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Water Quality

Ambient Water Quality Guidelines for Toluene

Overview Report

Prepared pursuant to Section 2(e) of the
Environment Management Act, 1981

Original signed by Margaret Eckenfelder
Assistant Deputy Minister
Environment and Lands HQ Division
November 27, 2000


TABLE OF CONTENTS

Summary

Tables

Preface

Introduction

Recommended Guidelines

Application of the Guidelines

References


Summary

This document is one in a series that establishes ambient water quality guidelines for British Columbia. It is based on a technical report prepared for the Canadian Council of Ministers of Environment (CCME) proposing Water Quality Guidelines for Toluene (July 1995 update). This overview report assesses those guidelines for use in British Columbia, assesses more recent information and makes amendments where appropriate to suit BC conditions. The guidelines are safe conditions or levels that have province-wide application and are set to protect various water uses. This report sets guidelines for toluene to protect drinking water, freshwater and marine aquatic life and livestock watering. Based on this evaluation, the CCME guidelines adopted by the province were for drinking water and livestock watering, while adjustments were deemed necessary to protect aquatic life in fresh and marine waters.

A major use of the guidelines is to set ambient water quality objectives. The objectives are the guidelines modified or adopted to protect the most sensitive designated water use in a particular body of water. The objectives are used in the preparation of waste management plans, pollution prevention plans, waste management permits, orders or approvals. The latter three are the only documents that have legal status. The guidelines are also used as a basis for evaluating contaminated sites and determining remediation requirements.

The guidelines are summarized in Table 1.


Tables

Table 1: Summary of Water Quality Guidelines for Toluene

Water Use
Maximum Total Toluene
Drinking Water - Aesthetics
0.024 mg/L
Freshwater Aquatic Life
0.039 mg/L
Marine and Estuarine Aquatic Life
0.33 mg/L
Recreation
none proposed
Crop Irrigation
none proposed
Livestock Watering
0.024 mg/L


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Preface

THE MINISTRY OF ENVIRONMENT, LANDS AND PARKS (now called Ministry of Water, Land and Air Protection) develops province-wide ambient water quality guidelines for variables that are important in the surface waters of British Columbia. This work has the following goals:

  1. to provide guidelines for the evaluation of data on water, sediment and biota
  2. to provide guidelines for the establishment of site-specific ambient water quality objectives

Ambient water quality objectives for specific waterbodies will be based on the guidelines and also consider present and future uses, waste discharges, hydrology/limnology/oceanography, and existing background water quality. The process for establishing water quality objectives is more fully outlined in Principles for Preparing Water Quality Objectives in British Columbia, copies of which are available from Water Quality Section of the Water Management Branch.

Neither guidelines nor objectives which are derived from them, have any legal standing. The objectives, however, can be used to calculate allowable limits or levels for contaminants in waste discharges. These limits are set out in waste management permits and thus have legal standing. The objectives are not usually incorporated as conditions of the permit.

The definition adopted for a guideline is:

A maximum and/or a minimum value for a physical, chemical or biological characteristic of water, sediment or biota, which should not be exceeded to prevent specified detrimental effects from occurring to a water use, including aquatic life, under specified environmental conditions.

The guidelines are province-wide in application, are use-specific, and are developed for some or all of the following specific water uses:

  • Raw drinking, public water supply and food processing
  • Aquatic life and wildlife
  • Agriculture (livestock watering and irrigation)
  • Recreation and aesthetics
  • Industrial (water supplies)

The guidelines are set after considering the scientific literature, guidelines from other jurisdictions, and general conditions in British Columbia. The scientific literature gives information on the effects of toxicants on various life forms. This information is not always conclusive because it is usually based on laboratory work which, at best, only approximates actual field conditions. To compensate for this uncertainty, guidelines have built-in safety factors which are conservative but reflect natural background conditions in the province.

The site-specific water quality objectives are, in most cases, the same as guidelines. However, in some cases, such as when natural background levels exceed the guidelines, the objectives could be less stringent than the guidelines. In relatively rare instances, for example if the resource is unusually valuable or of special provincial significance, the safety factor could be increased by using objectives which are more stringent than the guidelines. Another approach in such special cases is to develop site-specific guidelines by carrying out toxicity experiments in the field. This approach is costly and time-consuming and therefore seldom used.

