quality standards under section 303, then they become maximum acceptable
pollutant concentrations that can be used to derive enforceable permit limits
for discharges to such waters.
Water quality criteria adopted in State water quality standards could
have the same numerical values as criteria developed under section 304.
However, in many situations States might want to adjust water quality criteria
developed under section 304 to reflect local environmental conditions before
incorporation into water quality standards. Guidance is available from EPA to
assist States in the modification of section 304(a)(l) criteria, and in the
development of water quality standards. It is not until their adoption as
part of State water quality standards that the criteria become regulatory.
Martha G. Prothro
Director
Office of Water Regulations and Standards
111
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ACKNOWLEDGMENTS
Daniel J. Call
(freshwater author)
University of Wisconsin-Superior
Superior, Wisconsin
Jeffrey L. Hyland
Richard K. Peddicord
(saltwater authors)
Battelle Ocean Sciences
Duxbury, Massachusetts
Charles E. Stephan
(document coordinator)
Environmental Research Laboratory
Duluth, Minnesota
David .!. Hansen
(saltwater coordinator)
Environmental Research Laboratory
Narragansett, Rhode Island
IV
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CONTENTS
Page
Notices i i
Foreword i i i
Acknowledgments iv
Tables vi
Introduction 1
Acute Toxicity to Aquatic Animals 2
Chronic Toxictty to Aquatic Animals 4
Toxicity to Aquatic Plants 6
Bioaccumulation 6
Other Data 7
Unused Data 8
Summary 8
National Criteria 9
Implementation 10
References 25
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TABLES
Page
1. Acute Toxicity of 2,4,5-Trichlorophenol to Aquatic Animals 12
2. Chronic Toxicity of 2,4,5-Trichlorophenol to Aquatic Animals 16
3. Ranked Genus Mean Acute Values with Species Mean Acute-Chronic
Ratios 18
4. Toxicity of 2,4,5-Trichlorophenol to Aquatic Plants 21
5. Bioaccumulation of 2,4,5-Trichlorophenol by Aquatic Organisms 22
6. Other Data on Effects of 2,4,5-Trichlorophenol on Aquatic Organisms . 23
VI
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Introduction
2,4,5-Trichlorophenol (2,4,5-TCP) is a crystalline solid at room
temperature. It is soluble in water up to 2,000 mg/L, has an ionization
constant (pKa) of 7.0 to 7.4 (Ahlborg and Thunberg 1980; Doedens 1964; U.S.
EPA 1980), and a log n-octanol/water partition coefficient of 3.70 (Hansch
and Leo 1979). 2,4,5-TCP is used as an algicide, fungicide, and bactericide
and as an antimildew and preservation agent in cooling towers, pulp mills,
and in hide and leather processing (Ahlborg and Thunberg 1980; U.S. EPA
1980). It is also used in the production of the pesticides erbon,
fenchlorphos, fenoprop (2,4,5-TP), hexachlorophene, and 2,4,5-trichloro-
phenoxyacetic acid (2,4,5-T) (Ahlborg and Thunberg 1980; Buikema et al. 1979;
Doedens 1964; Kozak et al. 1979; Stolzenburg and Sullivan 1984).
Contamination of waters with 2,4,5-TCP and other chlorophenols has
resulted from the use of chlorophenoxyacetic acid herbicides containing
chlorophenolic impurities, from the chlorination of waste treatment plant
effluents, and from pulp bleaching (Ahlborg and Thunberg 1980; Buikema et al.
1979; Jolley et al. 1976; Rockwell and Larsen 1978). Residues have been
detected in fish and other organisms collected downstream from pulp mills
(Paasivirta et al. 1985). Considerable concern has been expressed that
2,3,7,8-tetrachlorodibenz'o-p-dioxin (TCDD) can be an impurity in 2,4,5-TCP
(Anonymous 1976; Firestone et al. 1972).
