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BC Env Chlorine Waterqualityguideline Technical

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WATER QUALITY GUIDELINE SERIES

Chlorine Water Quality Guidelines (Reformatted Guideline from


1989)

Technical Appendix

Ministry of Environment and Climate Change Strategy


Water Protection & Sustainability Branch

No . W QG -1 0
The Water Quality Guideline Series is a collection of British Columbia (B.C.) Ministry of Environment and Climate
Change Strategy water quality guidelines. Water quality guidelines are developed to protect a variety of water
values and uses: aquatic life, drinking water sources, recreation, livestock watering, irrigation, and wildlife. The
Water Quality Guideline Series focuses on publishing water quality guideline technical reports and guideline
summaries using the best available science to aid in the management of B.C.’s water resources. For additional
information on B.C.’s approved water quality parameter specific guidelines, visit:

https://www2.gov.bc.ca/gov/content/environment/air-land-water/water/water-quality/water-quality-
guidelines/approved-water-quality-guidelines

ISBN: 0-7726-1603-5

Document citation:
B.C. Ministry of Environment and Climate Change Strategy 2021. Chlorine Water Quality Guidelines (reformatted
from: British Columbia Ministry of Environments and Parks, 1989. Water quality criteria for chlorine). Water
Quality Guideline Series, WQG-10. Prov. B.C., Victoria B.C.

Original Author:
Singleton, Howard J.

Notes on Reformatted Version:


Sections of this report on industrial water use, drinking water and recreation have been removed. B.C. adopts
Health Canada drinking water and recreation guidelines and no longer develops or supports guidelines for
industrial water use.
Cover Photograph:
Location: Upper Dean River, B.C.
Acknowledgements
I would like to express my sincere appreciation to those individuals who provided valuable assistance in the
preparation and review of this document. They include:
Mr. M.D. Nassichuk and Mr. S. Samis of Fisheries and Oceans.
Mr. A. David of the Environmental Protection Service, Environment Canada. Dr. H.M. Richards, Provincial Health
Officer of the Ministry of Health.
Dr. M.J.R. Clark, Mr. R. Grace, Mr. L. McDonald, Mr. B. Moore, Mr. M.W. Macfarlane, Dr. J.E. Bryan, and 8. Carmichael
of the Waste Management Branch, Ministry of Environment.
Mr. R.J. Rocchini and Mr. L.W. Pommen of the Resource Quality Section, Water Management Branch, Ministry of
Environment.
Ms. L. Thomas, Ms. S. Kent, and Ms. D. Larkin, typists, Water Management Branch, Ministry of Environment.

Disclaimer: The use of any trade, firm, or corporation names in this publication is for the information and convenience of
the reader. Such use does not constitute an official endorsement or approval by the Government of British Columbia of any
product or service to the exclusion of any others that may also be suitable. Contents of this report are presented for
discussion purposes only. Funding assistance does not imply endorsement of any statements or information contained
herein by the Government of British Columbia.

WATER QUALITY GUIDELINE SERIES No. WQG-10 i


Contents
1. INTRODUCTION........................................................................................................................................ 1
2. FORMS AND TRANSFORMATIONS ........................................................................................................... 1
2.1 Chlorine in Freshwater..................................................................................................................... 1
2.2 Chlorine in Seawater ........................................................................................................................ 2
2.3 Analytical Techniques ...................................................................................................................... 3
3. OCCURRENCE IN THE ENVIRONMENT ..................................................................................................... 4
3.1 Natural Sources ................................................................................................................................ 4
3.2 Anthropogenic Sources .................................................................................................................... 4
3.2.1 Municipal and Domestic Uses .................................................................................................. 4
3.2.2 Industrial Uses .......................................................................................................................... 5
3.3 Chlorine Requirements for Domestic and Industrial Waters........................................................... 6
3.4 Residual Chlorine Concentrations in Receiving Waters ................................................................... 6
3.5 Concentrations in Biological Tissues ................................................................................................ 7
4. AQUATIC LIFE ........................................................................................................................................... 7
4.1 Mode of Toxic Action ....................................................................................................................... 7
4.2 Effects on Algae ............................................................................................................................... 8
4.2.1 Freshwater Algae ..................................................................................................................... 8
4.2.2 Marine and Estuarine Algae ..................................................................................................... 9
4.3 Effects on Aquatic Macrophytes .................................................................................................... 10
4.4 Effects on Invertebrates................................................................................................................. 10
4.4.1 Freshwater Invertebrates ...................................................................................................... 10
4.4.1.1 Acute Toxicity .............................................................................................................. 10
4.4.1.2 Chronic Toxicity ........................................................................................................... 11
4.4.2 Marine Invertebrates ............................................................................................................. 12
4.4.2.1 Acute Toxicity .............................................................................................................. 12
4.4.2.2 Chronic Toxicity ........................................................................................................... 13
4.5 Effects on Fish ................................................................................................................................ 13
4.5.1 Freshwater Fish ...................................................................................................................... 13
4.5.1.1 Acute Toxicity .............................................................................................................. 13
4.5.1.2 Chronic Toxicity ........................................................................................................... 15
4.5.2 Marine Fish............................................................................................................................. 15
4.5.2.1 Acute Toxicity .............................................................................................................. 16
4.5.2.2 Chronic Toxicity ........................................................................................................... 16
4.6 Criteria from the Literature ........................................................................................................... 17
4.6.1 Continuous Exposure ............................................................................................................. 17
4.6.2 Intermittent Exposure ............................................................................................................ 18
4.7 Recommended Criteria .................................................................................................................. 19
4.7.1 Freshwater Aquatic Life ......................................................................................................... 19
4.7.1.1 Continuous Exposure .................................................................................................. 19
4.7.1.2 Controlled Intermittent Exposures ............................................................................. 19
4.7.2 Marine and Estuarine Aquatic Life ......................................................................................... 20
4.7.2.1 Continuous Exposure .................................................................................................. 20
4.7.2.2 Controlled Intermittent Exposures ............................................................................. 20
4.7.3 Application of Criteria ............................................................................................................ 20
4.7.4 Rationale ................................................................................................................................ 22
4.7.4.1 Averaging Periods ....................................................................................................... 22
4.7.4.2 Continuous Exposure Criteria ..................................................................................... 23
4.7.4.3 Intermittent Exposure Criteria .................................................................................... 23
WATER QUALITY GUIDELINE SERIES No. WQG-10 ii
5. OTHER WATER-USE CATEGORIES .......................................................................................................... 24
5.1 Wildlife and Livestock Watering .................................................................................................... 25
5.2 Irrigation Water ............................................................................................................................. 25
6. RESEARCH AND DEVELOPMENT NEEDS................................................................................................. 27
7. REFERENCES ........................................................................................................................................... 59

WATER QUALITY GUIDELINE SERIES No. WQG-10 iii


LIST OF TABLES

Table 1. Chlorine requirements for various waters (White, 1972, as cited in Pierce, 1978; Palin, 1974, as
cited in Pierce, 1978). ................................................................................................................................. 28
Table 2. Summary of Toxicity of Chlorine to Freshwater Organisms ......................................................... 29
Table 2a. Toxicity of Chlorine to Freshwater Organisms, Not Included in Review by Mattice and Zittel
(1976) .......................................................................................................................................................... 36
Table 3. Summary of Data on Toxicity of Chlorine to Marine Organisms................................................... 41
Table 3a. Toxicity of Chlorine to Marine Organisms, Not Included in Review by Mattice and Zittel (1976)
.................................................................................................................................................................... 46
Table 4. Chlorine Criteria for Freshwater Aquatic Life ............................................................................... 53
Table 5. Chlorine Criteria for Marine Aquatic Life ...................................................................................... 56

WATER QUALITY GUIDELINE SERIES No. WQG-10 iv


LIST OF FIGURES

Figure 1. Toxicity of Chlorine to Freshwater Organisms ............................................................................. 57


Figure 2. Toxicity of Chlorine to Marine Organisms ................................................................................... 58

WATER QUALITY GUIDELINE SERIES No. WQG-10 v


1. INTRODUCTION
This document discusses the effects of total residual chlorine on the various water use categories which
include drinking water, aquatic life, wildlife, livestock watering, irrigation, recreation and aesthetics, and
industrial water supplies. Halogenated organic compounds, including those produced by oxidation of
organic matter by residual chlorine, are beyond the scope of this report and will be addressed in separate
criteria documents published in this series. It is “total residual chlorine”, as defined in Section 2, upon
which this document will focus.
Aquatic organisms are particularly sensitive to residual chlorine, and therefore a large portion of this
document focuses on the toxicity of residual chlorine to aquatic life. Because of the extensive amount of
literature on residual chlorine, much of the information presented in this document has been extracted
from recent reviews documenting the numerous toxicological studies pertaining to this contaminant. The
purpose of this document is not to re-review the extensive amount of original material already addressed
in recent publications, but instead, to focus on the most applicable information which could be used to
formulate appropriate criteria for British Columbia waters.
Where applicable, or where sufficient information exists, criteria are recommended to protect water users
from the deleterious effects of residual chlorine. As part of this criteria development process, water
quality standards, objectives, and criteria and accompanying rationales from other jurisdictions are
reviewed and their suitability for British Columbia waters are considered.

2. FORMS AND TRANSFORMATIONS

2.1 Chlorine in Freshwater


Chlorine is a powerful oxidizing agent with a high solubility in water. When elemental chlorine (Cl2) or
hypochlorite compounds (e.g. calcium hypochlorite) are added to freshwater at about pH 5 or greater,
chlorine hydrolyzes rapidly and completely to form hypochlorous acid according to the reaction:
Cl2 + H2O → HCl + HOCl

The HOCl is a weak acid and partially dissociates to form hypochlorite ions which are in equilibrium with
HOCl according to the equation:
HOCl ⇌ H+ + OC−

That portion of chlorine present as HOCl and OCl− in aqueous solution is referred to as “free available
chlorine” which is often abbreviated to “free chlorine”. The ratio between HOCl and OCl − is primarily a
function of pH with a dissociation constant of 3.3 × 10−8 at 20°C (McKee and Wolf, 1963). For example, 96
percent of the free available chlorine is present as HOCl at pH 6, 75 percent at pH 7, 22 percent at pH 8,
and only about 3 percent at pH 9. The normal temperature range of ambient water affects this ratio only
slightly (Alabaster and Lloyd, 1982; McKee and Wolf, 1963).
If chlorine is added to water which contains ammonia, such as sewage effluent, then the combination will
form chloramines (mono-, di-, tri-), nitrogenous compounds (e.g., N-chloramides), or a mixture of these
compounds (Alabaster and Lloyd, 1982; Pierce, 1978; Brungs, 1973). The relative concentrations of these
compounds are dependent primarily upon the initial chlorine: ammonia ratio and the pH of the solution
(Pierce, 1978). The portion of the chlorine that is present as chloramines (with the exception of
trichloramine) or combined with other nitrogenous compounds (with an N-Cl link) is referred to as
“combined available chlorine” (Alabaster and Lloyd, 1982; Pierce, 1978; Brungs, 1973).

WATER QUALITY GUIDELINE SERIES No. WQG-10 1


“Total residual chlorine” (often abbreviated to “residual chlorine” or simply “TRC” and sometimes referred
to as “total available chlorine”) is the sum of the “free available chlorine” plus the “combined available
chlorine”. This includes all the forms of chlorine which are able to act as an oxidant (Alabaster and Lloyd,
1982; Pierce, 1978; Brungs, 1973).
Initial loss of chlorine disinfectant is due to reaction with easily oxidized organic compounds, and with
readily oxidized inorganic ions including ferrous ion, sulphide, nitrite, and other reducing agents. By
definition, chlorine demand is the sum of the reducing agents available to react with free available
chlorine in a given time. After the demand is satisfied, combined available chlorine is formed that is
primarily monochloramine (NH2Cl), as follows:

HOCl + NH3 ⇌ NH2Cl + H2O

As additional chlorine is added beyond that needed to react with ammonia-nitrogen (5 mg/L for each 1
mg/L of NH3−N), dichloramine (NHCl2) begins to form and decompose as follows:

HOCl + NH2Cl ⇌ NHCl2 + H2O

This decomposition results in the loss of residual combined available chlorine, until breakpoint
chlorination occurs (near 8 mg/L Cl 2 for each mg N) as the ammonia present in the combined available
chlorine is oxidized to N 2 and the chlorine becomes chloride (Cl−) as follows:

2NHCl2 + H2O ⇌ N2 + H3+ + 3Cl− + HOCl

The breakpoint represents the minimal concentration of both residual chlorine and ammonia. Beyond the
breakpoint, excess free available chlorine remains in solution except as it is consumed by difficult to
oxidize organic and inorganic compounds (Pierce, 1978; Johnson, 1978). Tri chloramine (NCl3), or nitrogen
trichloride as it is sometimes called, may be formed beyond breakpoint by reaction of the excess
hypochlorous acid with dichloramine as follows:

HOCl + NHCl2 ⇌ NHCl3 + H2O

As noted in Section 1, halogenated organic compounds, including those produced by oxidation of organic
matter by residual chlorine are beyond the scope of this report and will be addressed in separate criteria
documents published in this series.

2.2 Chlorine in Seawater


Chlorine reacts differently in seawater than in freshwater because of the relatively high concentrations
of bromide (67 mg/L Br−) naturally present in seawater (salinity of 35 ppt) compared to the amount of
chlorine (0.5 to 10 mg/L) typically introduced from anthropogenic sources (Pierce, 1978). At pH 8 (typical
pH of seawater), the addition of chlorine to seawater, or any water high in bromide, results in the rapid
formation of hypobromous acid (HOBr) in equilibrium with hypobromite ions (OBr−) and all the chlorine
would be reduced to chloride ions (Cl−) according to the reactions:

HOCl +Br− ⇌ HOBr + Cl−


OCl− + Br− ⇌ OBr− + Cl−
HOBr− ⇌ OBr− + H+

WATER QUALITY GUIDELINE SERIES No. WQG-10 2


According to Pierce (1978), both HOBr and OBr− are unstable and undergo further decay to bromate
(BrO3−) and bromide ions (Br−) as follows:

2HOBr ⇌ 2H+ + 2 Br− + O2


2OBr− ⇌ 2Br− + O2
3HOBr ⇌ 3H+ + 2Br− + BrO3−
30Br− ⇌ 2Br− + BrO3−

If ammonia is present in the chlorinated seawater, then the hypobromous acid will react with the
ammonia to form bromamines (mono-, di-, tri-) as follows:
HOBr + NH3 ⇌ NH 2 Br + H2O monobromamine
HOBr + NH2Br ⇌ NHBr2 + H2O dibromamine
HOBr + NHBr2 ⇌NBr3 + H2O tribromamine

The relative concentrations of mono-, di-, and tribromamines are dependent upon the ammonia:bromide
ratio and the pH of the solution. Monobromamine formation is favoured by high ammonia:bromide ratio
at alkaline pH. Dibromamine formation is favoured at pH 6 to 9 range with ammonia:bromide ratio of 5
to 20. Tribromamine formation is favoured in more acid solutions (Pierce, 1978).
Like aqueous chlorine, aqueous bromine will participate in a breakpoint reaction with ammonia as follows:
3HOBr + 2NH3 → N2 + 3H2O + 3Br− + 3H+
30Br− + 2NH3 → N2 + 3H2O + 3Br−

To indicate that bromine is involved in the reaction when chlorine is added to seawater, the term
“chlorine-produced oxidants”, often abbreviated to “CPO”, is used to refer to the sum of these oxidative
products in seawater (U.S. EPA, 1985). Thus, this term will be used to describe the seawater data
presented herein.
Similar to reactions with chlorine, bromine can also participate in the oxidation of organic matter to form
brominated organic compounds. As noted in Section 1, halogenated organic compounds, including those
produced by oxidation of organic matter by the introduction of residual chlorine, will be addressed in
separate criteria documents published in this series.

2.3 Analytical Techniques


While there are a number of analytical tests for aqueous chlorine and its inorganic products, a review of
the literature indicated that it is generally agreed that the amperometric titration technique is the
preferred analytical method. The American Public Health Association (APHA), the American Water Works
Association (AWWA), and the Water Pollution Control Federation (WPCF) (1985) state that for the
measurement of TRC (or CPO) in natural or treated waters the amperometric method is the method of
choice because it provides the greatest sensitivity and is not subject to interference from colour, turbidity,
iron, manganese or nitrite nitrogen.
For toxicological concerns, it is important that the method measures TRC (in freshwater) or CPO (in
seawater) and not just one or more components, such as free, but not combined chlorine. Furthermore,
because of the reactivity of chlorine and the inability to preserve the sample adequately, the
measurement must be performed on-site, immediately after sample collection. Given a portable power
supply, amperometric titration can be performed in the field; however, APHA et al. (1985) state that this
technique requires a higher degree of skill and care than the colourimetric methods.

WATER QUALITY GUIDELINE SERIES No. WQG-10 3


Improvements to amperometric titration techniques for TRC (or CPO) have increased the reliability and
sensitivity of the measurements. For example, Marinenko et al. (1976) developed an amperometer with
internal calibration which improved the sensitivity from a few tenths of a mg/L to a few µg/L of TRC.
Stockmeier et al. (1987) modified the amperometric back-titration technique by using a more diluted
iodine titrant solution, and by using a microburette (0.01 ml divisions) with a screw advance device
allowing continuous control of titrant delivery within a few microlitres. The delivery tip of the
microburette is immersed in the titration solution and designed so that unintended diffusion of the titrant
into the solution is negligible. This eliminates the errors associated with estimating the volume of discrete
droplets.
A number of toxicological studies (Arthur and Eaton, 1971; Latimer et al., 1975; Dinnel et al., 1981; Roberts
et al., 1975; Larson, Hutchins, and Lamperti, 1977; Larson, Hutchins, and Schlesinger, 1977; Stober et al.,
1980; Thatcher et al., 1976) which involve the measurement of TRC, CPO or their components by
amperometric titration reported that detection levels as low as 0.5 to 2 µg/L have been attained.