Guidelines are subject to review and revision as new information becomes available, or as other circumstances dictate.

The guidelines apply to the ambient raw water source before it is diverted or treated for domestic use.

The Ministry of Health regulates the quality of water for domestic use after it is treated and delivered by a water purveyor.

Guidelines relating to public health at bathing beaches are the same as those used by the Ministry of Health which regulates the recreation and aesthetic use.


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Introduction

Toluene is a colourless liquid at room temperature with a gasoline-like aroma. It occurs naturally in coal and crude oil and is found in consumer products such as paints, cosmetics, upholstery, carpet cleaners, cigarette smoke, pesticides and gasoline. In Canada, toluene is used in the production of benzene and as an octane enhancer instead of lead in gasoline refining.

Toluene can enter aquatic environments during production, usage, storage, transportation and spills. Toluene has been detected throughout North America in effluents from municipalities, industries, industrialized river basins, ground water, sediments, soil and water. It is released into the air from burning oil, gas and coal. Physical, biological and chemical processes remove toluene from all media so there is little tendency for it to accumulate in environmental compartments. Toluene can be removed from water by volatilization and biodegradation, but does not tend to hydrolyze or adsorb to sediments. It may leach into ground water if released to land. Toluene is volatile with a half-life of up to two weeks in water. The log octanol-water partition coefficient, Kow, is 2.7.

The CCME noted that the following toxicity tests (lowest value shown) from the literature were deemed as primary:

Table 2: Freshwater Toxicity Tests

Species Exposure
Duration
Age/Size Response Toxicity
mg/L
References
Rainbow Trout
Oncorhynchus mykiss
Chronic Hatch 27-d LC50 0.020 Black et al
1982
Rainbow Trout
Oncorhynchus mykiss
Chronic 4-d
post-hatch
23-d LC50 0.030 Black et al
1982
 Rainbow Trout
Oncorhynchus mykiss
Acute  — 96-h LC50 5.8 Galassi et al
1982
Leopard Frog
Rana pipiens
Chronic 4-d
post-hatch
9-d LC50 0.39 Black et al
1982
Leopard Frog
Rana pipiens
Chronic fertilization
to hatch
5-d LC50 5.1 Black et al
1982
Salamander
Ambystoma gracile
Chronic 4-d
post-hatch
9.5-d LC50 0.85 Black et al
1982
Salamander
Ambystoma gracile
Chronic fertilization
to hatch
5.5-d LC50 1.1 Black et al
1982
Coho Salmon
Oncorhynchus kisutch
Chronic Fry 40-d EC50 2.8-5.0 Moles 1981
Coho Salmon
Oncorhynchus kisutch
Acute 0.3 g 96-h LC50 5.46 Moles 1981
Water Flea
Daphnia magna
Acute 24 hours 24-h EC50
(immobility}
7.0 Galassi et al
1988
Goldfish
Carassius auratus
Chronic 1-1.5 years 30-d LC50 14.6 Brenniman
et al 1976
Goldfish
Carassius auratus  
Acute 1-1.5 years 96-h LC50 22.8 Brenniman
et al 1976
Goldfish
Carassius auratus  
Acute 13-20 cm 72-hd LC50 25.3 Brenniman
et al 1976
Goldfish
Carassius auratus  
Acute 20-80 g 48-h LC50 27.6 Brenniman
et al 1976
Guppy
Lebistes reticulatus
Acute 96-h LC50 28.2 Galassi et al
1988
Fathead minnow
Pimphales promelas
Chronic 30-35 days 8-d LC50 44.1 Hall et al
1984, 1989
Fathead minnow
Pimphales promelas
Acute 30 days 96-h LC50 18-31 Devlin et al
1982
Fathead minnow
Pimphales promelas
Acute protolarvae 96-h LC50 25-36 Devlin et al
1982
Fathead minnow
Pimphales promelas
Acute embryo 96-h LC50 55-72 Devlin et al
1982


The most sensitive freshwater species to toluene was rainbow trout, Oncorhynchus mykiss, with a 27-d LC50 of 0.020 mg/L. Coho salmon, Oncorhynchus kisutch, exhibited a weight loss after 40-d exposure to 2.8 and 5.0 mg/L of toluene. The leopard frog, Rana pipiens, had a 9.5-d LC50 of 0.39 mg/L, while the salamander, Ambystoma gracile, had a 9.5-d LC50 of 0.85 mg/L. Daphnia magna had a 24-hr EC50 of 7.0 mg/L for immobilization.