At very low concentrations, some phenolic compounds impair the odor and/
or taste of water and fish. 2,4,5-TCP has a taste threshold concentra-
tion in water of 1 pg/L and an odor threshold concentration of 200 pg/L
(Dietz and Traud 1978). However, Shumway and Palensky (1973) did not observe
flavor impairment in rainbow trout exposed to 320 pg/L for 48 hr.
An understanding of the "Guidelines for Deriving Numerical National Water
Quality Criteria for the Protection of Aquatic Organisms and Their Uses"
1
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(Stephan et al. 1985), hereinafter referred to as the Guidelines, and the
response to public comment (U.S. EPA 1985a) is necessary in order to
understand the following text, tables, and calculations. Results of such
intermediate calculations as recalculated LCSOs and Species Mean Acute Values
are given to four significant figures to prevent round off error in
subsequent calculations, not to reflect the precision of the value. The
criteria presented herein supersede the aquatic life information in a
previous criteria document (U.S. EPA 1980) because these criteria are based
on additional information. The latest literature search for information for
this document was conducted in July, 1986; some more recent information was
included. Data that are in the files of the U.S. EPA's Office of Pesticide
Programs concerning the effects of 2,4,5-TCP on aquatic life and its uses
have not been evaluated for possible use in the derivation of aquatic life
criteria.
Acute Toxicity to Aquatic Animals
Data that can be used, according to the Guidelines, in the derivation of
Final Acute Values for 2,4,5-TCP are presented in Table 1. The rainbow
trout, Salmo gairdneri. was the most sensitive freshwater species with a
96-hr LC50 of 260 Mg/L. The cladoceran, Daphnia magna. was the most
resistant species, with a 48 hr EC50 of 2,660 pg/L. The range of acute
values for fish was from 260 ng/L in the trout to 3,060 MgA in the
guppy, Poecilia reticulata. A similar range for invertebrates extended from
336 Mg/L in.the amphipod, Gammarus pseudolimnaeus to 2,660 jug/L in
Daphnia.
The effect of pH on the acute toxicity of 2,4,5-TCP was examined with the
guppy, Poecilia reticulata (Saarikoski and Viluksela 1981,1982; Salkinoja-
Salonen et al. 1981). The 96-hr LCSOs at pH = 6, 7, and 8 were 990, 1,240,
2
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and 3,060 MgA. respectively. The freshwater criterion was not made
pH-dependent because data are available for only one species.
Freshwater Species Mean Acute Values (Table 1) were determined from the
available acute values. Genus Mean Acute Values (Table 3) were the same as
the Species Mean Acute Values. Of the ten freshwater genera for which mean
acute values are available, the most sensitive genus, Sal mo. is about 10
times more sensitive than the most resistant, Daphnia. The freshwater Final
Acute Value for 2,4,5-TCP was calculated to be 199.2 ng/L using the
procedure described in the Guidelines and the Genus Mean Acute Values in
Table 3. The Final Acute Value is lower than the lowest available Species
Mean Acute Value.
The stock of 2,4,5-TCP that was used in freshwater acute tests reported
by Sabourin et al. (1986) and Spehar (1986) was found to contain U.2 ng/g of
the contaminant, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) (Durhan 1986).
This resulted in estimated 2,3,7,8-TCDD concentrations in the exposure water
as high as 115 pg/L (Table 1). It is not known if 2,3,7,8-TCDD
concentrations of 115 pg/L or less had an effect upon the observed toxicity.
Concentrations of 2,3,7,8-TCDD were not determined in the other freshwater
acute tests.