3. OCCURRENCE IN THE ENVIRONMENT

3.1 Natural Sources


Not to be confused with chlorides which are ubiquitous throughout the environment and present in
almost all natural waters, chlorine in its “free available” form (Section 2.1) does not occur naturally except
under unique circumstances. According to Duce (1969, as cited in U.S. EPA, 1981) and the National
Research Council (1976, as cited in U.S. EPA, 1981, 1986) there are data indicating that chlorine is formed
in the stratosphere by the action of ozone on aqueous aerosol particles of chloride released to the
atmosphere from ocean spray, volcanoes, and forest fires. However, it is doubtful that this natural source
of chlorine would have a measurable effect on ambient waters. For the purpose of this document, it is
assumed that any total residual chlorine measured in ambient waters is the product of anthropogenic
activities which are discussed in the following section.

3.2 Anthropogenic Sources


Chlorine is produced in British Columbia through the electrolytic decomposition of seawater. The major
producer in British Columbia is Canadian Occidental Petroleum with plants located in Vancouver, Harmac,
and Squamish. Combined, these plants have the capacity to produce up to 237 kilotonnes of chlorine per
year which is about 15 to 20 percent of the national production level (Environment Canada, 1984).

3.2.1 Municipal and Domestic Uses


The primary municipal uses of chlorine include the disinfection of drinking water supplies, sewage
treatment, and swimming pool treatment. As a disinfectant, the bactericidal properties of chlorine are
well known and it has proven to be an effective agent for destroying or deactivating disease-producing
organisms (APHA, AWWA, and WPCF, 1985). A secondary benefit of chlorine is the overall improvement
of water quality by controlling nuisance organisms, reducing taste and odour, removing colour, iron and
manganese, and destroying hydrogen sulphide and cyanides (Pierce, 1978). These multi-purpose
treatment capabilities of chlorine are due to its powerful oxidizing property.
For domestic uses, there are a wide range of commercial products available with chlorine as the active
ingredient for cleaning, disinfecting, and bleaching in the household, and for disinfection and algae control
in private swimming pools.

WATER QUALITY GUIDELINE SERIES No. WQG-10 4


Since most of the chlorine used for domestic or municipal purposes enters the aquatic environment via
municipal sewers which contain ammonia, almost all of the total residual chlorine discharged is in the
“combined available” form (see Section 2).

3.2.2 Industrial Uses


Chlorine has a wide variety of industrial uses throughout the Province. Based on the total quantities of
chlorine used for various purposes across Canada (Pierce, 1978), it is estimated that industry accounts for
over 90 percent of the chorine used in British Columbia for the following purposes:
i) disinfection
ii) bleaching
iii) control of nuisance organisms
iv) oxidation of waste products
v) manufacture of chlorinated and non-chlorinated products.
As a disinfectant, chlorine is used in certain food and beverage processing industries such as fruit and
vegetable processing, cottage cheese processing, poultry processing, shellfish processing, fish packing,
and the brewing and malting industries (Pierce, 1978). However, in some food processing industries,
chlorine may cause undesirable tastes in canned or frozen products, or may cause corrosion in cans
(McKee and Wolf, 1963).
For bleaching purposes, chlorine is used in the pulp and paper industry and textile industry to remove
wanted colour from the products. Chlorine dioxide, a bleaching and delignifying agent, is produced on-
site in some pulpmills and does not dissociate or form chloramines or nitrogenous organic compounds
but instead it is reduced to chlorite (Pierce, 1978). Chlorine is also used for its bleaching property to
remove intense colour from wastewaters such as by the textile industry (Pierce, 1978).
For the control of nuisance organisms such as slime growths, barnacles, mussels, and algae, chlorine is
used in the cooling water systems of industrial facilities to prevent biofouling. This may be accomplished
by a continuous low dose of chlorine to the intake water or by intermittent higher doses (Pierce, 1978;
Mattice and Zittel, 1976). Chlorine is also used in the processing systems of pulp and paper mills to prevent
slime growths from developing (Pierce, 1978).
Chlorine is used in the treatment of some industrial wastewaters to destroy certain harmful waste
products by oxidation (Pierce, 1978). Examples of this form of treatment are as follows:
i) alkaline chlorination which is used in the mining and smelting industry to destroy cyanides;
ii) chloroxidation for phenol removal in wastewaters from coking operations, petrochemical
refining, plastics manufacture, steel mills, foundries, and various chemical industries;
iii) oxidation of hydrogen sulphide to form sulphates in pulp and paper mill and petroleum
refinery effluents; and
iv) oxidation of iron and manganese to form precipitates.
Chlorine is used in the manufacture of a vast array of organochlorine products such as polymers used in
paints, adhesives, packaging films, synthetic textiles, laminates, wire and cable covering, hoses, belting,
and fire-resistant materials, and in solvents, pesticides, and aerosol propellants.
Although chlorine is used widely in industry, as outlined above, only a few industries are likely to be a
source of residual chlorine entering the aquatic environment. According to McKee and Wolf (1963), the
industrial processes most likely to contain residual chlorine are those employing bleaching operations
such as textile mills or paper pulping operations, or those using chlorine in cooling waters.

WATER QUALITY GUIDELINE SERIES No. WQG-10 5


3.3 Chlorine Requirements for Domestic and Industrial Waters
The chlorine dosage used to treat domestic or industrial waters varies widely and depends upon the type
and degree of treatment required. Some typical chlorine dosages for domestic and industrial waters have
been compiled from White (1972, as cited in Pierce, 1978) and Palin (1974, as cited in Pierce, 1978) in a
table by Pierce (1978) which is reproduced in Table 1.

3.4 Residual Chlorine Concentrations in Receiving Waters


When considering the toxicological effects of residual chlorine in ambient waters, the amount of chlorine
normally added to domestic or industrial waters (Table 1) has little bearing on the residual chlorine
concentrations· that will occur in the environment. For example, Jolley (1975) reported that 99 percent of
the chlorine dose used to disinfect secondary treatment sewage is reduced to harmless chloride. Servizi
(1979) noted that chlorine residuals in municipal sewage effluent commonly range between 0.5 and 2.0
mg/L. In a 1975 survey of total residual chlorine in the final effluent of selected sewage treatment facilities
throughout British Columbia, Cook and Trasolini (1977) reported that out of 11 facilities studied, 5
exceeded 1.0 mg/L in more than 40 percent of the samples, 9 exceeded 0.02 mg/L in 50 percent of the
samples and 4 exceeded 0.02 mg/L in 90 percent of the samples. At two sites, total residual chlorine
concentrations of 0.17 mg/L (15 m downstream from the outfall) and 0.41 mg/L (25 m downstream) were
measured in the receiving waters.
Servizi (1979) reported that chlorine residuals decrease as a consequence of reaction with a wide variety
of substances in sewage, but a significant amount may persist for long periods. This persistence is likely
due to the formation of monochloramine which, according to Johnson (1978), may persist in natural
waters for days. Similarly, from a review of the literature, Brungs (1973) also concluded that residual
chlorine persists for periods longer than the few minutes or hours indicated by some authorities. For
example, Esvelt et al. (1973) reported that chlorine residuals in chlorinated sewage gradually decreased
with time but persisted for at least 3 days.
Martens and Servizi (1975) measured the rate of decay of residual chlorine in unaerated and aerated
sewage. Initial chlorine residuals of 1.2 to 1.1 mg/L in unaerated and aerated samples declined to 0.02
and <0.02 mg/L, respectively, in approximately 13 hours. About 75 percent of the initial chlorine residuals
were lost within the first 3 to 4 hours. In similar tests, Servizi and Martens (1974) reported that
approximately 50 hours were required for residual chlorine in primary sewage plant effluent and in
aerated lagoon effluent to decay from 2.6 to 1.2 mg/Land from 0.2 to 0.12 mg/L, respectively. In the same
study, when chlorinated sewage was mixed with the receiving river water in a 5 percent v/v mixture, a
chlorine residual of 0.12 mg/L was measured after 9 hours, but no residual was detected after 24 hours.
In another study, Baker and Cole (1974, as cited in Servizi, 1979) noted an almost complete absence of
chlorine demand of receiving waters. Based on a review of the literature, Servizi (1979) concluded that
there was no evidence of accelerated decay in chlorine residual when chlorinated sewage was mixed with
receiving waters. However, it would seem likely that the chlorine demand of ambient waters may vary
with the waterbody and that the rate of decay would be dependent upon the water quality characteristics
of that waterbody. Mattice and Zittel (1976) indicate the need for caution in predicting the toxicity of an
effluent in the receiving water because of the uncertainties regarding results of interaction of chlorine
with natural waters.
According to the Journal of Hazardous Materials (1977 as cited in Environment Canada, 1984),
experiments have shown that seawater typically has a 30-rninute chlorine demand of 1.5 mg/L and a 2-
day chlorine demand of about 3 mg/L.

WATER QUALITY GUIDELINE SERIES No. WQG-10 6


Based on decay rates of chlorine at varying concentrations in natural and artificial seawater, Goldman et
al. (1979) confirmed the results of other researchers that showed losses of residual chlorine in seawater
occur in two distinct phases. First, a very rapid and significant demand attributed to a true organic
demand, followed by a continuous loss at a reduced rate which does not appear to approach a saturation
limit, even after 10 days. The fate of the residual chlorine lost in the second phase has not as yet been
satisfactorily explained, but the Goldman et al. (1979) study indicated that it is associated with the
bromine chemical system in seawater. The authors (Goldman et al. (1979) recommended that until the
lost chlorine, which is not recoverable by current techniques, is clearly identified, it must remain suspect
as a potential biocide.

3.5 Concentrations in Biological Tissues


A recent review of the literature by the U.S. EPA (1985) stated that no freshwater or saltwater data on the
bioconcentration of total residual chlorine or chlorine-produced oxidants were found, or expected.
In terms of uptake by ingestion, McKee and Wolf (1963) noted that it is generally agreed that the small
amounts of chlorine present in chlorinated water are dissipated by reaction with saliva and gastric juices
as soon as the water is swallowed.

4. AQUATIC LIFE
The following discussion regarding the effects of chlorine on aquatic life (Sections 5.2 to 5.5 inclusive) will
focus upon the relevant data produced from the more sensitive tests taking into consideration the
relationship between exposure periods and concentrations which may influence the determination of
criteria levels. A more complete survey of the available toxicological data is presented in Tables 2 and 2a
for freshwater organisms and Tables 3 and 3a for marine and estuarine organisms. Graphical
representations of the data in these tables (harmful concentrations as a function of exposure periods) are
presented in Figures and 2, respectively.
Furthermore, for the purpose of this discussion, the boundaries between acute and chronic exposures are
120 hours for freshwater organisms and 2 hours for marine and estuarine organisms as determined by
Mattice and Zittel (1976). (Figures 1 and 2).

4.1 Mode of Toxic Action


The chemical mechanism by which residual chlorine incapacitates aquatic life is not completely
understood. Some researchers (Green and Stumpf, 1946, as cited in Alabaster and Lloyd, 1982; Albert,
1965, as cited in Alabaster and Lloyd, 1982) reported that intracellular enzymes containing sulphydryl (-
SH) groups, which are essential to cellular metabolism, become oxidized almost immediately by residual
chlorine in both plants and animals. Because of the strength of the covalent bond formed, enzymatic
activity is irreversibly terminated which may explain why fish exposed to residual chlorine usually do not
recover once equilibrium has been lost (Albert, 1965, as cited in Alabaster and Lloyd, 1982).
In fish, gills have been suggested as the primary site of residual chlorine toxicity based on the damage
observed to gill epitheleum following exposure (Penzes, 1971, as cited in Alabaster and Lloyd, 1982;
Valenzuela, 1976, as cited in Alabaster and Lloyd, 1982; Bass et al., 1977, as cited in Alabaster and Lloyd,
1982). Bass and Heath (1977) and Cairns et al. (1975) concluded that the primary mode of toxic action of
residual chlorine to fish was acute gill tissue damage coupled with mucous accumulation in the gills which
inhibited oxygen uptake resulting in death by asphyxiation. On the other hand, Fobes (1971, as cited in
Alabaster and Lloyd, 1982) reported no change in the respiration rate of excised fish gill tissue following
exposure to 1 mg/L residual chlorine.

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Acutely toxic concentrations of residual chlorine have been shown to alter the blood chemistry in fish.
Zeithoun et al. (1977) measured increases in phosphorus, magnesium, iron, copper, zinc, and potassium
levels and decreases in sodium levels in the blood plasma of 3-year old rainbow trout (Oncorhynchus
mykiss). They concluded that chlorine toxicity appeared to disturb the mineral hemeostasis in the blood.
Groethe and Eaton (1975) attributed the acute toxicity of monochloramine to anoxia (severe oxygen
deficiency) caused by the oxidation of haemoglobin to methaemoglobin in the blood. Similarly, Buckley
(1976a) noted a slight increase in methaemoglobin, a slight decrease in haemoglobin, and a temporary
reduction in the percentage of immature erythrocytes in the blood of young coho salmon (Oncorhynchus
kisutch) when exposed to 0.07 mg/L residual chlorine in a mixture of sewage and seawater. In another
study, Buckley (1976b) reported that concentrations of 3 to 50 µg/L residual chlorine in a mixture of
sewage and river water caused mild to severe symptoms of haemolytic anaemia. The haematological
changes were attributed to the oxidative nature of residual chlorine.

4.2 Effects on Algae

4.2.1 Freshwater Algae


The available data indicate a wide range in the sensitivity of algae to residual chlorine.
Carlson (1976, as cited in Brungs, 1976) performed long-term (3.5 months) multi species bioassays
investigating the effects of chloramine on fish reproduction, invertebrates and algae. Chloramine
concentrations of 1, 4.3, and 11.4 µg/L had no apparent effect upon the reproductive behaviour of the
fish, or upon the standing crop of invertebrates. However, growth of peri phyton on the walls of the test
chamber were delayed in all three test concentrations when compared to controls, and periphyton
standing crop decreased in biomass with increasing chloramine concentration (Pt. 113, Figure 1).
Trotter et al. (1987) exposed attached, filamentous, green algae (Stigeoclonium subsecundum) to
intermittent (6 hours/week) doses of chlorine. The toxicity was found to be dependent upon the algal
biomass. If sufficient biomass was present, then an initial peak of 500 µg/L residual chlorine had no effect
upon the final biomass. If, however, an insufficient biomass was present, all the algal cells would be killed
within a week. Microscopic observations revealed that, compared to controls, the larger algal cultures
adjusted to the chlorine doses by producing a shorter and denser filament growth. This change in
morphology protected the basal algae by reducing the circulation of chlorine-laden water through the
thick algal mat while the terminal cells of longer filaments were killed (Pt. 110, Figure 1).
Eiler and Delfino (1974) studied the biological effects of chlorinated cooling water discharged to the
Mississippi River from a nuclear power station. They concluded that the periodic concentrations of
chlorine in the heated effluent appeared to have a more significant impact on the biotic communities in
the river than the increased water temperature. Productivity of periphytic algae was reduced at times
downstream from the plant. Residual chlorine concentrations measured weekly in the river over a one-
year period were always below the analytical detection limit of 10 µg/L.
For phytoplankton, Toetz et al. (1977) reported that an initial chlorine concentration of 28 µg/L depressed
uptake of nitrates by 50 percent after 24 hours (Pt. 111, Figure 1). Since the concentration reported was
that measured initially, the actual concentration of residual chlorine during incubation was probably
lower. The authors suggested that residual chlorine may destroy or inactivate enzymes in the cell
membrane that are responsible for the uptake of nitrate.
Brooks and Liptak (1979) exposed Lake Michigan phytoplankton to different concentrations of chlorine (0
to 1.5 mg/L) in separate tests for a single 20-minute period. Below 100 µg/L residual chlorine, only slight
reductions in chlorophyll a were noted, and following an initial decrease, carbon uptake rates achieved

WATER QUALITY GUIDELINE SERIES No. WQG-10 8


nearly complete recovery after 24 hours. At or above 1 000 µg/L residual chlorine, the photosynthetic
system of the algae was irreversibly destroyed. Between 100 and 1 000 µg/L, intermediate effects were
observed (Pt. 112, Figure 1).
Brook and Baker (1972, as cited in Alabaster and Lloyd, 1982) reported an EC50 of 320 µg/L residual
chlorine for reduction of photosynthesis and respiration of phytoplankton.