The results from static renewal testing undertaken by BC Environment in partnership with the Canadian Petroleum Producers Institute in 1999 for Daphnia magna at a nominal hardness of 100 mg/L CaCO3 are as follows:


Table 3: Daphnia magna Data

Bioassay
mg/L
Daphnia magna 21-d LC25
15.0
Daphnia magna 21-d LOEC
36.8
Daphnia magna 21-d NOEC
8.7


The CCME classified the following as secondary. These secondary studies included two separate studies conducted independently and which had 48-h EC50 values for immobilization of Daphnia magna of 11.5 and 14.9 mg/L. Another secondary study had a 72-h EC50 of 12.5 mg/L for growth inhibition for the green algae, Selenastrum capricornutum. In marine water, sensitive species included the coho salmon, Oncorhynchus kisutch, that exhibited avoidance behaviour at 1.4 to 1.8 mg/L, pink salmon with a 24-h LC50 of 5.4 mg/L and adult bay shrimp, Crago franciscorum, with a 96-h LC50 of 4.3 mg/L.


Table 4: Marine Toxicity Tests

Species Exposure
Duration
Age/Size Response Toxicity
mg/L
References
Data Quality
Bay Shrimp
Crago franciscorum
Acute Adult 96-h LC50 4.3 Benville and Korn, 1977
secondary
Pink Salmon
Oncorhynchus gorbuscha
Acute 1-2 g 24-h LC50 5.4 Thomas and Rice, 1979
secondary
Pink Salmon
Oncorhynchus gorbuscha
Acute Fry 96-h LC50 6.52 Rice and Thomas, 1989
primary
Pink Salmon
Oncorhynchus gorbuscha
Acute Fry 48-h LC50 7.76 Rice and Thomas, 1989
primary
Sheepshead Minnow
Cyprinodon variegatus
Acute Juvenile 96-h LC50 13.0 Ward et al, 1981 primary
Kelp Shrimp
Eualus suckleyi
Acute 1 g 96-h LC50 19.8 Rice and Thomas, 1989
primary
Shore Crab
Hemigrapus nudus
Chronic 8-d LC50 23.5-52.7 Gharrett and
Rice, 1987
primary


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Recommended Guidelines

These guidelines are based on a review of the technical background information used to prepare the CCME Water Quality Guidelines for Toluene, July 1995 update, as well as recent information from the literature and other sources. The guidelines have been revised where appropriate to suit BC conditions, and are summarized in Table 1.


1. DRINKING WATER SUPPLY

An aesthetic objective of 0.024 mg/L for toluene in drinking water has been recommended by the Federal-Provincial Subcommittee on Drinking Water, Health Canada, 1993 and is adopted for ambient conditions.


Rationale

This concentration yields no objectionable taste or smell and no adverse health effects. Without treatment prior to entering a water distribution system, toluene concentrations will change little from ambient concentrations, especially when the time from withdrawal to use is short. Therefore, the recommended concentration for water distribution systems will be the ambient water quality concentration for toluene.


2. FRESHWATER AQUATIC LIFE

The maximum concentration of toluene should not exceed the BC guideline of 0.039 mg/L. This guideline has been revised from the CCME guideline of 0.002 mg/L.


Rationale

We found that the data quality from the researchers was considered by CCME to be as satisfactory, ranked primary data, based on the requirements of the CCME Protocol. However, using the same Protocol, we have applied professional judgement since we have serious concerns about the results for the species used in guideline development by CCME.

The CCME guideline was established using the most sensitive species for an early life stage chronic test for rainbow trout, Oncorhynchus mykiss. The results are in a 1982 research paper from the University of Kentucky that is not widely available. This 27-d LC50 was 0.02 mg/L, twenty times more sensitive than reported by the same authors for the leopard frog, Rana pipiens, or forty times more sensitive than the next most sensitive species that they reported, a salamander, Ambystoma gracile. In fact, the most sensitive species reported by independent researchers was for coho salmon, Oncorhynchus kisutch, with a 40-d weight decrease at 2.8 mg/L toluene, which is 140 times higher than the study used by CCME. All other authors report even higher concentrations for other species.