Tests of the acute toxicity of 2,4,5-TCP to resident North American
saltwater animals have been performed with six species of invertebrates and
five species of fish (Table 1). The range of acute values for invertebrates
extends from 492 Mg/L for the amphipod, Rhepoxvnius abronius (Battelle
Ocean Sciences 1987) to 3,830 ng/L for adult mysids, Mvsidopsi s bahia
(U.S. EPA 1978). The range of acute values for saltwater fish is narrower,
from 566 jug/L for both juvenile English sole, Parophys vetulus. and adult
Pacific sand lance, Ammodvtes hexapterus (Battelle Ocean Sciences 1987) to
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1,660 ng/L for both juvenile sheepshead minnows, Cvprinodon variegatua
(Heitrauller et al. 1981) and juvenile inland silversides, Menidia beryl 1ina
(Hughes and Pruell 1987).
The 24- and 96-hr LCSOs differed little with both mysids and sheepshead
minnows (Heitmuller et al. 1981; U.S. EPA 1978). In contrast, mortalities
continued throughout acute tests with polychaete worms, archiannelids, and
inland silversides (Battelle Ocean Sciences 1987). Rao et al. (1981) found
that 2,4,5-TCP was about twice as toxic to molting grass shrimp as it was to
intermolt shrimp. The effect of environmental factors such as salinity and
temperature on the acute toxicity of 2,4,5-TCP to saltwater animals is not
known.
Of the ten genera for which saltwater Genus Mean Acute Values are
available (Table 3), the most sensitive genus, Rhepoxynius. is about 7.8
times more sensitive than the most resistant, Mysidoosis. The six most
sensitive genera are within a factor of 1.8 and include four invertebrates
and two fishes. The saltwater Final Acute Value for 2,4,5-TCP was calculated
to be 472.9 Mg/L, which is lower than the mean acute value for the most
sensitive tested saltwater species.
Chronic Toxicitv to Aquatic Animals
The available data that are useable according to the Guidelines con-
cerning the chronic toxicity of 2,4,5-TCP are presented in Table 2. In a
seven-day life-cycle test with Ceriodaphnia dubia. all organisms died at a
concentration of 1,480 ^g/L (Spehar 1986). A concentration of 746 ng/L
did not cause mortality, but significantly reduced production of young. A
concentration of 375 pg/L affected neither survival nor reproduction. The
resulting chronic value was 528.9 ng/L and the acute-chronic ratio was
3.294 (Table 2).
4
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In a 90-day early life-stage test with rainbow trout (Spehar 1986), a
concentration of 441 /ig/L caused 100% mortality of swim-up larvae. A
concentration of 208 ng/L did not affect hatchability or swim-up larvae,
but significantly (P <, 0.05) decreased survival of juveniles. No adverse
effects were observed at 108 Mg/L or below. The chronic value and
acute-chronic ratio were 149.9 MgA and 1-734, respectively (Table 2).
Fathead minnows, Pimephal es promelaj.. exposed to 160 pg/L were not
adversely affected in an early life-stage test (Spehar 1986). Reduced growth
and approximately 50% mortality occurred at 342 p.g/L. Complete mortality
was observed at 673 and 1,322 Mg/L. The chronic value was 233.9 ng/L
and the acute-chronic ratio was 5.421 (Table 2).
The stock 2,4,5-TCP that was used in the freshwater chronic tests
reported by Spehar (1986) contained up to 14.2 ng/g of 2,3,7,8-TCDD (Durhan
1986). This resulted in estimated maximum 2,3,7,8-TCDD concentrations in the
exposure water of 40.9 pg/L in the Ceri odaphnia test, 6.3 pg/L in the rainbow
trout test, and 18.8 pg/L in the fathead minnow test. It is not known at
present if 2,3,7,8-TCDD at these concentrations had any effect upon the
observed toxicity.