4.2.2 Marine and Estuarine Algae


A review of the available literature indicated that marine and estuarine algae generally demonstrated a
similar wide range of sensitivity to residual chlorine as freshwater algae. The lowest residual chlorine
concentration reported to have a harmful effect on marine. and estuarine algae was 9 µg/L. Davis and
Coughlan (1978, as cited in Ho and Roberts, 1985), and Roberts and Illowsky (n.d., as cited in Ho and
Roberts, 1985) reported 2 or 3 h EC50's (photosynthetic inhibition) of 9 to 100 µg/L residual chlorine for
mixed phytoplankton communities (Pt. 70, Figure 2).
Eppley et al. (1976) observed decreases in marine phytoplankton photo- synthesis after 20 hours of
exposure to power plant chlorination at a concentration as low as 10 µg/L total residual chlorine (Pt. 71,
Figure 2). Similarly, Bender et al. (1977, as cited in Ho and Roberts, 1985) reported that over a range of
three salinities and three temperatures, four estuarine species of nanoplankton in unialgal cultures
exhibited 4-h EC50's (inhibition of carbon uptake) of 10 to 470 µg/L residual chlorine (Pt. 69, Figure 2).
Ho and Roberts (1985) exposed indigenous phytoplankton populations of the lower James River in Virginia
to mixtures of chlorinated sewage and estuarine river water. Based on the chlorine residual measured in
the sewage, an EC50 of 70 µg/L residual chlorine was calculated as the average concentration which
inhibited photosynthetic activity in the mixtures. The exposure period was not reported.
Gentile et al. (1974, as cited in Brungs, 1976) reported that the growth rates of 11 species of marine
phytoplankton were decreased by 50 percent on exposure to residual chlorine concentrations which
ranged between 76 and 330 µg/L for 24 hours (Pt. 10, Figure 2).
Carpenter et al. (1972) exposed marine phytoplankton to several continuously maintained residual
chlorine concentrations. The lowest concentration tested, which was less than the detection limit of 100
µg/L, reduced productivity by 79 percent.
Stone et al. (1973, as cited in Brungs, 1976) tested the long-term effects of chlorinated municipal
wastewater upon San Francisco Bay biota (composed of decomposers, producers and herbivores). An
average residual chlorine concentration of 60 µg/L in a mixture of one percent wastewater in seawater
reduced biomass accumulation to less than 30 percent of that produced in unchlorinated wastewater/
seawater mixtures. At this same concentration, chlorophyll was reduced to 50 percent of that measured
in the controls. No biota survived in bioassays receiving residual chlorine concentrations higher than 60
µg/L.
Goldman and Quinby (1979) measured the recovery rates of marine phytoplankton entrained in the
chlorinated cooling water of two power plants. Chlorination of the cooling water was intermittent (15 or
30 minutes, twice daily) and the residual chlorine at discharge ranged from 80 to 110 µg/L at one plant
and from 20 to 80 µg/L at the other plant. At both pl ants, regrowth of phytoplankton entrained in the
heated, chlorinated cooling water after discharge was virtually identical (as measured by cell number,
ATP, or chlorophyll a) to the intake control samples within a few days which indicated that phytoplankton
surviving chlorination are capable of quickly re-establishing prechlorination growth rates (Pts. 72, 73, 74,
Figure 2).

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4.3 Effects on Aquatic Macrophytes
Very few data were available regarding the toxic effects of residual chlorine to vascular aquatic
macrophytes. Interest in this topic was generated by field observations during related studies.
Whigham and Simpson (1978, as cited in Watkins and Hammerschlag, 1984) noted reductions in
macrophyte biomass, changes in species composition, and elimination of species in freshwater tidal wet-
lands receiving chlorinated sewage effluent. The authors attributed these changes to chlorine in the
effluent; however, no chlorine measurements were made to confirm their suspicions. Similar changes
were noted by Wester and Rawles (1979, as cited in Watkins and Hammerschlag, 1984) in selected areas
of the upper Potomac and Anacostia estuaries and appeared to be associated with electric generating and
waste treatment plant outfalls, both of which are potential sources of residual chlorine. However, the
numerous confounding factors common to field observations made meaningful conclusions difficult
regarding the cause of the changes.
In laboratory tests, Watkins and Hammerschlag (1984) exposed Eurasian water milfoil (Myriophylum
spicatum) to a series of intermittent and continuous concentrations of total residual chlorine over 96
hours. A continuous 96-hour exposure to 50 µg/L total residual chlorine significantly reduced shoot length
growth by 16.2 percent and dry weights by 30 percent when compared to control plants (Pt. 114, Figure
1). Concentrations required to achieve a 50 percent reduction in the growth under continuous
chlorination occurred in the 100 to 400 µg/L range. Results from the intermittent chlorination tests
indicated an insensitivity of growth reduction at all concentrations below 1 000 µg/L during the 96-hour
test period.

4.4 Effects on Invertebrates

4.4.1 Freshwater Invertebrates

4.4.1.1 Acute Toxicity


There is a considerable range in the acute toxicity of residual chlorine to invertebrates. The large range
seems dependent on a number of factors including the exposure period, the species tested, and variations
in test procedures. Also, some of the data are questionable due to conflicting results, mortality in control
tests or unverified results.
The lowest total residual chlorine concentration reported in the literature to be acutely toxic to freshwater
invertebrates was 1 µg/L. This chloramine concentration, cited by Arthur and Eaton (1971) as a personal
communication with K.E. Biesinger, was reported to kill all Daphnia magna individuals in 3 to 5 days (Pt.
118, Figure 1). However, the original study does not appear to have been published to verify these results.
Ward et al. (1976) studied the effects of chlorinated municipal wastewater, primarily of domestic origin,
upon Daphnia magna. The authors reported 100 percent mortality of 3-day-old D. magna exposed to 70
µg/L residual chlorine for 10.5 hours (Pt. 119, Figure 1). One-day-old D. magna suffered 30 percent
mortality at 11 µg/L after 48 hours yielding a 48-h LC50 of 17 µg/L (Pt. 120, Figure 1). However, control
test mortalities revealed that inherent properties of the unchlorinated effluent were toxic to this species.
Arthur et al. (1975) performed two separate tests, each with duplicates (i.e., total of 4 tests) at various
residual chlorine concentrations using Daphnia magna exposed to secondary-treated sewage. After 7 days
exposure at 2 µg/L, both duplicates in test No. 1 had only 1 mortality each out of 10 individuals which was
similar to the mortality rate in each of the unchlorinated control tests. At 4 µg/L, 50 percent of the
individuals survived after 7 days, but the duplicate showed 90 percent survival which exceeded the 70
percent survival in the corresponding unchlorinated control test. In test No. 2 at 2 µg/L residual chlorine,
the survival rate after 7 days was zero percent and 50 percent in each of the duplicates, compared to 70
WATER QUALITY GUIDELINE SERIES No. WQG-10 10
and 90 percent survival, respectively, in the controls. At total residual chlorine concentrations of 7 µg/L
or greater, no Daphnia survived. In view of the inconsistencies in these data, the 7-day LC50 would appear
to lie somewhere between 2 and 7 µg/L total residual chlorine (Pt. 117, Figure 1).
Grossnickle (1974, as cited in Brungs, 1976) exposed rotifers (Keratella cochlearis) to total residual
chlorine continuously for periods of 1, 4, and 24 hours. The 1, 4, and 24-h LC50's were 32, 27, and 13.5
µg/L, respectively (Pt. 127, Figure 1). Similarly, Beeton et al. (1976, as cited in Brungs, 1976) exposed the
same species of rotifer to a mixture of hypochlorite and monochloramine. The 4-h LC50 was 19 µg/L total
residual chlorine (Pt. 128, Figure 1).
Ward and DeGraeve (1980) measured the acute toxicity of chlorinated effluent from a treatment plant
receiving both domestic and industrial wastewaters. The 48-h LC50's for various invertebrate species,
including aquatic insect larvae, ranged from 41 µg/L total residual chlorine for copepods to 1 120 µg/L for
the amphipod Gammarus sp. (Pt. 126, Figure 1). When compared to tests using unchlorinated
wastewater, the authors concluded that the majority of the toxicity measured was associated with
chlorination and not merely the inherent toxicity of the unchlorinated effluent.
Arthur and Eaton (1971) exposed the amphipod Gammarus pseudolimnaeus to various chloramine
concentrations under continuous flow conditions. The 96-h LC50 for this species was 220 µg/L total
residual chlorine (Pt. 21, Figure 1).
Arthur et al. (1975) reported a 7-day LC50 for caddisfly (Tricoptera) larvae of 550 µg/L total residual
chlorine and a 3-day LC50 of 480 µg/L for stonefly (Plecoptera) larvae tested in chlorinated sewage (Pts.
32 and 36, Figure 1).
Latimer et al. (1975) investigated the effects of a single 30-minute dose of chlorine at different
temperatures on two species of copepods (Limnocalanus macrurus and Cyclops bicuspidatus thomasi) to
simulate the effect of intermittent chlorination of power plant cooling water. The 0.5-h LC5's
(concentration causing 5 percent mortality over the 30-minute exposure period) were used to predict
“safe” concentrations. The “safe” 30-minute total residual chlorine concentrations predicted for L.
macrurus and C. b. thomasi were 900 and 500 µg/L, respectively (Pts. 124 and 125, Figure 1).
Greg (1974, as cited in Brungs, 1976) reported that temperature exerted an influence on residual chlorine
toxicity but the degree varied widely depending upon the species tested. Generally, 2 and 4-day LC50
values for a variety of freshwater invertebrates and aquatic insect larvae exposed continuously to residual
chlorine ranged between 10 and 100 µg/L (Pts. 28, 30, 31, 33, 34, 35, 37, 44, 45, 47, Figure 1). However,
it was suspected that. nearly lethal temperatures may have played a major role in some of the tests, as
indicated by high control mortalities.

4.4.1.2 Chronic Toxicity


A review of the few available studies investigating the chronic effects of residual chlorine to freshwater
invertebrates indicated a wide range of sensitivities depending on the species, the effect studied, and the
exposure period.
Arthur et al. (1975) noted decreased reproduction in Daphnia magna after 2 weeks exposure to 2 µg/L
total residual chlorine in secondary treated municipal sewage, although duplicate tests at this
concentration yielded somewhat inconsistent results. When compared to unchlorinated control tests,
obvious decreases in reproduction occurred at 4 µg/L and greater (Pt. 117, Figure 1). Decreased
reproduction in the amphipod Gammarus pseudolimnaeus was noted at 19 µg/L total residual chlorine
after 20 weeks exposure and decreased survival of adults occurred at 54 µg/L after 16 weeks exposure
(Pts. 23 and 24, Figure 1). The authors concluded that the highest mean total residual chlorine

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concentrations having no long-term adverse effects on amphipods and Daphnia were 12 µg/L and 2 to 4
µg/L, respectively.
Arthur and Eaton (1971) exposed G. pseudolimnaeus to chloramine for periods up to 15 weeks. While the
96-h LC50 for this species was 220 µg/L, 80 percent mortality occurred at 35 µg/L after 15 weeks and
reproductive success was markedly reduced in chloramine concentrations of 3.4 to 16 µg/L after 15 weeks
(Pts, 20, 21, 22, Figure 1).
The U.S. EPA (1985) calculated a 365-day LC50 of 31 µg/L total residual chlorine for the crayfish
Pacifastacus trowbridgii based on studies performed by Larson et al. (1978) (Pt. 129, Figure 1).

4.4.2 Marine Invertebrates

4.4.2.1 Acute Toxicity


A review of the toxicological data has revealed that, generally invertebrates are the most sensitive marine
organisms to short-term exposures of chlorine-produced oxidants (CPO).
Dinel et al. (1981) demonstrated that egg fertilization success in sand dollars (Dendraster excentricus) and
sea urchins (Strongylocentrotus droebachiensis) was reduced by 50 percent when exposed to CPO
concentrations as low as 2 to 13 µg/L for 5 minutes (Pt. 121 and 122, Figure 2). In an earlier study,
Muchmore and Epel (1973) showed that the CPO concentration required to reduce egg fertilization
success of another sea urchin species (Strongylocentrotus purpuratus) to 1 to 6 percent after 5 minutes
exposure was 125 µg/L. Mattice and Zittel (1976) assessed this earlier data (Pt. 41, Figure 2) and
determined an acute toxicity threshold of 67 µg/L for an exposure period of 5 minutes.
Of the various species of marine arthropods tested, rotifers (Brachionus plicatilis) have shown the greatest
sensitivity to CPO. Capuzzo (1979) determined a 30-minute LC50 of <10 µg/L CPO for rotifers exposed to
chloramine in a test with a 5°C temperature increase. Under the same test conditions, but using free
chlorine, the 30-minute LC50 was 90 µg/L. Similar tests with no temperature change produced 30-minute
LC50’s of 20 and 180 µg/L CPO when exposed to chloramines or free chlorine, respectively. (Pts. 93 to 96,
Figure 2). It is apparent from these tests that rotifers are more sensitive to chloramines than to free
chlorine, especially when exacerbated with temperature increases. This same trend of sensitivity was
noted for other marine invertebrates including copepods, lobsters, and oysters.
Capuzzo (1979) showed that 30-minute LC50's for the eastern oyster (Crassostrea virginica) exposed to
chloramine during no temperature change and a 5°C temperature change of the test water were 10 µg/L
or less. When exposed to free chlorine under the same temperature conditions, the LC50's were 120 and
80 µg/L CPO, respectively, especially at increased temperatures (Pts. 86 and 87, Table 3a). It should be
noted that several other studies (Roberts et al., 1975; Scott and Middaugh, 1977; U.S. EPA, 1981;
Roosenburg, Rhoderick, Block, Kennedy, Gullans, et al., 1980) using the eastern oyster have indicated that
this species may not be as sensitive to chlorine as indicated by Capuzzo (1979), even after longer
exposures, This eastern oyster species is not found in British Columbia waters. The species of oyster
common in British Columbia coastal waters is Crassostrea gigas which was introduced from Japan many
years ago. While the two species are closely related, no toxicological data were available for the effects
of chlorine on C. gigas.
Lobster (Homarus americanus) larvae have shown a considerable range of sensitivity to CPO depending
upon the form of chlorine (chloramine or free chlorine) introduced and upon the particular response
tested. The lowest concentration found to have a deleterious effect was 30 µg/L CPO on exposure to
chloramine for 60 minutes which reduced the respiration rate by 50 percent (Capuzzo, 1977) (Pt. 117,
Figure 2). Under identical test conditions, but using free chlorine, the 60-minute EC50 for the same

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response was 80 µg/L indicating a greater sensitivity to chloramine (Pt. 118, Figure 2). Lobsters are not
indigenous to British Columbia coastal waters and attempts to introduce them here have proven
unsuccessful.

4.4.2.2 Chronic Toxicity


The toxicological data indicate that invertebrates are the most sensitive marine organisms to chronic
exposures of CPO. This high sensitivity of invertebrates was also noted for acute exposures (Section
4.4.2.1).
The lowest CPO concentration reported to have a detrimental effect on marine invertebrates was a 48-h
LC50 of 1 µg/L (Pt. 91, Figure 2), calculated by Roberts et al. (1975) for the hard clam (Mercenaria
mercenaria). However, it should be noted that due to the limitations of analytical detection of the study,
this was an extrapolated value and therefore may be somewhat questionable. This same study (Roberts
et al., 1975) also reported that the 48-h LC50 for retarded hinge development in hard clam larvae was 6
µg/L CPO (Pt. 90, Figure 2). In addition, Roberts et al. (1975) noted reduced shell deposition in juvenile
eastern oysters exposed to CPO for 96 hours. An extrapolated 96-h EC50 of 23 µg/L was derived because
the lowest concentration tested was 40 µg/L (Pt. 78, Figure 2).
Hawk and Block (in press, as cited in Scott, 1981) noted reduced glycogen levels in the adductor muscles
of adult oysters (C. virginica) exposed to 4 µg/L CPO for 96 hours (Pt. 85, Figure 2). However, it is unclear
if this response is harmful to the animals in terms of survival, growth, longevity or reproductive success.
Roberts and Gleeson (1978) determined 48-h LC50's of 26 and 29 µg/L CPO for eastern oyster larvae (Pt.
77, Figure 2), and for the copepod Acartia tonsa (Pt. 98, Figure 2), respectively, in constant addition
systems.
Hillman et al. (1979) showed inhibited shell growth in adult littleneck clams (Protothaca staminea)
exposed to 25 µg/L CPO for 8 months (Pt. 92, Figure 2).
Roberts (1977) reported a 96-h LC50 of 24 µg/L CPO for intertidal mud crab (Panopeus herbstii) larvae (Pt.
110, Figure 2) while the lowest 120-h LC50 for the larvae of a species of hermit crab (Pagurus longicarpus)
was 54 µg/L CPO (Pt. 111, Figure 2).
All other long-term (>2-hour exposure period} toxicological results for marine invertebrates exceed a CPO
concentration of 30 µg/L (Figure 2).

4.5 Effects on Fish


Due to the large amount of data pertaining to the toxicological effects of residual chlorine on fish, the
following discussion will focus upon the relevant data produced from the more sensitive tests taking into
account the relationship between exposure period and concentration, and any other factors which may
influence the determination of criteria levels.