The difficulty in testing toluene due to its volatility can lead to problems in getting accurate toxicity measurements. For this reason, we believe that results from a flow-through test with constant replacement are the ideal. Unfortunately, the results in the literature do not always meet this ideal.

Since the rainbow trout, Oncorhynchus mykiss, study that reported the 27-d LC50 of 0.02 mg/L was a flow-through test, we examined the acute to chronic ratios where available for the same species. We know on the basis of the CCME Protocol that the acute/chronic ratio should be about 2:1 for most species since the application factor recommended by CCME is 0.05 for acute data and 0.10 for chronic data. The actual ratios calculated from data in the literature were:

Table 5: Acute to Chronic Ratios

Species Age/Size Toxicity
Test
Toxicity
mg/L
Ratio References
Data Quality
Guppy
Lebistes reticulatus
96-h LC50
Static
28.2 0.413:1 Galassi et al,
1988 primary
2-3
months
14-d LC50
Static
68.3 Kuneman, 1981 secondary
Fathead Minnow
Pimphales promelas
30 days 96-h LC50
Flow Thru
22.0 0.498:1 Devlin et al, 1982 primary
30-35 days 8-d LC50
Flow Thru
44.1 Hall et al, 1984 primary
Green Alga
Chlorella vulgaris
3-h EC50
207 0.845:1 Hutchison et al, 1980 secondary
10-d EC50 245 Rice and Thomas, 1989
primary
Coho Salmon
Oncohynchus kisutch
 
0.3 g 96-h LC50
Flow Thru
5.46 1.400:1 Moles, 1981 primary
Fry 40-d EC
(weight)
Flow Thru
3.90 Moles, 1981 primary
Goldfish
Carassius auratus
 
1-1.5 years 96-h LC50
Flow Thru
22.8  1.561:1 Brennimen
et al, 1976
primary
1-1.5 years 30-d LC50
Flow Thru
14.6 Brennimen
et al, 1976
primary
Water Flea
Daphnia magna
 
24 hours 24-h LC50
Static
7.00  1.866:1 Galassi et al,
1988 primary
24 hours 16-d LC50
3.75 Hermens et al,
1992 secondary
Fathead Minnow
Pimphales promelas
  
 Larvae  96-h LC50
Flow Thru
17.03 Marchini et al,
1992 primary
7-d LC50
Flow Thru
9.39 1.813:1
7-d (growth)
Flow Thru
10.6 1.607:1
7-d (biomass)
Flow Thru
7.62 2.235:1
 Rainbow Trout
Oncorhynchus mykiss
96-h LC50
Static
5.8  290:1 Galassi et al,
1988 primary
4 days 27-d LC50
Flow Thru
0.02 Black et al, 1982 primary


As can be seen, the ratio for all species except the rainbow trout study are in the 0.4:1 to 2.2:1 range, while that for rainbow trout, at 290:1 is over 100 times greater than any other species or study. This can be explained by either of two possibilities: the acute data used are too high or the chronic data from the study in question are too low. We tend to believe that the latter is the case, since rainbow trout and coho salmon are both salmonids and, although one would not expect identical results, one would expect that the toxicity would be similar. This is the case for the acute data, 5.8 and 5.46 mg/L, respectively, but not for the chronic data, even though the acute tests were static, but primary, data.

The chronic data themselves seem quite low in comparison to other work. The principle investigators have published toxicity data for other variables that we have questioned in the past. These include data for copper which were reported as causing skeletal defects in the range from 1-5 µg/L but in the same paper, these researchers proposed a copper guideline at the 3-5 µg/L level. We find this interesting since the authors did not suggest that a guideline was needed to protect the most sensitive effect levels and that no safety factor was needed.

Although the research for the critical paper was reported in 1982, there have been no further studies reported in the literature on rainbow trout that yielded comparable results. This in itself seems strange. BC Environment, with the help of the Canadian Petroleum Producers Institute (CPPI), arranged for tests to be done through Environment Canada on early life stage rainbow trout, Oncorhynchus mykiss, and Daphnia magna. The tests unfortunately were not flow-through in nature, but static renewal tests and did not yield results for rainbow trout that we deemed to be helpful in establishing a guideline. The results for testing Daphnia magna are presented above.