The chronic toxicity of 2,4,5-TCP has been measured in salt water with
the inland silverside, Menidi a beryl 1ina (Hughes and Pruell 1987). In this
early life-stage test, 86% of the embryos exposed to 104 MgA died before
hatching. Survival of both embryos and fry was reduced at 59.6 Mg/L, but
no effects were detected at 25.1 ng/L. The resulting chronic value was
38.68 Mg/L. and the acute-chronic ratio was 42.92 (Table 2).
The available Species Mean Acute-Chronic Ratios are 3.294, 5.421, and
1.734 in fresh water and 42.92 in salt water (Table 3). The freshwater Final
Acute-Chronic Ratio of 3.140 was calculated as the geometric mean of the
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three ratios, whereas 42.92 was used as the saltwater Final Acute-Chronic
Ratio. Division of the freshwater and saltwater Final Acute Values by the
respective Final Acute-Chronic Ratios results in freshwater and saltwater
Final Chronic Values of 63.44 and 11.02 ng/L, respectively. These Final
Chronic Values are lower than the lowest available respective chronic values
in fresh and salt water.
Toxicitv to Aquatic Plants
Two toxicity tests with exposure periods of four or more days have been
conducted on 2,4,5-TCP with aquatic plants (Table 4). An EC50, based on
reduction of chlorophyll a., was 1,200 ng/L for the freshwater green alga,
Selenastrum capricornutum (U.S. EPA 1978). The EC50, based on reduction in
chlorophyll a., was 890 pg/L for the saltwater diatom, Skeletonema
costatum. whereas the EC50 based on cell counts was 960 ng/L (U.S. EPA
1978). These concentrations are above the Final Acute Values for 2,4,5-TCP.
A Final Plant Value, as defined in the Guidelines, cannot be obtained because
no test in which the concentrations of 2,4,5-TCP were measured and the
endpoint was biologically important has been conducted with an important
aquatic plant species.
Bioaccumulation
In a bioconcentration test with the fathead minnow, equilibrium of
^C-labeled 2,4,5-TCP between water and fish occurred within 24 to 48 hr at
exposure concentrations of 4.8 and 49.3 ng/l (Call et al. 1980). At the
higher concentration, 78.6% of the radiolabel was associated with 2,4,5-TCP
at the end of the 28-day uptake phase. The BCF was 1,410 and the half-life
was 12 hr (Table 5).
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Inland siIversides, Menidia beryl!ina. that survived a 28-day early life-
stage toxicity test accumulated 2,4,5-TCP to concentrations between 47.2 and
71.3 times the concentration measured in test solutions (Table 5). Biocon-
centration factors for grass shrimp, Palaemonetes pugio. exposed for one hour
to 14C-trichlorophenol were 13 for intermolt and 32 for new molt stages
(Table 6). Concentrations after 12 hours of exposure of intermolts were
highest in the digestive tract and hepatopancreas and lowest in the cephalo-
thorax and abdomen. Shrimp depurated 96% of accumulated 2,4,5-TCP in 24 hr
(Rao et al. 1981).
No U.S. FDA action level or other maximum acceptable concentration in
tissue, as defined in the Guidelines, is available for 2,4,5-TCP. Therefore,
a Final Residue Value cannot be calculated.
Other Data
Additional data on the lethal and sublethal effects of 2,4,5-TCP on
aquatic species are presented in Table 6. Exposures of an alga, Chlorella
pyrenoidosa. to 2,4,5-TCP for 3 days at concentrations from 1,000 to
10,000 ng/L reduced chlorophyll by 12 to 100% (Huang and Gloyna 1967,
1968). The 24-hr EC50 for the protozoan, Tetrahymena pyriformis. was
680 jug/L (Yoshioka et al. 1985). A 24-hr exposure to 1,912 jug/L caused
100% mortality of lymnaeid snails (Batte and Swanson 1952). A 24-hr EC50 of
2,080 M8/L **s obtained with the cladoceran, Daphnia magna (Devillers and
Chambon 1986). A 48-hr exposure of rainbow trout to 2,4,5-TCP at
1,000 /ig/L resulted in 100% mortality (Shumway and Palensky 1973). LCSOs
of 900. 533, and 1,700 ng/L were obtained at 24 hr with the brown trout,
guppy, and goldfish, respectively.