4.5.1 Freshwater Fish

4.5.1.1 Acute Toxicity


In an extensive review of the literature regarding the toxicity of chlorine to aquatic organisms, Brungs
(1976) concluded that most of the 96-h LC50 values for the more sensitive freshwater fish (trout, salmon,
and minnows) ranged between 40 and 80 µg/L total residual chlorine.
Other data, not included in the review by Brungs (1976) have indicated that. concentrations of total
residual chlorine less than 40 µg/L are acutely toxic to fish. For example, Cairns and Conn (1979, as cited
in Servizi, 1979) produced minimum and average 96-h LC50‘s of 10 and 40 µg/L, respectively, for rainbow

WATER QUALITY GUIDELINE SERIES No. WQG-10 13


trout (Oncorhynchus mykiss) exposed to residual chlorine in secondary-treated municipal sewage using
continuous-flow bioassays (Pt. 140, Figure 1).
Rosenberger (1972, as cited in Mattice and Zittel, 1976) determined mortality thresholds for coho salmon
(Oncorhynchus kisutch) of 16 and 4 µg/L for exposure periods of 24 and 96 hours, respectively (Pt. 50,
Figure 1). These data were included in the review by Mattice and Zittel (1976) who rated the results as
“good” in terms of their overall scientific validity, based upon the experimental procedure, analytical
technique, and reporting of the data.
Truchan and Basch (1971, as cited in Mattice and Zittel, 1976) reported some mortality of the gizzard shad
(Dorosoma cepedianum) exposed to 620 µg/L total residual chlorine in a power plant discharge after 10
minutes (Pt. 49, Figure 1). Mattice and Zittel (1976) evaluated this study and rated the data as good.
Holland et al. (1960, as cited in Mattice and Zittel, 1976) reported 100 percent mortality of coho fingerlings
exposed to 150 µg/L monochloramine (measured as total residual chlorine) for less than 48 minutes (Pt.
51, figure 1). This result was rated good by Mattice and Zittel (1976).
Hubbs (1930, as cited in Mattice and Zittel, 1976) reported 100 percent mortality of roseyface shiners
(Notropis rubellus) exposed to 70 µg/L total residual chlorine for 180 minutes (Pt. 83, Figure 1). This result
was also rated good by Mattice and Zittel (1976).
Pike (1971, as cited in Mattice and Zittel, 1976) reported 50 percent mortality to brown trout (Salmo
trutta) exposed to 90, 50, and 20 µg/L free chlorine for periods of 180, 360 and 660 minutes, respectively
(Pt. 63, Figure 1). It should be noted that the measurement of free chlorine (orthotolidine method) may
have under estimated the concentration of total residual chlorine required to cause mortality (i.e., the
free chlorine measurement may have been conservative with respect to environmental protection in this
particular context).
In field studies, Basch et al. (1971, as cited in Basch and Truchan, 1974) placed caged rainbow trout
upstream (control site) and at various locations downstream from four Michigan municipal wastewater
treatment plants while the plants were chlorinating at normal levels. In three of these caged fish studies,
average concentrations of total residual chlorine as low as 20 µg/L were lethal to rainbow trout after 96
hours. The lowest 96-h LC50 reported was 14 µg/L (Pt. 54, Figure 1). On request, the plants stopped
chlorinating and new fish were placed in the cages. During the discharge of unchlorinated effluent, the
trout survived exposure to undiluted effluent indicating that residual chlorine was the toxic constituent.
Mattice and Zittel (1976) rated these results as good.
Similarly, in British Columbia. Servizi and Martens (1974) placed young sockeye salmon (Oncorhynchus
nerka) in cages at various locations downstream from three chlorinated domestic wastewater discharges.
At a residual chlorine concentration of 1 000 µg/L, 100 percent mortality was recorded in 18 minutes.
When the total residual chlorine ranged between 200 and 220 µg/L, 50 percent of the fish died after 3 to
4 hours of exposure. The authors concluded that mortality of so eke ye salmon and rainbow trout was
likely when total residual chlorine in the receiving water was 20 µg/L or greater.
Tsai (1973) studied fish species diversity and occurrence above and below 149 domestic wastewater
treatments in Virginia, Pennsylvania, and Maryland. No fish were found in water containing residual
chlorine which exceeded 370 µg/L. Tsai's graphically presented data indicated that brown trout (Salmo
trutta) and brook trout (Salvenlinus fontinalis) did not occur where total residual chlorine concentrations
exceeded about 20 µg/L.
DeGraeve and Ward (1977) studied the ability of fathead minnows (Pimephales promelas) and lake trout
(Salvelinus narnaycush) to acclimate to residual chlorine. The authors found that fish previously exposed
to sublethal chlorine concentrations for longer than about 2 hours were capable of tolerating higher levels

WATER QUALITY GUIDELINE SERIES No. WQG-10 14


of total residual chlorine for longer periods of time when compared to control fish that were not
previously exposed.

4.5.1.2 Chronic Toxicity


The lowest concentration of total residual chlorine shown to produce harmful effects to freshwater fish
on long-term exposure was 3 µg/L, Buckley (1976b) demonstrated that fingerling coho salmon, exposed
for 12 weeks to mixtures of secondary-treated domestic wastewater and river water diluent containing 3
to 50 µg/L total residual chlorine, developed mild to severe symptoms of haemolytic anemia (Pt. 132,
Figure 1).
Dandy (1972) reported depressed locomotory activity of brook trout exposed to 5 µg/L total residual
chlorine for 7 days. The 7-day lethal threshold for brook trout was reported as 10 µg/L total residual
chlorine (Pt. 65, Figure 1). These results were rated as good by Mattice and Zittel (1976) whereas the.
results of an earlier (1935) study by Coventry et al. (1935, as cited in Mattice and Zittel, 1976), which
reported the same 7-day lethal threshold concentration (10 µg/L) for brook trout was considered
questionable (Pt. 66, Figure 1).
Larson, Hutchins, and Lamperti (1977) reported a decrease in the growth of juvenile coho salmon, when
compared to controls, at chloramine concentrations of 22 to 23 µg/L (measured as total residual chlorine)
after 3 weeks exposure (Pt. 133, Figure 1). Growth and food conversion efficiency in test fish were not
affected at a total residual chlorine concentration of 5 µg/L. The authors concluded that the threshold
concentration for reduction in growth occurred between 11 and 23 µg/L, but this was probably influenced
by fish size, history of exposure to the toxicant, and the age-season complex.
The avoidance of total residual chlorine by fish was highly variable and dependent on a number of factors
including the total residual chlorine concentration, water temperature, and the species tested.
Giattina et al. (1981) studied the avoidance of total residual chlorine by fish in field surveys and laboratory
tests. Whitetail shiners (Notropis galacturus) avoided 40 µg/L total residual chlorine (intermittent
chlorination) when field temperatures ranged between 30 and 35°C. When field temperatures were falling
from 26 to 7°C, the fish avoided 230 to 420 µg/L. Based on published acute toxicity tests using intermittent
chlorination, the authors concluded that most fish species generally avoided chlorine residuals of 50
percent or less of the median lethal concentrations.
From field studies using caged rainbow trout, data obtained by Osborne et al. (1981) indicate that,
contrary to popular belief, fish do not congregate below sewage outfalls, but instead they avoid
chlorinated sewage. However, fish moved in and out of the chlorinated sewage, presumably to feed.
Sprague and Drury (1969, as cited in Katz and Harder, 1976) found that salmon avoided total residual
chlorine concentrations of 1, 10, and 1 000 µg/L, but seemed to be attracted to 100 µg/L. The authors
interpreted this phenomenon as a “physiological trap” involving the sense organs. Katz and Harder (1976)
offered another interpretation of this particular phenomenon. Since chlorine reacts with ammonia
(excreted from the gills of fish) to form chloramines, it is possible that at the 100 µg/L concentration,
breakpoint chlorination (Section 2) occurred at the gills. At the breakpoint, no chlorine residuals are
present which indicate chlorine-free water to the fish and thus misleads them into turning around and re-
entering the chlorinated water.

4.5.2 Marine Fish


While there is a considerable amount of data regarding the toxicity of CPO to marine fish, the majority of
the studies focus upon lethal responses. Few data were available regarding sublethal responses in marine
fish. Furthermore, there was a paucity of data regarding exposure periods exceeding 96 hours.

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4.5.2.1 Acute Toxicity
A review of the available toxicological data indicated that marine fish generally appear to be more tolerant
to acute exposures of CPO than marine invertebrates or phytoplankton.
The lowest concentration of CPO reported to have a lethal effect on marine fish after acute exposure (less
than 2 hours) was 75 µg/L. Alderson (1970, as cited in Mattice and Zittel, 1976) reported 50 percent
mortality to plaice (Pleuronectes platessa) larvae exposed to 75 µg/L CPO (introduced as free chlorine) for
75 minutes (Pt. 47, Figure 2). Mattice and Zittel (1976) rated the results of this study as good. While plaice
are not indigenous to British Columbia coastal waters, there are several closely related species which do
inhabit these waters.
Other available data regarding lethal concentrations of CPO to marine fish exposed for 2 hours or less
were all greater than 100 µg/L, regardless of the life state, or whether the fish were exposed to free
chlorine or chloramine, or of any temperature change during the test.
Less severe effects such as avoidance or di stress were noted at much lower concentrations. For example,
Stober et al. (1980) determined an avoidance threshold of 2 µg/L CPO for coho salmon. While an exposure
period is not given, a response, such as avoidance, usually occurs quickly, Avoidance is not a severe effect
and thus, is not likely to have an immediately harmful effect on fish. Nevertheless, avoidance may disturb
migration patterns, such as inhibiting or stalling the passage of salmon through estuaries on their return
to spawn. On the other hand, avoidance may be merely an initial response which may be overcome by
gradual acclimation.
Avoidance of CPO by other marine fish species occurred at higher levels. Middaugh et al. (1977)
reported avoidance of spot (Leiostomus xanthurus) to 50 and 180 µg/L CPO after 30 minutes exposure
(Pt, 159, Figure 2), and Stober et al. (1980) reported an avoidance threshold of 175 µg/L for shiner perch
(Cymatogastor aggregata). Hose and Stoffel (1980) found that avoidance of chlorinated seawater by the
blacksmith (Chromis punctipinnis), indigenous to warm temperate waters, was significant at CPO
concentrations of 80 to 1 00 µg/L.
Holland et al. (1960, as cited in Mattice and Zittel, 1976) observed signs of distress, but no
mortality, in Chinook salmon (Oncorhynchus tshawytscha) exposed to 100 µg/L for 60 minutes (Pt, 54,
Figure 2).

4.5.2.2 Chronic Toxicity


The lowest CPO concentration reported in the literature to have a harmful effect on marine fish after an
exposure period of more than 2 hours was >23 µg/L. Thatcher (1977) reported 96-h LC50's of >23 µg/L for
juvenile pink salmon (Oncorhynchus gorbuscha) and 32 µg/L CPO for juvenile coho salmon (O. kisutch) in
laboratory bioassays designed to simulate chlorinated cooling water in seawater (Pts. 132 and 131, Figure
2).
On the other hand, Buckley (1976a) reported a 96-h LC50 of 70 µg/L CPO for juvenile coho salmon exposed
to a mixture of chlorinated sewage and seawater diluent (Pt. 128, Figure 2). However, in a previous study
which investigated changes in blood chemistry and blood cell morphology, Buckley et al. (1976)
determined a maximum safe concentration of between 3 and 9 µg/L CPO for yearling coho salmon
exposed to chlorinated sewage and seawater for 12 weeks (Pt. 129, Figure 2).
Alderson (1970, as cited in Mattice and Zittel, 1976) noted 50 percent mortality to plaice larvae on
exposure to 28 µg/L CPO introduced as free chlorine) for 96 hours (Pt. 47, Figure 2).
Esvelt et al. (1973) reported 50 percent mortality to golden shiners (Notemigonus chrysoleucas) exposed
to between 30 and 230 µg/L for 96 hours (Pt. 65, Figure 2).

WATER QUALITY GUIDELINE SERIES No. WQG-10 16


Roberts et al. (1975) reported 48 and 96-h LC50's of 38 and 37 µg/L CPO, respectively, for Atlantic
silversides (Menida menida) in estuarine water (Pts. 134, Figure 2). The ambient ammonia levels (100 to
300 µg/L) in the diluent water indicated that only combined chlorine, primarily as monochloramine,
should be present. However, no monochloramine was detected at the detection limit of 20 µg/L.

4.6 Criteria from the Literature


Criteria, objectives, and standards to protect aquatic life from TRC (in freshwater) or CPO (in seawater)
have been compiled from a number of jurisdictions and tabulated in Tables 4 and 5, respectively.

4.6.1 Continuous Exposure


Recent criteria to protect freshwater aquatic life from continuous exposure to TRC generally range
between about 2 and 20 µg/L. For continuous exposure of marine and estuarine aquatic life, a similar
range of CPO concentrations has been recommended by various jurisdictions over the years.
The most recent (1985) U.S. EPA (1985) criteria to protect freshwater aquatic life from continuous
exposure to TRC specify that the 1-hour average concentration should not exceed 19 ug/L and the 4-day
average should not exceed 11 µg/L, To protect marine aquatic life, the U.S. EPA (1985) criteria specify a
1-hour average of 13 µg/L CPO and a 4-day average of 7.5 µg/L CPO. These criteria do not apply to
situations of specifically controlled intermittent exposures.
The U.S. EPA (1985) has introduced a new concept to its most recent aquatic life criteria. It permits the
criteria to be exceeded an average of once every three years. The reasoning behind this concept is based
on the U.S. EPA's best scientific judgement that three years is the average amount of time it would take
to an unstressed system to recover from a pollution event (Stephan et al., 1985).
The U.S. EPA criteria were derived using a somewhat complex statistical procedure developed by Stephan
et al. (1985) and are intended to protect at least 95% of a group of diverse genera. If a sensitive species
Ls economically, recreationally, or socially important, then the criterion is based on toxicity data for that
sensitive species. The U.S. EPA criterion to protect aquatic life from acute toxicity is based on the “Final
Acute Value” (a Genus Mean Acute Value derived using statistical procedures based on 96-h LC50' s). In
the case of an important sensitive species, the criterion is based upon the “Species Mean Acute Value”
which becomes the “Final Acute Value” The “Final Acute Value” is divided by a safety factor of two to
determine the “Criterion Maximum Concentration”, which is the criterion level (specified as a 1-hour
average) designed to protect aquatic life from acute effects.
The U.S. EPA 4-day average criterion level, which is designed to protect organisms from the chronic effects
of chlorine, is derived by dividing the “Final Acute Value” by the geometric mean of the acute-chronic
ratios (inverse of the application factor) for sensitive organisms. This value has been called the “Criterion
Continuous Concentration” by the U.S. EPA.
The most recent Canadian criterion for total residual chlorine was determined by the Canadian Council of
Resource and Environment Ministers (CCREM) (1987) in 1987. It recommends that the concentration of
TRC, as measured by the amperometric (or equivalent) method, should not exceed 2 µg/L. This criterion
applies only to freshwater. It is not clear whether the criterion applies to controlled intermittent
exposures as well as continuous exposure.
The use of separate criteria for warm and cold freshwater aquatic life by some jurisdictions is considered
no longer valid. Brungs (1976) reported that additional data for some warm-water fish no longer support
this distinction.
The British Columbia Pollution Control Objectives for Municipal Waste Discharges (B.C. Ministry of
Environment, 1979), Forest Products Industries (B.C. Ministry of Environment, 1977), Chemical and

WATER QUALITY GUIDELINE SERIES No. WQG-10 17


Petroleum Industries (B.C. Ministry of Environment, 1980), and Food-Processing, Agriculture and Other
Miscellaneous Industries (B.C. Ministry of Environment, 1980) specify that TRC should not be detectable
(as measured by the amperometric method) outside the initial dilution zone. As noted in Section 2.3,
detection limits for the amperometric titration technique can vary depending upon improvements to the
technique and operator skill. This “non-detectable” approach could result in the uneven application of
criteria throughout the Province and, in some cases, result in criteria that may be underprotective or
overprotective.

4.6.2 Intermittent Exposure


The popular approach to protect aquatic life from controlled, intermittent exposures to TRC or CPO is to
base the criteria on an exposure time- concentration relationship. This approach which was first
introduced by Mattice and Zittel (1976) in 1976 and later recommended by the American Fisheries Society
(DeGraeve et al., 1979), is demonstrated in Figures 1 and 2, where the safe level can be obtained directly
from the “Acute Toxicity Threshold”. A modification to their concept by Brungs (1977) has refined the
criteria to take into account the additive toxic effect of intermittent exposures. To accomplish this, the
exposure time over a 24-hour period was totalled and the acceptable toxicant concentration was read
from time-concentration graphs (Figures 1 and 2) for freshwater or marine situations as appropriate.
This additive approach may be, at times, overprotective. Brooks et al. (1982) showed that totalled
intermittent exposures were often less toxic than continuous exposures of similar duration. This indicated
that sane recovery occurred during the intervals between exposures. However, in some cases, totalled
intermittent exposures yielded similar, and at times, identical results to continuous exposures of the same
duration (Pts. 152, Table 2a). These latter data support the additive concept conceived by Brungs (1977).
The U.S. EPA has recently (1988) reviewed applications for two electric generating plants to intermittently
discharge TRC at levels beyond the “best available technology economically achievable” requirements of
the Clean Water Act. To discharge concentrations of contaminants which exceed maximum
concentrations specified under the Act, a variance must be obtained by the applicant. To grant a variance
for any applicant, the U.S. EPA must ensure that State Water Quality Standards are met and that the
proposed concentrations will not be detrimental to water uses in the area.
The two applications reviewed by the U.S. EPA include a freshwater discharge to the Mississippi River in
the State of Mississippi (U.S. EPA, 1988a), and a marine discharge to an estuary in California (U.S. EPA,
1988b). The Mississippi discharge has been officially approved and the California discharge has been
tentatively approved pending the outcome of a 30-day public comment and notice period. Since Water
Quality Standards for the two states are different, the impact assessments and the determination of
receiving water objectives have been approached in a different manner for each discharge. Mississippi
requires that the concentration of toxic pollutants shall not exceed 0.1 of the 96-h LC50 based on available
data. The U.S. EPA interpreted the 96-h LC50 as 38 µg/L TRC which is the “Final Acute Value” derived by
the U.S. EPA for continuous exposure (Section 4.6.1). Thus, it was established that a level of 3.8 µg/L TRC
may not be exceeded at the edge of the initial dilution zone. An additional condition of the variance
stipulated that intermittent chlorine discharges are restricted to a maximum total duration of 2 hours per
day (U.S. EPA, 1988a).
For the marine discharge in California, the California Ocean Plan standard for intermittent discharges of
TRC had to be considered before a variance could be granted by the U.S. EPA. The California standard is
based on the duration of chlorination as outlined in the beginning of this Section (4.6.2) and is derived by
the equation:

log y= −0.33 (log x) + 2.1

WATER QUALITY GUIDELINE SERIES No. WQG-10 18


where x is the duration of uninterrupted chlorine discharge in minutes and y is the water quality objective
for TRC (in µg/L) to apply at the edge of the mixing zone when chlorine is being discharged. This standard
is similar to, and appears to be taken from, the acute toxicity threshold derived by Mattice and Zittel
(1976) (Figure 2). Under the conditions of the California Ocean Plan, intermittent discharges of chlorine
are limited to a maximum total duration of 2 hours per day per outfall (U.S. EPA, 1988b).