We therefore question the validity of the rainbow trout chronic data. This is based on its low concentration relative to other work, the extremely high ratio produced in relation to acute studies, which seem to be of the right order-of-magnitude, and the fact that no other researchers have reproduced the results in the last twenty years. Of interest is the fact the US EPA has an alert level of 17.5 mg/L, while Quebec has a chronic guideline of 0.026 mg/L and an acute guideline of 0.58 mg/L.

In developing their guideline, the CCME applied a safety factor of 10:1. This was appropriate since toluene has high volatility, the guideline was based on a chronic study, toluene has low bioaccumulation potential and would not be expected to remain in the environment for prolonged periods of time. The half-life is up to two weeks in water. The LOEC/NOEC ratio for freshwater aquatic life, fathead minnow, is low, 1.5:1.

We therefore used the next most sensitive species from the literature, the leopard frog, Rana pipiens, which had a 9.5-d LC50 of 0.39 mg/L and applied the safety factor of 10:1 to produce a guideline of 0.039 mg/L. Although the research was performed by the same researchers as produced the data for rainbow trout, we do not have as much information available (e.g., no acute/chronic ratio) on which to refute these data which are still approximately one order of magnitude lower than the next independent tests. We have no acute to chronic ratios, data from no other researchers on the leopard frog, or data for other similar species or data for other chemical compounds that might help us to validate the data. Therefore, we use the Ministry's precautionary principle in accepting these data at this time. By so doing, this yields a guideline of 0.039 mg/L that is about twice the level of concern raised for rainbow trout.


3.0 MARINE AND ESTUARINE LIFE

The maximum concentration of toluene should not exceed 0.33 mg/L. This guideline has been revised from the CCME guideline of 0.21 mg/L.


Rationale

The critical study used by the CCME to derive the guideline was classified as secondary data. In BC, we eliminated this study for determining the BC guideline, since the concentrations reported for the test were not measured but were estimated. The next lowest critical study with measured values had a 96-h LC50 of 6.52 mg/L for pink salmon, Oncorhynchus gorbuscha.

We maintained the safety factor used by CCME of 20:1 for BC based on not having a chronic study or a LOEC to NOEC ratio. Although toluene has a relatively short half-life and low potential to bioaccumulate, a safety factor of 0.05 was applied to the reference level for three reasons:

  • the reference level was determined by acute rather than chronic toxicity testing,
  • a LOEC to NOEC ratio was not available for conversion of the data, and
  • there were few available studies on marine organisms.


4. CROP IRRIGATION

No water quality guideline for this use is recommended, as there are insufficient data on the adverse effects of toluene in irrigation water.


5. LIVESTOCK WATERING

Guidelines for livestock watering for BC are the same as for CCME, 0.024 mg/L.


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Application of the Guidelines

Toluene is a very volatile substance. The water quality guidelines recommended in this document are based primarily on controlled, laboratory bioassays that do not account for factors that may modify the toxicity of toluene in the field.


Setting Water Quality Objectives

Care must be exercised when the water quality guidelines are applied to assess environmental impacts of toluene, since there will be situations where toluene concentrations are continuously renewed, e.g., discharge from an industrial operation, or with the potential for only a minimal amount of volatilization e.g., under ice cover. In these types of situations, a site-specific study should be undertaken and appropriate site-specific water quality objectives developed based on species present and actual toluene persistence and concentrations.

In many cases, water quality objectives will be the same as the guidelines. When concentrations of toluene in developed waterbodies are constantly maintained due to a continuous source or an environmental condition that prevents its degradation, then water quality objectives that are more stringent than the recommended guidelines may be justified. In some cases, socioeconomic or other factors may justify objectives that are less stringent than the guidelines. Site-specific impact studies would be required in such cases.

Methods (e.g., water effects ratio, resident species toxicity in the field, etc.) are available to adapt the recommended guidelines to a given site by considering these factors. Where necessary, these methods can be employed to set site-specific water quality objectives. Because these approaches are costly and time consuming, they are seldom used.