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Ribo and Kaiser (1983) reported a 30-min EC50 of 1,300 jug/L, based on
reduction in light production by the photoluminescent bacterium,
Photobacterium phosphoreum (Table 6). Rao et al. (1981) found that exposure
to 500 and 750 Mg/L for 9 days inhibited limb regeneration by the grass
shrimp, Palaemonetes pugio. Limb regeneration was not affected in
100 jug/L.
Unused Data
Some data on the effects of 2,4,5-TCP on aquatic organisms were not used
because the tests were conducted with species that are not resident in North
America (e.g., Hattori et al. 1984; Hosaka et al. 1984; Nagabhushanam and
Vaidya 1981). Kaiser et al. (1984), LeBlanc (1984). and Persson (1984)
compiled data from other sources. Bringmann and Kuhn (1982) cultured
organisms in one water and conducted tests in another. Dojlido (1979) did
'>
not specify which trichlorophenol was used. Blackman et al. (l955a,b)
conducted tests at pH below 6.5.
Results were not used when the test procedures were not adequately
described (Knie et al. 1983). Studies by Kobayashi et al. (1984) on the
sulfate conjugating enzyme system and McKim et al. (1985) on the efficiency
of chemical uptake by fish gills did not provide data pertinent to water
quality criteria.
Summary
The acute toxicity of 2,4,5-trichlorophenoi to freshwater animals ranged
from 260 ng/L for the rainbow trout to 2,660 ^g/L for Daphnia magna.
The acute toxicity of 2,4,5-TCP to the guppy increased as the pH of the water
decreased. Chronic toxicity values for three freshwater species ranged from
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150 to 529 ng/L, and the three acute-chronic ratios ranged from 1.734 to
5.421. A freshwater alga was affected at a concentration of 1,220 ng/L.
A BCF of 1,410 was obtained with the fathead minnow.
Acute values for 2,4,5-trichlorophenol are available for eleven saltwater
animal species in ten genera and range from 492 ^g/L for the amphipod,
Rhepoxvnius abronius. to 3,830 MgA fฐr tne mysid, Mysidopsis bahia. The
six most sensitive species include three crustaceans, two fishes, and a
polychaete worm and their acute values are all within a factor of 1.8. The
only saltwater species with which a chronic test has been conducted is the
inland silverside, Menidia beryl 1ina. The chronic value is 38.68 pg/L,
and the acute-chronic ratio is 42.92. The saltwater diatom, Skeletonema
costatum. was affected by 890 Mg/L- BCFs determined with the inland
silverside ranged from 47 to 71.
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 2,4,5-tri-
chlorophenol does not exceed 63 ng/L more than once every three years on
the average and if the one-hour average concentration does not exceed
100 ng/L more than once every three years on the average. Because
sensitive freshwater animals appear to have a narrow range of acute
susceptibilities to 2,4,5-trichlorophenol, this criterion will probably be as
protective as intended only when the magnitudes and/or durations of
excursions are appropriately small.
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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
2,4,5-trichlorophenol does not exceed 11 ng/L more than once every three
years on the average and if the one-hour average concentration does not
exceed 240 ng/L more than once every three years on the average. Because
sensitive saltwater animals appear to have a narrow range of acute
susceptibilities to 2,4,5-trichlorophenol, this criterion will probably be as
protective as intended only when ฑhe magnitudes and/or durations of
excursions are appropriately small.
Implementation
As discussed in the Water Quality Standards Regulation (U.S. EPA 1983a)
and the Foreword to this document, a water quality criterion for aquatic life
has regulatory impact only after it has been adopted in a sttate 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. 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
1983b,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 1983b), but also site-specific, and possibly
pollutant-specific, durations of averaging periods and frequencies of allowed
excursions (U.S. EPA 1985b). The averaging periods of "one hour" and "four
10
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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
aquatic 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 1985b). 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 1985b), 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 1985b,1987).
11
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