4.7 Recommended Criteria


Criteria to protect aquatic life from the harmful effects of TRC in freshwater, and CPO in estuarine and
coastal marine waters of British Columbia, are modified from criteria developed by other sources and take
into account appropriate toxicological data to tailor the criteria for aquatic life found in local waters. These
criteria are designed to protect aquatic life from both continuous and controlled, intermittent exposures.

4.7.1 Freshwater Aquatic Life


“Total residual chlorine” is the sum of the “free available chlorine” plus the “combined available chlorine”.
This includes all the forms of chlorine which are able to act as an oxidant.

4.7.1.1 Continuous Exposure


(a) The average concentration of total residual chlorine should not exceed 2 µg/L. This is the threshold of
chronic toxicity. The averaging period should not be less than 4 days nor more than 30 days. A
minimum of 5 samples, equally spaced in time, should be used to calculate the average.

4.7.1.2 Controlled Intermittent Exposures


(a) The total residual chlorine concentration should be time-related and should not exceed the numerical
value (in µg/L) given by the formula (1074(duration)−0.74), where duration is the uninterrupted
exposure period (in minutes). This is the threshold of acute toxicity.
(b) The total duration of exposure in any consecutive 24-hour period should not exceed 2 hours.
(c) The maximum concentration of total residual chlorine should not exceed 100 µg/L regardless of the
exposure period.

WATER QUALITY GUIDELINE SERIES No. WQG-10 19


Examples based on these criteria (rounded to nearest µg/L) are as follows:
Duration of Exposure TRC Concentration
(minutes) µg/L
≤25 100 [as per 4.7.1.2(c)]
30 87
45 64
60 52
90 38
120 31
>120 apply continuous exposure criterion
(4.7.1.1)

4.7.2 Marine and Estuarine Aquatic Life


In marine or estuarine waters, the term “chlorine-produced oxidants” is used because of the high levels
of bromide naturally present in seawater. Bromide, in the presence of residual chlorine, forms “free
available bromine” or “combined available bromine” which are able to act as oxidants.

4.7.2.1 Continuous Exposure


(a) The average concentration of chlorine-produced oxidants should not exceed 3 µg/L. This is the
threshold of chronic toxicity. The averaging period should not be less than 2 hours nor more than 30
days. A minimum of 5 samples, equally spaced in time, should be used to calculate the average.

4.7.2.2 Controlled Intermittent Exposures


(a) The chlorine-produced oxidant concentration should be time-related and should not exceed the
numerical value (in µg/L) given by the formula (20.36(duration)−0.4), where duration is the
uninterrupted exposure period (in minutes). This is the threshold of acute toxicity. The total duration
of exposure in any consecutive 24-hour period should not exceed 2 hours.
(b) The maximum concentration of chlorine-produced oxidants should not exceed 40 µg/L regardless of
the exposure period.
Examples based on these criteria (rounded to nearest µg/L) are as follows:
Duration of Exposure TRC Concentration
(minutes) µg/L
≤0.2 40 [as per 5.7.2.2(c)]
5 11
10 8
15 7
30 5
60 4
90 3
apply continuous exposure criterion
>120
(5.7.2.1)

4.7.3 Application of Criteria


The lower limits for the duration of the averaging periods for continuous exposure and time-related
concentrations for intermittent exposures specified in the criteria imply a requirement for frequent
monitoring. However, longer averaging periods are acceptable because beyond the acute- chronic
intercepts (Fig. 1 and Fig. 2) harmful effects are no longer time dependent. Thus, to allow flexibility in

WATER QUALITY GUIDELINE SERIES No. WQG-10 20


monitoring programs, the averaging period could be as long as 30 days. Such monitoring is necessary only
if dilution calculations indicate that the criteria might possibly be exceeded at the edge of the initial
dilution zone of a discharge containing chlorine.
To determine whether monitoring is necessary, a worst-case scenario should be formulated using site-
specific information which include the effluent concentration of TRC and the minimum dilution available
at the edge of the site-specific initial dilution zone. If the average criterion value for continuous exposure
is not exceeded by the calculated estimate under worst-case conditions, then monitoring is unnecessary
regardless of whether the exposure is intermittent or continuous. If calculations show that the average
criterion value for continuous exposure could be exceeded, for freshwater or seawater as. Appropriate,
then monitoring should be initiated.
When monitoring for TRC or CPO is necessary, the amperometric method of analysis, using modifications
to improve the detection limit (discussed in Section 2.3), is the recommended method. Furthermore, it is
recommended that an individual, experienced in the operation of an amperometer, be designated to
perform the analyses (see Research and Development Needs, Section 6). While frequent monitoring may
be necessary to determine if criteria are being met, usually only a short-term monitoring program is
necessary. Such a monitoring program should be performed at times when minimum dilution is available,
in keeping with the worst-case scenario.
An initial assessment should be made to determine whether exposure at the edge of the initial dilution
zone is continuous or intermittent. In some situations, this determination may be obvious. For example,
if a discharge is continuously chlorinated then, in all likelihood, the exposure will be continuous, and the
appropriate criteria will apply. However, if a discharge is intermittently chlorinated it does not necessarily
follow that exposure is intermittent. For example, if the discharge is to a moving body of water such as a
river then, in all likelihood, exposure will be intermittent. On the other hand, if TRC is discharged
intermittently to a relatively motionless body of water such as a lake, exposure may be intermittent or
continuous depending upon whether residuals persist between the chlorination periods. If residuals do
persist through the periods of non-chlorination, then the situation should be treated as continuous
exposure and the continuous exposure criteria should apply. If residuals do not persist at the edge of the
initial dilution zone, then the intermittent exposure criteria should apply.
While the monitoring schedule should be somewhat flexible to determine if criteria are being met, enough
samples should be taken to provide a relatively accurate profile of the exposure characteristics. For
continuous exposure situations, at least 5 samples, equally spaced in time, are recommended to
determine an average concentration over the averaging periods. The minimum duration of the averaging
periods is 4 days for fresh- water and only 2 hours for marine or estuarine waters but may be as long as
30 days as noted earlier in this Section.
For an intermittent exposure situation, some knowledge of the chlorination schedule, including the start
times, duration of the chlorination period, and daily frequency, would be helpful prior to monitoring. This
prior knowledge would provide an indication of when to start monitoring so that samples could be
collected over the entire exposure period. Monitoring should be continued as frequently as possible over
the chlorination period and until the concentration at the edge of the initial dilution zone drops below the
continuous exposure criterion (i.e., 2 or 3 µg/L for fresh or marine water as appropriate). The
concentrations measured over the uninterrupted duration of exposure should be averaged and the
average value should not exceed the appropriate freshwater (5.7.1.2(a)) or marine and estuarine
(5.7.2.2(b)) criterion. No individual sample should exceed 100 µg/L TRC in freshwater or 40 µg/L CPO in
marine or estuarine water, as per Sections 5.7.1.2(c) or 5.7.2.2(c). Since the intermittent exposure criteria
formulae [5.7,1.2(a) or 5.7.2.2(a)] are based on the acute toxicity threshold, application of these criteria
at the edge of the initial dilution zone could lead to acutely toxic conditions for a short time within the

WATER QUALITY GUIDELINE SERIES No. WQG-10 21


initial dilution zone, depending upon the dilution available and upon the exposure time of organisms in
the initial dilution zone. These items should be considered on a site-specific basis.
It should be noted that while intermittent exposures are not restricted by a lower average criterion, they
are restricted in terms of a maximum exposure period of 2 hours in any consecutive 24-hour period. If the
duration of exposure at the edge of the initial dilution zone exceeds 2 hours in any consecutive 24-hour
period, then the continuous criterion should be applied.
In situations where the criteria have not been met, then one or more of the following corrective measures
should be taken:
i) reduce the chlorine discharge rate,
ii) use an alternative form of treatment,
iii) dechlorinate the effluent.

4.7.4 Rationale
The criteria recommended in this document for the protection of marine, estuarine and freshwater
aquatic life in British Columbia have been based, in part, upon the exposure duration-concentration
concept originally developed by Mattice and Zittel (1976). Certain modifications have been made to
provide a more appropriate level of protection to aquatic life in British Columbia. The addition of more
recent toxicological data has allowed a greater refinement of the threshold levels as shown in the
exposure duration-concentration relationships (Figures 1 and 2). These graphs serve as the basis upon
which the criteria were derived.
The toxicity threshold lines were drawn to enclose valid data points so that concentrations above the
threshold lines would be harmful while concentrations below the threshold lines would be acceptable
from a toxicological perspective. Thus, these threshold lines are a graphical representation of the criteria.
While these graphs may be open to different interpretations, it is believed that the approach used here
will provide adequate protection to aquatic organisms without being too restrictive.
The criteria are expressed in terms of total residual chlorine for freshwater aquatic life and chlorine-
produced oxidants for marine and estuarine aquatic life. A review of the toxicological data failed to
support any justification for separating the chemical components of TRC or CPO.

4.7.4.1 Averaging Periods


The averaging periods for the continuous exposure criteria were determined directly from the exposure
duration-concentration graphs (Figures and 2) for freshwater or marine water as appropriate. The point
of intersect between the acute and chronic thresholds was chosen as the minimum duration for the
averaging periods for continuous exposure. For freshwater, this intersect occurs at 5 000 minutes (Figure
1) and the averaging period was rounded off to 4 days (5 760 minutes). For marine and estuarine waters,
the intersect for the minimum duration of the averaging period occurs at 2 hours (Figure 2). Beyond the
acute-chronic intercepts harmful effects are no longer time-dependent. Thus, to provide some flexibility
in monitoring programs, averaging periods of up to 30 days were considered acceptable. The most recent
criteria developed by the U.S. EPA (1985) for continuous exposure specify averaging periods of 4 days and
1 hour for both freshwater and seawater situations. These U.S. EPA averaging periods have been based
on philosophical assumptions and apply to all contaminants whereas the British Columbia averaging
periods are tailored specifically for chlorine.

WATER QUALITY GUIDELINE SERIES No. WQG-10 22


4.7.4.2 Continuous Exposure Criteria
a) Freshwater Aquatic Life
The chronic toxicity threshold for freshwater organisms (Figure 1) was increased slightly (to 2.0 µg/L) from
that (1.5 µg/L) originally determined by Mattice and Zittel (1976). Close scrutiny of the studies upon which
the original limit was based indicated that there was little justification for such a low value. Nevertheless,
given the high margin of error likely in analytical precision at such low values, there is probably little
difference between the two values. The U.S. EPA (1985) 4-day average criterion of 11 µg/L TRC for
continuous exposure was not considered protective enough given the numerous data points, some of
which include economically and recreationally important species, which occur below that concentration
(see Figure 1). On the other hand, the CCREM (1987) criterion of 2 µg/L TRC, specified as a maximum, is
more restrictive than the British Columbia average criterion because, by definition, a maximum does not
allow for any excursions beyond that limit. In view of the relationship between safe concentrations and
the duration of exposure as shown in Figure 1, it is not unreasonable to assume that occasional minor
fluctuations over the criterion average concentration would be acceptable, provided that:
i) the duration and magnitude of the increases do not exceed the acute threshold value given by the
formula in Section 4.7.1.2(a), and;
ii) the average criterion is met over the duration of the averaging period.
Because the average criterion concentration for TRC in freshwater is at or near the minimum detectable
concentration (MDC), a maximum criterion concentration was considered unnecessary for continuous
exposure situations. The low average criterion and its proximity to the MDC would limit the magnitude
and number of fluctuations over the average criterion value because, when calculating an average
concentration, the MDC should be used for all samples in which TRC is not detected. A maximum criterion
concentration (i.e., the formula for the acute toxicity threshold given in Section 4.7.1.2(a)) would only be
necessary if the MDC was considerably lower than the average criterion which, for TRC, is unlikely given
the present analytical capabilities.

b) Marine and Estuarine Aquatic Life


The chronic toxicity threshold for marine and estuarine aquatic life has been readjusted considerably from
that originally determined by Mattice and Zittel (1976). The addition of more recent data to the exposure
duration- concentration relationship (Figure 2) indicates that marine and estuarine organisms are
considerably more sensitive to CPO than originally believed. As noted in Figure 2, the chronic toxicity
threshold which represents the British Columbia criteria has been reduced from 20 µg/L to 3 µg/ L to take
into account most of the recent data. While one data point (91) is below the chronic toxicity threshold
(continuous criterion) for British Columbia waters, this value was extrapolated from tests using higher
concentrations. As an extrapolated value, this result was considered questionable because it was outside
the limits of the test. One data point (129) situated on the chronic toxicity threshold was determined by
one researcher to be the no-effect level for coho salmon.
The U.S. EPA (1985) 4-day average criterion of 7.5 µg/L CPO for continuous exposure was not considered
protective enough in view of the lower concentrations which have been shown to be detrimental to
economically or recreationally important species. The CCREM (1987) has not recommended criteria for
marine or estuarine aquatic life.

4.7.4.3 Intermittent Exposure Criteria


These criteria were derived by enclosing the valid data points by the acute toxicity thresholds and
determining the formulae for these thresholds for freshwater (Figure 1) and marine and estuarine

WATER QUALITY GUIDELINE SERIES No. WQG-10 23


organisms (Figure 2) as appropriate. The formulae are designed for use in situations that involve the
discharge of non-recycled cooling water from industries that use “shock chlorination” to prevent bio-
fouling of the heat exchangers. “Shock chlorination” is the term used to describe intermittent chlorination
at elevated concentrations as opposed to low-dose chlorination delivered on a continuous basis.
This exposure time-concentration approach for setting criteria for intermittent discharges of TRC was first
introduced by Mattice and Zittel (1976) in 1976 and recommended later by the American Fisheries Society
(DeGraeve et al., 1979) in 1979. Recently the U.S. EPA (1988b) has adopted this time-related approach for
an intermittent TRC discharge in California (see Section 4.6.2).
To address the problem of toxic carry-over effects between intermittent exposures, the approach used by
the U.S. EPA (1988a, 1988b) was adopted whereby the exposure was limited to a maximum total duration
of 2 hours per day. This limit should allow enough time between exposures for complete recovery of
aquatic organisms and thus prevent toxic carry-over. For continuous exposure situations, a time-related
maximum criterion was unnecessary because the average criterion limits the magnitude and duration of
any fluctuations (see Section 4.7.4.2(a)).

a) Freshwater Aquatic Life


The acute toxicity threshold upon which the British Columbia criterion was derived is basically the same
as that originally determined by Mattice and Zittel (1976) (see Figure 1). The addition of more recent data
did not warrant readjustment of the threshold. While three new data points were addressed at or below
the acute toxicity threshold indicating possible toxic conditions, two of these data points (127, 128) were
considered questionable because other tests using the same organism over a similar exposure period
showed less toxicity. The other data point (118) was secondarily referenced as a personal communication,
but the original data were never published to verify this result.
Since it is not unreasonable to assume that there is probably an upper TRC concentration which will be
toxic to aquatic organisms regardless of the exposure duration, and because few data were available for
exposure periods less than about 30 minutes, a maximum criterion of 100 µg/L TRC, regardless of the
exposure period, was specified for freshwater situations.

b) Marine and Estuarine Aquatic Life


The acute toxicity threshold for British Col um bi a marine and estuarine aquatic life has been reduced
considerably from that originally determined by Mattice and Zittel (1976) to take into account more recent
data. Only two data points (121, 122) were excluded from the acute toxicity threshold which represents
the British Columbia criterion. While no irregularities regarding test procedures for these two values were
noted, the results were considered anomalous because other tests using the same organisms over the
same exposure period showed less toxicity.
For marine and estuarine situations, the acute toxicity threshold was well defined for exposure periods of
less than one minute. Nevertheless, to protect against the occurrence of any individual sample from
exceeding a concentration that may be harmful, a maximum criterion of 40 µg/L CPO, regardless of the
exposure period, was specified.