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References

  1. Benville, P. and S. Korn. 1977. The Acute toxicity of Six Monocyclic Aromatic Crude Oil Components to Striped Bass (Morone saxatilis) and Bay Shrimp (Crago franciscorum). Calif. Fish and Game 63(4): 204-209.
  2. Black, J., W. Birge, W. McDonnell, A. Westerman, B. Ramey and D. Bruser. 1982. The Aquatic toxicity of organic Compounds to Embryo-Larval Stages of Fish and Amphibians. Research Report No. 133. Water Resources Research Institute, University of Kentucky.
  3. Brenniman, G., R. Hartung and W. Weber. 1976. A Continuous Flow Bioassay Method to Evaluate the Effects of Outboard Motor Exhausts and Selected Aromatic Toxicants on Fish. Water Res. 10: 165-169.
  4. Devlin, E., J. Brammer and R. Puyear. 1982. Acute Toxicity of Toluene to Three Age Groups of Fathead Minnows (Pimephales promelas). Bull. Environ. Contam. Toxicol. 29: 12-17.
  5. Galassi, S., M. Mingazzini, L. Vigano, D. Cesareo and M. L. Tosato. 1988. Approaches to Modeling Toxic Responses of Aquatic Organisms to Aromatic Hydrocarbons. Ecotoxicol. Environ. Saf. 16, 158-169.
  6. Gharrett, J. and S. Rice. 1987. Influence of Simulated Tidal Cycles on Aromatic Hydrocarbon Uptake and Elimination by the Shore Crab, Hemigrapus nudus. Marine Biology 95: 365-370.
  7. Hall, L., L. Kier and G. Phipps. 1984. Structure-Activity Relationship Studies on the Toxicities of Benzene Derivatives. I. An Additivity Model. Environ. Toxicol. Chem. 3: 355-365.
  8. Hall, L., E. Maynard and L. Kier. 1989. QSAR Investigation of Benzene Toxicity to Fathead Minnow Using Molecular Connectivity. Environ. Toxicol. Chem. 8(9): 783-789.
  9. Hermens, J., H. Canton and R. DeJong. 1984. Quantitative Structure Activity Relationships and Toxicity Studies of Mixtures of Chemicals with Anesthetic Potency: Acute Lethal and Sub-Lethal Toxicity to the Daphnia magna. Aquatic Toxicol. 5: 143-154.
  10. Hutchison, T. C., J. A. Hellebust, D. Tam, D. MacKay, R. A. Mascarenhas and W. Y. Shiu. 1980. The Correlation of the Toxicity to Algae of Hydrocarbons and Halogenated Hydrocarbons with Their Physical-Chemical Properties. Environmental Science and Research. 16: 577-586.
  11. Kauss, P. B., and T. C. Hutchinson. 1975. The Effects of Water Soluble Petroleum Components on the Growth of Chlorella vulgaris Beijerinck. Environ. Pollut. 9: 157-174.
  12. Konemann, H. 1981. Fish Toxicity Tests with Mixtures of More than Two Chemicals: A Proposal for a Quantitative Approach and Experimental Results. Toxicology 19: 229-238.
  13. Marchini, S., M. Tosato, T. Norberg-King, D. Hammermeister and M. Hoglund. 1992. Lethal and Sub-Lethal Toxicity of Benzene Derivatives to Fathead Minnow, Using a Short-term Test. Environ. Toxicol. Chem. 11(2): 187-195.
  14. Moles, A. 1981. Reduced Growth of Coho Salmon Fry Exposed to Two Petroleum Components, Toluene and Naphthalene in Freshwater. Trans. Am. Fish. Soc. 110: 430-436.
  15. Rice, S. and R. Thomas. 1989. Effect of Pre-Treatment Exposures of Toluene or Naphthalene on the Tolerance of Pink Salmon (Oncorhynchus gorbususcha) and Kelp Shrimp (Eualis suckleyi). Comp. Biochem. Physiol. C. 289-293.
  16. Thomas, R. and S. Rice. 1979. The Effect of Exposure Temperatures on Oxygen Consumption and Opercular Breathing Rates of Pink Salmon Fry to Toluene, Naphthalene, and Water-Soluble Fractions of Cook Inlet Crude Oil and No. 2 Fuel Oil. Marine Pollution: Functional responses. Academic Press, Inc, New York. pp 39-52.
  17. Ward, G. and P. Parrish. 1981. Early Life Stage Toxicity Tests with Saltwater Fish: Effects of Eight Chemicals on Survival, Growth, and Development of Sheepshead Minnows (Cyprinodon variegatus). J. Toxicol. Environ. Health. 8: 225-240.


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