5. OTHER WATER-USE CATEGORIES


A search of the literature indicated that total residual chlorine criteria, developed specifically for the
protection of other water-use categories which include wildlife, livestock watering, irrigation, recreation
and aesthetics, and industry have been established only in a few instances. The small amount of
information pertaining to the toxic effects of TRC on water users in these categories generally indicates a

WATER QUALITY GUIDELINE SERIES No. WQG-10 24


high tolerance to TRC. Moreover, the presence of small to moderate amounts of TRC may actually be
beneficial in some cases because of its bactericidal qualities.
In practice, most waterbodies which are used for other purposes in addition to aquatic life will be
protected by the criteria for aquatic life because, in the case of multi-use waters, the criteria for the most
sensitive designated use will apply. For TRC, aquatic life is by far the most sensitive of the various water-
use categories.

5.1 Wildlife and Livestock Watering


No known TRC criteria have been established for these particular categories by other jurisdictions. Recent
U.S. EPA (1981, 1986) reviews of toxicological studies which used experimental animals to investigate
possible harmful effects to humans of TRC in drinking water generally indicate a high tolerance to TRC.
The U.S. EPA (1981, 1986) concluded that TRC is not bioaccumulated, nor is there any substantive
evidence that it is mutagenic, teratogenic or carcinogenic. In 1982, the U.S. EPA (1981) proposed an upper
limit of 10 mg/L TRC in drinking water for humans, based primarily on taste considerations. A similar
concentration likely would be acceptable for wildlife or livestock. However, because a concentration of
this magnitude would be extremely unlikely in ambient waters, TRC criteria for wildlife and livestock
watering are considered unnecessary.

5.2 Irrigation Water


A search of the literature revealed that criteria for TRC in irrigation water has been recommended by only
.one jurisdiction. In 1979, Manitoba (Manitoba Clean Environment Commission, 1979) recommended
acceptable limits of <50 µg/L TRC to protect crops and provide good quality irrigation water, and 50 µg/L
to protect against significant crop damage and provide acceptable quality irrigation water. It is not clear
how these levels were derived, as no rationale for these criteria was provided. Nevertheless, in 1983,
Manitoba (Manitoba Department of Environment and Workplace Safety and Health, 1983) dropped these
TRC requirements for irrigation water.
In a 1963 review of the literature, McKee and Wolf (1963) noted that no injury to terrestrial plants occurs
when irrigation water contains 50 µg/L TRC or less. However, they also reported that while roots from
tomato cuttings in chlorinated water were not affected by 5.0 mg/L TRC, growth was retarded at 10 mg/L.
In a more recent (1987) study, Frink and Bugbee (1987) exposed 11 species of potted foliage plants, 8
species of potted flowering plants, and 4 species of vegetable seedlings, in soilless media to irrigation
water containing 0, 2, 8, 18, 37 or 77 mg/L TRC. Growth and appearance were determined after 12 weeks
for potted plants and 6 weeks for seedlings. When compared to controls, growth of Pelargonium hortorum
(geranium) and begonia declined at 2 mg/L, capsicum (pepper) and tomato at 8 mg/L, Kalanchoe
blossfeldiana, lettuce, and Tradescantia albiflora at 18 mg/L, broccoli, Tagetes erecta (marigold), and
petunia at 37 mg/L, and Plectranthus coleoides (Swedish Ivy), Impatiens walleriana, Chrysalidocarpus
lutescens (Madagascar palm), and Hedera helix (English Ivy) at 77 mg/L. Germination of vegetable seeds
was not affected by any of the chlorine treatments. It was suggested that TRC was more likely a system!
C poison than a contact poison because chlorosis was general and not pronounced where water remained
on the foliage. The authors concluded that a TRC concentration of 1 mg/L should not adversely affect the
growth or appearance of most potted plants and vegetable seedlings grown in soilless media.
Based on these findings, it appears that there is considerable interspecies variation in the sensitivity of
plants to TRC. Furthermore, it seems likely that plants grown in soil are more tolerant to TRC than those
grown in soilless media, As compared to the more inert components of soilless media, the reducing agents

WATER QUALITY GUIDELINE SERIES No. WQG-10 25


of natural soil probably provide protection to plants by consuming much of the TRC thus preventing
uptake by the roots.
While a TRC concentration as high as 1 mg/L TRC in ambient waters is unlikely, it seems appropriate that
this concentration be considered a guideline for irrigation waters used for plants grown hydroponically or
in soilless media. Since plants grown in soil appear to be considerably more tolerant to TRC coupled with
the unlikely occurrence of TRC concentrations in the mg/L range in ambient waters, a criterion or guideline
for TRC in irrigation water was considered unnecessary for crops grown in soil.

WATER QUALITY GUIDELINE SERIES No. WQG-10 26


6. RESEARCH AND DEVELOPMENT NEEDS
o To improve the minimum detectable concentration for TRC and CPO to at least the criterion levels
and preferably below by modifying the amperometric technique as outlined in Section 2.3.
o To have individuals, experienced in the amperometric technique, on hand to perform on-site TRC
analyses when required.
o To obtain more toxicological data regarding the chronic exposure (>96 hours) of marine and
freshwater organisms to residual chlorine.

WATER QUALITY GUIDELINE SERIES No. WQG-10 27


Table 1. Chlorine requirements for various waters (White, 1972, as cited in Pierce, 1978; Palin, 1974, as cited in
Pierce, 1978).
Application Probable chlorine requirement (mg/l)
Algae control 3-5
Bacterial slime prevention 3-5
BOD reduction 10-20
Color removal 5-100 (or more depending upon type of wastewater)
Cyanide destruction 6.8 times cyanide content
Hydrogen sulfide removal 8.4 times H 2 S content (oxidation to sulfate)
Iron bacteria control 2 -10
Iron precipitation 0.63 times iron content
Manganese precipitation 1.3 times manganese content
Sewage – disinfection
Raw fresh domestic waste 8-15
Raw septic domestic waste 15-30
Primary sedimentation effluent 8-15
Recirculated biofilter effluent 5-8
Secondary biofilter effluent 3-8
Trickling filter effluent 3-10
Activated sludge effluent 2-8
Sand filtered effluent 2-5
Septic tank effluent 30-45

Water – disinfection
Cooling (once-through) 5-15 (intermittent)
Cooling (open recirculation) 3-5
Chilling 20
Washdown 50
Disinfection (tanks and mains) 10-50
Reproduced from Pierce (1978)

WATER QUALITY GUIDELINE SERIES No. WQG-10 28


Table 2. Summary of Toxicity of Chlorine to Freshwater Organisms
Concentration Duration
Data Point and Scientific Name Descriptive Name Effect Reference
(mg/l)* (min)
Plants:
Chlorophyta
50% decrease in National Research Council, 1976, as
1. Chlorella pyrenoidosa 0.18 1,440
growth cited in U.S. EPA, 1981
50% decrease in
2. Chlorella pyrenoidosa 0.4 300 Les, 1968, as cited in U.S. EPA, 1981
growth
3. Chlorella pyrenoidosa 0.6 1,200 43% mortality Les, 1968, as cited in U.S. EPA, 1981
4. Chlorella variegata 2 4,320 Decreased growth U.S. EPA, 1973
5. Scenedesmus obliquus 2 4,320 Decreased growth U.S. EPA, 1973
Mortality Knox et al., 1948, as cited in U.S. EPA,
6. Scenedesmus sp. 10 5,760
threshold 1986
Chrysophyta
7. Gomphonema parvulum 2 4,320 Decreased growth U.S. EPA, 1973
8. Nitzschia palea 2 4,320 Decreased growth U.S. EPA, 1973
Cyanophyta
9. Cylindrospermum licheniforme 2 4,320 Decreased growth U.S. EPA, 1973
10. Microcystis aeruginosa 2 4,320 Decreased growth U.S. EPA, 1973
Miscellaneous N.G. † 0.4 N.G. Stops Growth Servizi and Martens, 1974
Invertebrate animals:
Protozoa (many species) 2-8 <1 Some mortality Cohen, 1933, as cited in U.S. EPA, 1986
Arthropoda-crustacea
Gottlieb et al., 1981, as cited in U.S. EPA,
11. Asellus aquaticus Water louse 0.5 60 No reproduction
1986
50% mortality Crump and Guess, 1980, as cited in U.S.
12. Asellus racovitzas lsopod 0.613 1,440
(15°C) EPA, 1981
Chang et al., 1981, as cited in U.S. EPA,
13. Cyclops sp. 1 30 Some mortality
1986
Mortality Knox et al., 1948, as cited in U.S. EPA,
14. Daphnia magna Water flea 4 2,880
threshold 1986
EPA unpub., as cited in Alabaster and
15. Daphnia magna Water flea 0.125 240 100% mortality
Lloyd, 1982
Decreased
16. Daphnia magna Water flea 0.002 20,160 Done, 1961, as cited in U.S. EPA, 1986
reproduction ‡
17. Daphnia magna Water flea 0.5 4,320 100% mortality U.S. EPA, 1981

WATER QUALITY GUIDELINE SERIES No. WQG-10 29


Concentration Duration
Data Point and Scientific Name Descriptive Name Effect Reference
(mg/l)* (min)
Chang et al., 1981, as cited in U.S. EPA,
18. Daphna sp. Water flea 0.5 60 Some mortality
1986
50% mortality Crump and Guess, 1980, as cited in U.S.
19. Gammarus minus Scud 0.023 2,880
(15°C) EPA, 1981
Vogt et al., 1982, as cited in U.S. EPA,
20. Gammarus pseudolimnaeus Scud 0.035 151,200 80% mortality
1986
Vogt et al., 1982, as cited in U.S. EPA,
21. Gammarus pseudolimnaeus Scud 0.22 5,760 50% mortality
1986
Almost 0 Vogt et al., 1982, as cited in U.S. EPA,
22. Gammarus pseudolimnaeus Scud 0.0034 151,200
reproduction 1986
Decreased survival
23. Gammarus pseudolimnaeus Scud 0.054 161,280 Done, 1961, as cited in U.S. EPA, 1986

Decreased
24. Gammarus pseudolimnaeus Scud 0.019 201,600 Done, 1961, as cited in U.S. EPA, 1986
reproduction ‡
25. Gammarus pseudolimnaeus Scud 0.135 43,200 No effect ‡ Done, 1961, as cited in U.S. EPA, 1986
26. Gammarus pseudolimnaeus Scud 0.900 1,440 50% mortality ‡ Done, 1961, as cited in U.S. EPA, 1986
27. Orconectes virilis Crayfish 0.780 10,080 50% mortality ‡ Done, 1961, as cited in U.S. EPA, 1986
Arthropoda-insecta
Crump and Guess, 1980, as cited in U.S.
28. Centroptilum sp. Mayfly 0.071 1,440 50% mortality (6°C)
EPA, 1981
National Research Council, 1976, as
29. Chironomus sp. Midge larvae 7 1,440 80% mortality
cited in U.S. EPA, 1981, 1986
50% mortality Crump and Guess, 1980, as cited in U.S.
30. Ephemerella lata Mayfly 0.027 2,880
(15°C) EPA, 1981
50% mortality Crump and Guess, 1980, as cited in U.S.
31. Hydropsyche binda Caddisfly 0.396 482
(25°C) EPA, 1981
32. Hydropsyche sp. Caddisfly 0.55 10,080 50% mortality ‡ Done, 1961, as cited in U.S. EPA, 1986
50% mortality Crump and Guess, 1980, as cited in U.S.
33. Iron humeralis Mayfly 0.046 480
(15°C) EPA, 1981
Crump and Guess, 1980, as cited in U.S.
34. Isonychia sp. Mayfly 0.0093 2,880 50% mortality (6°C)
EPA, 1981
50% mortality Crump and Guess, 1980, as cited in U.S.
35. Peltoperla maria Stonefly 0.020 2,880
(15°C) EPA, 1981
36. Pteronarcys sp. Stonefly 0.480 4,320 50% mortality ‡ Done, 1961, as cited in U.S. EPA, 1986
50% mortality Crump and Guess, 1980, as cited in U.S.
37. Stenonema ithaca Mayfly 0.502 480
(25°C) EPA, 1981
Annelida

WATER QUALITY GUIDELINE SERIES No. WQG-10 30


Concentration Duration
Data Point and Scientific Name Descriptive Name Effect Reference
(mg/l)* (min)
38. Nais communis Oligochaete worm 1.0 35 95% mortality Moore and Calabrese, 1980
Hoyano et al., 1973, as cited in U.S. EPA,
39. Nais sp. Oligochaete worm 1.0 34 100% mortality
1986
Kanarek and Young, 1982, as cited in
40. Nais sp. Oligochaete worm 0.5 30 Disintegration
U.S. EPA, 1986
Nematoda
Patton et al., 1972, as cited in U.S. EPA,
Cheilobus quadrilabiatus Nematode worm 91 30 50% mortality
1986
Patton et al., 1972, as cited in U.S. EPA,
41. Diplogaster nudicapitatus Nematode worm 13.0 120 50% mortality
1986
Hoyano et al., 1973, as cited in U.S. EPA,
42. Trilobus gracilis Nematode 20.0 150 100% mortality
1986
Hoyano et al., 1973, as cited in U.S. EPA,
42. Trilobus gracilis Nematode (immature) 3.0 90 100% mortality
1986
Mollusca
43. Campeloma decisum Operculate snail >0.810 20,160 50% mortality ‡ Done, 1961, as cited in U.S. EPA, 1986
50% mortality Crump and Guess, 1980, as cited in U.S.
44. Goniobasis virginica Operculate snail 0.044 5,760
(25°C) EPA, 1981
50% mortality Crump and Guess, 1980, as cited in U.S.
45. Nitocris (Anculosa) carinata Operculate snail 0.086 5,760
(25°C) EPA, 1981
46. Physa inlegra Pulmonate snail >0.810 20,160 50% mortality ‡ Done, 1961, as cited in U.S. EPA, 1986
50% mortality Crump and Guess, 1980, as cited in U.S.
47. Physa heterostropha Pulmonate snail 0.258 5,760
(25°C) EPA, 1981
Vertebrate animals:
Amphibia
48. Rana catesbeiana Tadpole 2.4 510 100% mortality Muegge, 1956, as cited in U.S. EPA, 1986
Fish:
Clupeidae
49. Dorosoma cepedianum Gizzard shad 0.62 10 Some mortality Goldman et al., 1979
Salmonidae
Mortality
50. Oncorhynchus kisutch Coho salmon 0.016 1,440 Groethe and Eaton, 1975
threshold
Mortality
50. Oncorhynchus kisutch Coho salmon 0.004 5,760 Groethe and Eaton, 1975
threshold
Fish:

WATER QUALITY GUIDELINE SERIES No. WQG-10 31


Concentration Duration
Data Point and Scientific Name Descriptive Name Effect Reference
(mg/l)* (min)
76% mortality (free
51. Oncorhynchus kisutch Coho salmon fingerlings 0.2 1,152 Jacangelo and Olivieri, 1985
Ocl)
100% mortality
51. Oncorhynchus kisutch Coho salmon fingerlings 0.75 180 Jacangelo and Olivieri, 1985
(NH2Cl)
100% mortality
51. Oncorhynchus kisutch Coho salmon fingerlings 0.15 <48 Jacangelo and Olivieri, 1985
(NHCl2)
51. Oncorhynchus kisutch Coho salmon fingerlings 0.2 <1 Immediate distress Jacangelo and Olivieri, 1985
52. Oncorhynchus kisutch Coho salmon 0.230 720 50% mortality ‡ Done, 1961, as cited in U.S. EPA, 1986
Dennis et al., 1978, as cited in U.S. EPA,
53. Oncarhynchus tshawytscha Chinook salmon fry 1.0 12 100% mortality
1986
Strange et al., 1951, as cited in U.S. EPA,
54. Salmo gairdneri Rainbow trout 0.02 7,200 50% mortality ‡
1986
Strange et al., 1951, as cited in U.S. EPA,
54. Salmo gairdneri Rainbow trout 0.014 5,760 50% mortality ‡
1986
Strange et al., 1951, as cited in U.S. EPA,
54. Salmo gairdneri Rainbow trout 0.029 5,760 50% mortality ‡
1986
Mickey and Holden, 1971, as cited in
55. Salmo gairdneri Rainbow trout 0.7 2,220 100% mortality
U.S. EPA, 1981
Valenzuela, 1976, as cited in Alabaster
56. Salmo gairdneri Rainbow trout 0.2 300 50% mortality
and Lloyd, 1982
Valenzuela, 1976, as cited in Alabaster
56. Salmo gairdneri Rainbow trout 0.5 50 50% mortality
and Lloyd, 1982
Baker and Cole, 1974, as cited in Servizi,
57. Salmo gairdneri Rainbow trout 0.108 672 60% mortality
1979
Baker and Cole, 1974, as cited in Servizi,
57. Salmo gairdneri Rainbow trout 0.354 330 40% mortality
1979
Eichelsdoerfer et al., 1975, as cited in
58. Salmo gairdneri Rainbow trout 0.4 120 100% mortality
Moore and Calabrese, 1980
50% mortality (20- British Columbia Ministry of Health,
59. Salmo gairdneri Rainbow trout 0.04 5,760
80mm) 1982
Eichelsdoerfer et al., 1975, as cited in
60. Salmo gairdneri Rainbow trout fingerlings 0.2 240 100% mortality
Moore and Calabrese, 1980
Urbach and Gottlieb, 1946, as cited in
61. Salmo trutta Brown trout 0.35 1,440 Mortality §
U.S. EPA, 1981
Watson and Kibler, 1933, as cited in U.S.
62. Salmo trutta Brown trout 0.5 120 50% mortality
EPA, 1986
Watson and Kibler, 1933, as cited in U.S.
63. Salmo trutta Brown trout 0.09 180 50% mortality
EPA, 1986

WATER QUALITY GUIDELINE SERIES No. WQG-10 32


Concentration Duration
Data Point and Scientific Name Descriptive Name Effect Reference
(mg/l)* (min)
Watson and Kibler, 1933, as cited in U.S.
63. Salmo trutta Brown trout 0.05 360 50% mortality
EPA, 1986
Watson and Kibler, 1933, as cited in U.S.
63. Salmo trutta Brown trout 0.02 660 50% mortality
EPA, 1986
Sheldon and Lovell, 1949, as cited in U.S.
64. Salmo trutta Brown trout fingerlings 0.5 90 50% mortality
EPA, 1986
Mortality Wlodkowski and Rosenkranz, 1975, as
65. Salvelinus fontinalis Brook trout 0.01 10,080
threshold cited in U.S. EPA, 1986
Wlodkowski and Rosenkranz, 1975, as
65. Salvelinus fontinalis Brook trout 0.005 10,080 Activity depressed
cited in U.S. EPA, 1986
Mortality Rosenkranz, 1973, as cited in U.S. EPA,
66. Salvelinus fontinalis Brook trout 0.01 10,080
threshold 1986
Rosenkranz, 1973, as cited in U.S. EPA,
66. Salvelinus fontinalis Brook trout 0.05 2880 100% mortality
1986
British Columbia Ministry of Health,
67. Salvelinus fontinalis Brook trout 0.06 5,760 50% mortality
1982
Muhlendahl et al., 1978, as cited in U.S.
68. Salvelinus fontinalis Brook trout 10.0 1,440 100% mortality
EPA, 1986
69. Salvelinus fontinalis Brook trout 0.360 720 50% mortality ‡ Done, 1961, as cited in U.S. EPA, 1986
50% mortality Vogt et al., 1979, as cited in U.S. EPA,
70. Salvelinus fontinalis Brook trout 0.102 5,760
(20°C) 1986
Esocidae
100% mortality Mickey and Holden, 1971, as cited in
71. Esox lucius Northern pike 0.7 1,800
(temp 4.5°-7°C) U.S. EPA, 1981
100% mortality Wilkins et al., 1979, as cited in U.S. EPA,
72. Esox vermiculatus Grass pickerel 1 60
(after 24 hr) 1986
Catastomidae
Shy and Struba, 1980, as cited in U.S.
73. Catostomus commersonii White sucker 1 60 100% mortality
EPA, 1981
74. Catostomus commersonii White sucker 0.248 720 50% mortality ‡ Done, 1961, as cited in U.S. EPA, 1986
Cyprinidae
75. Carassius auratus Goldfish 1.6 240 100% mortality Muegge, 1956, as cited in U.S. EPA, 1986
76. N.G. Goldfish 1.0 480 Some mortality Bass and Heath, 1977
Kjellstrand et al., 1974, as cited in
77. N.G. Goldfish 0.3 1440 100% mortality
Moore and Calabrese, 1980
78. Carassius auratus Goldfish 1.0 5760 100% mortality U.S. EPA, 1981

WATER QUALITY GUIDELINE SERIES No. WQG-10 33


Concentration Duration
Data Point and Scientific Name Descriptive Name Effect Reference
(mg/l)* (min)
79. Cyprinus carpio Carp 0.72 65 Some mortality Goldman et al., 1979
Mickey and Holden, 1971, as cited in
80. Cyprinus carpio Carp 0.7 6000 80% mortality
U.S. EPA, 1981
Eaton et al., 1973, as cited in Moore and
Notemigonus crysoleucas Golden shiner >3,000 0.17 Death
Calabrese, 1980
81. Notemigonus crysoleucas Golden shiner 0.8 240 100% mortality Muegge, 1956, as cited in U.S. EPA, 1986
Wilkins et al., 1979, as cited in U.S. EPA,
82. Notropis cornutus Common shiner 0.7 76 100% mortality
1986
Wilkins et al., 1979, as cited in U.S. EPA,
83. Notropis rubellus Roseyface shiner 0.07 180 100% mortality
1986
Wilkins et al., 1979, as cited in U.S. EPA,
84. Notropis rubellus Roseyface shiner 0.7 79 100% mortality
1986
85. Pimephales notatus Minnow bluntnose 0.7 61 100% mortality Johnson, 1978
Vogt et al., 1982, as cited in U.S. EPA,
86. Pimephales promelas Fathead minnow larvae 0.108 43,200 60% mortality
1986
68% decreased Vogt et al., 1982, as cited in U.S. EPA,
87. Pimephales promelas Fathead minnow larvae 0.108 43,200
growth 1986
50% decreased Vogt et al., 1982, as cited in U.S. EPA,
88. Pimephales promelas Fathead minnow 0.043 10,080
spawning 1986
89. Pimephales promelas Fathead minnow 0.08-0.19 5,760 50% mortality Duce, 1969, as cited in U.S. EPA, 1981
Threshold
90. Pimephales promelas Fathead minnow 0.05 5,760 Duce, 1969, as cited in U.S. EPA, 1981
mortality
Strange et al., 1951, as cited in U.S. EPA,
91. Pimephales promelas Fathead minnow 0.02 7,200 50% mortality
1986
92. Pimephales promelas Fathead minnow 0.185 720 50% mortality ‡ Done, 1961, as cited in U.S. EPA, 1986
93. Pimephales promelas Fathead minnow 0.110 100,800 No spawning ‡ Done, 1961, as cited in U.S. EPA, 1986
Wilkins et al., 1979, as cited in U.S. EPA,
94. Rhinichthys atronaus Minnow 0.7 79 100% mortality
1986
Mickey and Holden, 1971, as cited in
95. Scardinius erythrophthalmus Rudd 0.7 2,460 100% mortality
U.S. EPA, 1981
Mickey and Holden, 1971, as cited in
96. Tinca tinca Tench 0.7 6,000 20% mortality
U.S. EPA, 1981
Ictaluridae
97. Ictalurus melas Black bullhead ~4.5 1,440 50% mortality Muegge, 1956, as cited in U.S. EPA, 1986
98. Ictalurus melas Black bullhead 1.36 25 Some mortality Goldman et al., 1979
Anguillidae

WATER QUALITY GUIDELINE SERIES No. WQG-10 34


Concentration Duration
Data Point and Scientific Name Descriptive Name Effect Reference
(mg/l)* (min)
Mortality Mickey and Holden, 1971, as cited in
99. Anguilla anguilla Eel 0.7 6,000
threshold U.S. EPA, 1981
Poeciliidae
Mortality Crump and Guess, 1982, as cited in U.S.
100. Gambusia affinis Mosquitofish 0.5-1.0 4,320
threshold EPA, 1986
Serranidae
Druckrey, 1968, as cited in U.S. EPA,
101. Morone saxatilis Striped bass 0.3 1,440 50% mortality
1981
Druckrey, 1968, as cited in U.S. EPA,
101. Morone saxatilis Striped bass 0.25 2,880 50% mortality
1981
Centrarchidae
102. Lepomis cyanellus Green sunfish 2 1,440 60% mortality Muegge, 1956, as cited in U.S. EPA, 1986
Rosenkranz, 1973, as cited in U.S. EPA,
Lepomis cyanellus Green sunfish 0.4 N.G. Eventual mortality
1986
Sheldon and Lovell, 1949, as cited in U.S.
103. Micropterus dolomieui Smallmouth bass 0.5 900 50% mortality
EPA, 1986
104. Micropterus salmoides Largemouth bass 0.494 1,440 50% mortality ‡ Done, 1961, as cited in U.S. EPA, 1986
105. Pomoxis nigromaculatus Black crappie 1.36 25 Some mortality Goldman et al., 1979
Percidae
106. Perca flavescens Yellow perch 0.72 65 Some mortality Goldman et al., 1979
107. Perca flavescens Yellow perch 0.365 720 50% mortality ‡ Done, 1961, as cited in U.S. EPA, 1986
108. Stizostedion vitreum vitreum Walleye 0.267 720 50% mortality ‡ Done, 1961, as cited in U.S. EPA, 1986
Miscellaneous
Eun et al., 1984, as cited in U.S. EPA,
109. N.G. Freshwater minnows, “killies” 0.3 120 No distress
1986
Reproduced from Mattice and Zittel (1976)

* Mg/l and ppm were treated as equivalent units.


† Not given
‡ Wastewater chlorination.
† Measured time of first “agitation.” But death occurred about 1 min later.

WATER QUALITY GUIDELINE SERIES No. WQG-10 35


Table 2a. Toxicity of Chlorine to Freshwater Organisms, Not Included in Review by Mattice and Zittel (1976)
Concentration Duration
Data Point and Scientific Name
Descriptive Name (µg/L)* (min) Effect Reference
Plants:
Chlorophyta
110. Stigeoclonium subsecundum 500 10080 100% mortality Trotter et al., 1987
Miscellaneous:
Phytoplankton 50% reduction in
111. N.G. 28 1440 Toetz et al., 1977
NO3 uptake
Phytoplankton 275 30 EC50 14C uptake Brooks and Liptak, 1979
112. N.G.
spring
Phytoplankton 160 30 EC50 14C uptake Brooks and Liptak, 1979
112. N.G.
summer
112. N.G. Phytoplankton 620 30 EC50 14C uptake fall Brooks and Liptak, 1979
Phytoplankton 760 30 EC50 14C uptake Brooks and Liptak, 1979
112. N.G.
winter
Periphyton 1 151200 Decrease in Carlson, 1976, as cited in Brungs, 1976
113. N.G.
biomass
Periphyton 4 151200 Decrease in Carlson, 1976, as cited in Brungs, 1976
113. N.G.
biomass
Periphyton 11 151200 Decrease in Carlson, 1976, as cited in Brungs, 1976
113. N.G.
biomass
Magnoliaphyta:
114. Myriophyllum spicatum Eurasion watermilfoil 50 5760 Reduced growth Watkins and Hammerschlag, 1984
Fanwort 150-3000 8640 Slight chlorosis Zimmerman and Berg, 1934, as cited in
115. Cabomba caroliniana
Alabaster and Lloyd, 1982
150-3000 8640 Slight chlorosis Zimmerman and Berg, 1934, as cited in
115. Elodea canadensis
Alabaster and Lloyd, 1982
Invertebrates:
Protozoa
500 60 Reduced Osborne, 1982
116. Many species community
respiration
Arthropoda-crustacea:
117. Daphnia magna Water flea 2 10080 LC50 Arthur et al., 1975
117. Daphnia magna Water flea 4-14 10080 LC50 Arthur et al., 1975
118. Daphnia magna Water flea 1 4320 100% mortality Arthur and Eaton, 1971

WATER QUALITY GUIDELINE SERIES No. WQG-10 36


Concentration Duration
Data Point and Scientific Name
Descriptive Name (µg/L)* (min) Effect Reference
119. Daphnia magna Water flea 70 630 100% mortality Ward et al., 1976
120. Daphnia magna Water flea 17 2880 LC50 Ward et al., 1976
120. Daphnia magna Water flea 11 2880 30% mortality Ward et al., 1976
121. Daphnia magna Water flea 45 2880 LC50 Ward and DeGraeve, 1980
122. Gammarus sp. Amphipod 1102 2880 LC50 Ward and DeGraeve, 1980
123. Epischura lacustris Copepod 63 2880 LC50 Ward and DeGraeve, 1980
Arthropoda-crustacea:
124. Limnocalanus macrurus Copepod 900 30 5% mortality Latimer et al., 1975
125. Cyclops bicuspidatus thomasi Copepod 500 30 5% mortality Latimer et al., 1975
126 Ass't copepod 41 2880 LC50 Ward and DeGraeve, 1980
Rotifer 32 60 LC50 Grossnickle, 1974, as cited in Brungs,
127. Keratella cochlearis
1976
Rotifer 27 240 LC50 Grossnickle, 1974, as cited in Brungs,
127. Keratella cochlearis
1976
Rotifer 13 1440 LC50 Grossnickle, 1974, as cited in Brungs,
127. Keratella cochlearis
1976
Rotifer 19 240 LC50 Beeton et al., 1976, as cited in Brungs,
128. Keratella cochlearis
1976
129. Pacifastacus trowbridgii Crayfish 31 525600 LC50 (Calculated) Larson et al., 1978
Anthropoda-insecta:
130. Hexaginia sp. Mayfly larvae 357 2880 LC50 Ward and DeGraeve, 1980
131. Order Plecoptera Stonefly larvae 781 2880 LC50 Ward and DeGraeve, 1980
Vertebrate Animals:
Fish:
Salmonidae
Coho salmon 3 120960 mild Buckley, 1976b
132. Oncorhynchus kisutch haematological
changes
Coho salmon 50 120960 severe Buckley, 1976b
132. Oncorhynchus kisutch haematological
changes
133. Oncorhynchus kisutch Coho salmon 23 30240 decrease in growth Larson, Hutchins, and Lamperti, 1977
133. Oncorhynchus kisutch Coho salmon 11 30240 decrease in growth Larson, Hutchins, and Lamperti, 1977

WATER QUALITY GUIDELINE SERIES No. WQG-10 37


Concentration Duration
Data Point and Scientific Name
Descriptive Name (µg/L)* (min) Effect Reference
Coho salmon 57 5760 LC50 Lamperti, 1976, as cited in U.S. EPA,
134. Oncorhynchus kisutch
1985
135. Oncorhynchus kisutch Coho salmon 59 5760 LC50 Ward and DeGraeve, 1978
Sockeye salmon 1000 18 100% mortality Servizi and Martens, 1974
136. Oncorhynchus nerka
LC50
136. Oncorhynchus nerka Sockeye salmon 200 180 LC50 Servizi and Martens, 1974
Vertebrate Animals:
Fish:
Salmonidae**
137. Salmo gairdneri Rainbow trout 69 5760 LC50 Ward and DeGraeve, 1978
138. Salmo gairdneri Rainbow trout 440 1440 LC50 Osborne et al., 1981
Rainbow trout 3860 8 Change in blood Zeithoun et al., 1977
139. Salmo gairdneri
characteristics
Rainbow trout 2470 19 Change in blood Zeithoun et al., 1977
139. Salmo gairdneri
characteristics
Rainbow trout 2750 20 Change in blood Zeithoun et al., 1977
139. Salmo gairdneri
characteristics
Rainbow trout 1090 29 Change in blood Zeithoun et al., 1977
139. Salmo gairdneri
characteristics
Rainbow trout 10 5760 LC50 (minimum) Cairns and Conn, 1979, as cited in
140. Salmo gairdneri
Servizi, 1979
Rainbow trout 40 5760 LC50 (average) Cairns and Conn, 1979, as cited in
140. Salmo gairdneri
Servizi, 1979
141. Salmo gairdneri Rainbow trout 990 30 LC50 (10°C) Brooks and Seegert, 1977
141. Salmo gairdneri Rainbow trout 940 30 LC50 (15°C) Brooks and Seegert, 1977
142. Salmo gairdneri Rainbow trout 132 5760 LC50 Marking et al., 1984
143. Salmo clarki Cutthroat trout (juv.) 75 5760 LC50 Larson et al., 1978
143. Salmo clarki Cutthroat trout (juv.) 82 5760 LC50 Larson et al., 1978
143. Salmo clarki Cutthroat trout (juv.) 83 5760 LC50 Larson et al., 1978
143. Salmo clarki Cutthroat trout (juv.) 95 5760 LC50 Larson et al., 1978
143. Salmo clarki Cutthroat trout (juv.) 94 5760 LC50 Larson et al., 1978
144. Salvelinus fontinalis Brook trout 107 5760 LC50 Larson, Hutchins, and Schlesinger, 1977
144. Salvelinus fontinalis Brook trout (al.) 91 5760 LC50 Larson, Hutchins, and Schlesinger, 1977
144. Salvelinus fontinalis Brook trout (fry) 82 5760 LC50 Larson, Hutchins, and Schlesinger, 1977

WATER QUALITY GUIDELINE SERIES No. WQG-10 38


Concentration Duration
Data Point and Scientific Name
Descriptive Name (µg/L)* (min) Effect Reference
144. Salvelinus fontinalis Brook trout (juv.) 91 5760 LC50 Larson, Hutchins, and Schlesinger, 1977
144. Salvelinus fontinalis Brook trout (juv.) 88 5760 LC50 Larson, Hutchins, and Schlesinger, 1977
145. Salvelinus namaycush Lake trout 60 5760 LC50 Ward and DeGraeve, 1978
Cyprindinae:
146. Carassius auratus Goldfish 153 5760 LC50 Ward and DeGraeve, 1978
146. Carassius auratus Goldfish 210 5760 LC50 Ward and DeGraeve, 1978
147. Carassius auratus Goldfish 490 1 lJ40 LC50* Tsai and McKee, 1980
147. Carassius auratus Goldfish 390 2880 LC50* Tsai and McKee, 1980
147. Carassius auratus Goldfish 360 4320 LC50* Tsai and McKee, 1980
147. Carassius auratus Goldfish 350 5760 LC50* Tsai and McKee, 1980
148. Notemigonus crysoleucas Golden shiner 40 5760 LC50 Ward and DeGraeve, 1978
149. Notropis anogenus Pugnose shiner 45 5760 LC50 Ward and DeGraeve, 1978
149. Notropis anogenus Pugnose shiner 29 5760 100% mortality Ward and DeGraeve, 1980
150. Notropis cornutus Common shiner 51 5760 LC50 Ward and DeGraeve, 1978
151. Notropis atherinoides Emerald shiner 350 40 LC50* Seegert et al., 1979
152. Notropis atherinoides Emerald shiner 260 15 LC50 Brooks et al., 1982
152. Notropis atherinoides Emerald shiner 180 30 LC50 Brooks et al., 1982
152. Notropis atherinoides Emerald shiner 100 120 LC50 Brooks et al., 1982
152. Notropis atherinoides Emerald shiner 100 30x4 LC50 Brooks et al., 1982
153. Notropis atherinoides Emerald shiner 230 30 LC50 Fandrei and Collins, 1979
154. Pimephales promelas Fatheat minnow 95 5760 LC50 Seegert et al., 1979
154. Pimephales promelas Fatheat minnow 82 5760 LC50 Seegert et al., 1979
155. Pimephales promelas Fatheat minnow 45 43200 LC50 Ward et al., 1976
156. Pimephales promelas Fatheat minnow 120 5760 LC50 Ward and DeGraeve, 1980
Ictaluridae:
Channel catfish 90 5760 LC50 Roseboom and Richey, 1977, as cited in
157. Ictalurus punctatus
U.S. EPA, 1985
158. Ictalurus punctatus Channel catfish 70 50400 Gill hyperplasia* Mitchell and Cech, 1983
Poeciliidae:
159. Gambusia affinis Mosquitofish 410 60 LC50 Mattice et al., 1981
Centrarchidae:

WATER QUALITY GUIDELINE SERIES No. WQG-10 39


Concentration Duration
Data Point and Scientific Name
Descriptive Name (µg/L)* (min) Effect Reference
Bluegill 330 5760 LC50 Roseboom and Richey, 1977, as cited in
160. Lepomis macrochirus
U.S. EPA, 1985
Bluegill 250 5760 LC50 Roseboom and Richey, 1977, as cited in
160. Lepomis macrochirus
U.S. EPA, 1985
Bluegill 180 5760 LC50 Roseboom and Richey, 1977, as cited in
160. Lepomis macrochirus
U.S. EPA, 1985
161. Lepomis sp. Sunfish 278 5760 LC50 Ward and DeGraeve, 1978
161. Lepomis sp. Sunfish 195 5760 LC50 Ward and DeGraeve, 1978
162. Micropterus salmoides Largemouth bass 241 5760 LC50 Ward and DeGraeve, 1978
163. Pomoxis sp. Crappie 127 5760 LC50 Ward and DeGraeve, 1978
Percidae:
164. Stizostedion vitreum Walleye 108 5760 LC50 Ward and DeGraeve, 1978
165. Perca flavescens Yellow perch 700 30 LC50 (30°C) Brooks and Seegert, 1977
165. Perca flavescens Yellow perch 8000 30 LC50 (10°C) Brooks and Seegert, 1977
N.G. Not Given
* Chloramines tested or suspected
** Taxonomic classifications for rainbow trout (Salmo gairdneri) and cutthroat trout (Salmo clarki) recently have been changed to Oncorhynchus mykiss and Oncorhynchus clarki, respectively.
juv. Juvenile
Al. Alevin

WATER QUALITY GUIDELINE SERIES No. WQG-10 40


Table 3. Summary of Data on Toxicity of Chlorine to Marine Organisms
Concentration Duration
Data Point and Scientific Name Descriptive Name Effect Reference
(mg/l)* (min)
Plants:
71% decrease in
1. N.G.† Phytoplankton <0.1 240 Johnson, 1978
productivity
50% decrease in
N.G. Phytoplankton 0.03 N.G. Latimer et al., 1975
photosynthesis ‡
Chlorophyta
Beeton et al., 1976, as cited in Brungs,
2. Chlamydomonas sp. 1.5 5-10 Decreased growth
1976
50% decrease in
3. Dunaliella tertiolecta 0.11 1,440 Ward et al., 1976
growth
Chrysophyta
50% decrease in
4. Asterionella japonica 0.4 0.27 Esvelt et al., 1973
growth
50% decrease in
4. Asterionella japonica 0.2 2 Esvelt et al., 1973
growth
50% decrease in
5. Chaetoceros decipiens 0.14 1,440 Ward et al., 1976
growth
50% decrease in
6. Chaetoceros didymum 0.125 1,440 Ward et al., 1976
growth
50% decrease in
7. Detonula confervacea 0.8 0.6 Esvelt et al., 1973
growth
50% decrease in
8. Skeletonema costatum 0.095 1,440 Ward et al., 1976
growth
50% decrease in
8. Skeletonema costatum 0.6 1.7 Esvelt et al., 1973
growth
50% decrease in
9. Thalassiosira nordenskioeldii 0.195 1,440 Ward et al., 1976
growth
50% decrease in
10. Thalassiosira pseudonana 0.075 1,440 Ward et al., 1976
growth
50% decrease in
10. Thalassiosira pseudonana 0.2 6.8 Ward et al., 1976
growth
50% decrease in
10. Thalassiosira pseudonana 0.5 0.3 Esvelt et al., 1973
growth
50% decrease in
11. Thalassiosira rotula 0.33 1,440 Bass and Heath, 1977)
growth

WATER QUALITY GUIDELINE SERIES No. WQG-10 41


Concentration Duration
Data Point and Scientific Name Descriptive Name Effect Reference
(mg/l)* (min)
Chrysophyceae
50% decrease in
12. Monochrysis lutheri 0.2 1,440 Ward et al., 1976
growth
50% decrease in
13. Rhodomonas baltica 0.11 1,440 Ward et al., 1976
growth
Phaeophyta
50% decrease in Wester and Rawles, 1979, as cited in
14. Macrocystis pyrifera Giant kelp 5-10 5,760
photosynthesis Watkins and Hammerschlag, 1984
lnvertebrate animals:
Cnidaria
N.G. Sea anemone 1.0 21,600 No effect Capuzzo, Goldman, et al., 1977
Slight decrease in
15. Bimeria franciscana Hydroid 2.5 180 Larson et al., 1978
growth
Annelida
17% decrease in
16. Phragmatopoma californica Polychaete worm 0.2 5 Capuzzo, 1979
sperm motility ‡
70% decrease in
17. Phragmatopoma californica Polychaete worm 0.4 5 Capuzzo, 1979
sperm motility ‡
Mollusca
~46% decrease in
Crassostrea virginica Oyster 0.2 N.G. Arthur and Eaton, 1971
ciliary beat rate
18. Crassostrea virginica Oyster 1.0 20-90 Pumping threshold Arthur and Eaton, 1971
50% decrease in
19. Crassostrea virginica Oyster 0.18 4,320 Roberts et al., 1975
time open
Hawk and Block, in press, as cited in
20. Ostrea edulis Oyster larvae 0.5 2 Swimming stopped
Scott, 1981
Whigham and Simpson, 1978, as cited in
N.G. Oysters 2.5 10 No effect (30°C)
Watkins and Hammerschlag, 1984
21. Mytilus edulis Mussel 1.0 21,600 100% mortality Capuzzo, Goldman, et al., 1977
21. Mytilus edulis Mussel 2.5 7,200 100% mortality Capuzzo, Goldman, et al., 1977
Young won't
Mytilus edulis Mussel 0.02-0.05 N.G. attach-attached Mattice and Zittel, 1976
ones will move
Crepidula and Littorina Gastropods 0.2 N.G. Stops growth Roberts and Gleeson, 1978
30% mortality @ Dychdala, 1977, as cited in U.S. EPA,
22. Acartia tonsa Copepod 0.75 2
25°C after 96 hr 1986

WATER QUALITY GUIDELINE SERIES No. WQG-10 42


Concentration Duration
Data Point and Scientific Name Descriptive Name Effect Reference
(mg/l)* (min)
70% mortality @ Dychdala, 1977, as cited in U.S. EPA,
23. Acartia tonsa Copepod 0.75 2
25°C after 96 hr 1986
24. Acartia tonsa Copepod 1 120 50% mortality Ward et al., 1976
24. Acartia tonsa Copepod 10.0 0.7 50% mortality Ward et al., 1976
90% mortality-after
25. Acartia tonsa Copepod 2.5 5 Dinnel et al., 1981
3 hr
26. Eurytemora affinis Copepod 1 360 50% mortality Ward et al., 1976
26. Eurytemora affinis Copepod 10.0 2 50% mortality Ward et al., 1976
27. Pseudodiaptomus coronatus Copepod 2.5 45 50% mortality Ward et al., 1976
27. Pseudodiaptomus coronatus Copepod 10 5 50% mortality Ward et al., 1976
80% mortality-after
28. Balanus improvisus Barnacle larvae 2.5 5 Dinnel et al., 1981
3 hr
29. N.G. Barnacles 1.0 21,600 Most dead Capuzzo, Goldman, et al., 1977
Threshold Hawk and Block, in press, as cited in
30. Elminius modestus Barnacle nauplii 0.5 10
mortality Scott, 1981
Heavy losses-no Hawk and Block, in press, as cited in
31. Elminius modestus Barnacle nauplii 1 10
growth Scott, 1981
No mortality after
32. Corophium sp. Tube dwelling amphipod 10 410 Esvelt et al., 1973
24 hr
25% mortality after
33. Gammarus tigrinus Amphipod 2.5 180 Dinnel et al., 1981
96 hr
34. Melita nitida Amphipod 2.5 120 50% mortality Dinnel et al., 1981
35. Melita nitida Amphipod 2.5 5 Some mortality Dinnel et al., 1981
36. Callinectes sapidus Blue crab 10 1,140 50% mortality Roberts et al., 1975
36. Callinectes sapidus Blue crab 0.1 5,760 50% mortality Roberts et al., 1975
37. Crangon septemspinosus Sand shrimp 0.15 900 50% mortality Roberts et al., 1975
38. Crangon septemspinosus Sand shrimp larvae 5 10 42% mortality Ward et al., 1976
38. Crangon septemspinosus Sand shrimp larvae 10 5 55% mortality Ward et al., 1976
98% mortality-after
39. Palaemonetes pugio Grass shrimp 2.5 180 Dinnel et al., 1981
96 hr
Ectoprocta
40. Bugula sp. 2.5 2,880 100% mortality Capuzzo, Goldman, et al., 1977
40. Bugula sp. 10 1,440 100% mortality Capuzzo, Goldman, et al., 1977
Echinodermata

WATER QUALITY GUIDELINE SERIES No. WQG-10 43


Concentration Duration
Data Point and Scientific Name Descriptive Name Effect Reference
(mg/l)* (min)
1-6% fertilization
41. Strongylocentrotus purpuratus Sea urchin 0.125 5 Capuzzo, 1979
success ‡
78% fertilization
42. Urechis caupo Echiuroid 0.2 5 Capuzzo, 1979
success‡
0% fertilization
43. Urechis caupo Echiuroid 0.4 5 Capuzzo, 1979
success‡
Chordata
44. Botryllus sp. 10 1,440 100% mortality Capuzzo, Goldman, et al., 1977
45. Molgula sp. 1 4,320 100% mortality Capuzzo, Goldman, et al., 1977
Vertebrate animals:
Pleuronectidae
46. Limanda ferruginea Yellowtail flounder 0.1 1,440 50% mortality Ward et al., 1976
47. Pleuronectes platessa Plaice larvae 0.028 5,760 50% mortality Cairns et al., 1975
47. Pleuronectes platessa Plaice larvae 0.05 460 50% mortality Cairns et al., 1975
47. Pleuronectes platessa Plaice larvae 0.075 75 50% mortality Cairns et al., 1975
48. Pleuronectes platessa Plaice larvae 0.25 4,320 Mortality threshold Cairns et al., 1975
49. Pseudopleuronectes americanus Winter flounder 2.5 15 50% mortality Ward et al., 1976
49. Pseudopleuronectes americanus Winter flounder 10 0.3 50% mortality Ward et al., 1976
50. Pseudopleuronectes americanus Winter flounder eggs 10 20 No mortality Ward et al., 1976
Salmonidae
51. Oncorhynchus gorbuscha Pink salmon 0.05 5,760 50% mortality Jacangelo and Olivieri, 1985
50% mortality
52. Oncorhynchus gorbuscha Pink salmon 0.5 7.5 U.S. EPA, 1981
(13.6°C)
50% mortality
52. Oncorhynchus gorbuscha Pink salmon 0.25 15 U.S. EPA, 1981
(13.6°C)
53. Oncorhynchus kisutch Coho salmon 0.08 <7,200 50% mortality Jacangelo and Olivieri, 1985
Distressed-no
54. Oncorhynchus tshawytscha Chinook salmon 0.1 60 Jacangelo and Olivieri, 1985
mortality
55. Oncorhynchus tshawytscha Chinook salmon 0.25 130 Mortality threshold Jacangelo and Olivieri, 1985
55. Oncorhynchus tshawytscha Chinook salmon 1 23 Mortality threshold Jacangelo and Olivieri, 1985
50 % mortality
56. Oncorhynchus tshawytscha Chinook salmon 0.5 7.5 U.S. EPA, 1981
(11.7°C)
50 % mortality
56. Oncorhynchus tshawytscha Chinook salmon 0.25 30 U.S. EPA, 1981
(11.7°C)

WATER QUALITY GUIDELINE SERIES No. WQG-10 44


Concentration Duration
Data Point and Scientific Name Descriptive Name Effect Reference
(mg/l)* (min)
Threshold
57. N.G. Young salmon 0.05 33,123 Jacangelo and Olivieri, 1985
mortality
Atherinidae
58. Menidia menidia Atlantic silverside 0.58 90 50% mortality Goldman and Quinby, 1979
58. Menidia menidia Atlantic silverside 1.2 30 50% mortality Goldman and Quinby, 1979
Clupeidae
59. Alosa aestivalis Blueback herring 0.67 60 50% mortality Goldman and Quinby, 1979
59. Alosa aestivalis Blueback herring 1.2 15 50% mortality Goldman and Quinby, 1979
60. Brevoortia tyrannus Atlantic menhaden 0.22 60 50% mortality Brungs, 1973
60. Brevoortia tyrannus Atlantic menhaden 0.7 10 50% mortality Brungs, 1973
61. Brevoortia tyrannus Atlantic menhaden 0.21 300 50% mortality Goldman and Quinby, 1979
61. Brevoortia tyrannus Atlantic menhaden 1.2 30 50% mortality Goldman and Quinby, 1979
62. Brevoortia tyrannus Atlantic menhaden larvae 0.5 3 0 mortality Ward and DeGraeve, 1980
Gasterosteidae
63. Gasterosteus aculeatus † Threespine stickle-back 0.09-0.13 5,760 50% mortality Watkins and Hammerschlag, 1984
Ameiuridae
64. Ameiurus catus White catfish 0.1 2,880 50% mortality Watkins and Hammerschlag, 1984
Cyprinidae
65. Notemigonus chrysoleucas Golden shiner 0.03-0.23 5,760 50% mortality Watkins and Hammerschlag, 1984
Bothidae
Threshold
66. Paralichthys sp. Flounder 0.3 5 Ward and DeGraeve, 1980
mortality
Mugilidae
Threshold
67. Mugil cephalus Striped mullet juveniles 0.3 5 Ward and DeGraeve, 1980
mortality
Miscellaneous
Slight irritant Grossnickle, 1974, as cited in Brungs,
68. N.G. Marine fish 1.0 <1
response 1976
Reproduced from Mattice and Zittel (1976)

mg/l and ppm were treated as equivalent units.


† Not given.
‡ Wastewater chlorination.

WATER QUALITY GUIDELINE SERIES No. WQG-10 45


Table 3a. Toxicity of Chlorine to Marine Organisms, Not Included in Review by Mattice and Zittel (1976)
Concentration Duration
Data Point and Scientific Name Descriptive Name Effect Ref.
(µg/L) (Min.)
Plants:
Miscellaneous:
EC50 (inhibition of Bender et al., 1977, as cited in Ho and
69. N.G Nanoplankton 10 240
carbon uptake Roberts, 1985
Davis and Coughlan, 1978, as cited in Ho
EC50
and Roberts, 1985; Roberts and
70. N.G. Phytoplankton 9 120 (photosynthetic
Illowsky, n.d., as cited in Ho and
inhibition)
Roberts, 1985
EC50
71. N.G. Phytoplankton 10 1440 (photosynthetic Eppley et al., 1976
inhibition)
photosynthetic
71. N.G. Phytoplankton 70 N.G. Ho and Roberts, 1985
inhibition
50% chlorophyll Stone et al., 1973, as cited in Brungs,
71. N.G. Phytoplankton 60 N.G.
reduction 1976
2-3 day delay in
72. N.G. Phytoplankton 20 120-180 Goldman and Quinby, 1979
peak ATP (10°CΔT)
2-3 day delay in
73. N.G. Phytoplankton 60 120-180 Goldman and Quinby, 1979
peak ATP (11°CΔT)
5 day delay in peak
74. N.G. Phytoplankton 80 120-180 Goldman and Quinby, 1979
ATP (17.5°CΔT)
shifts in
75. N.G. Phytoplankton 50-100 43200-86400 composition of Sanders and Ryther, 1979
phyto community
Invertebrates:
Mollusca:
76. Crassostrea virginica E. Oyster (larvae) 750 120 LC50 Roberts et al., 1975
76. Crassostrea virginica E. Oyster (larvae) 270 1440 LC50 Roberts et al., 1975
76. Crassostrea virginica E. Oyster (larvae) 110 2880 LC50 Roberts et al., 1975
77. Crassostrea virginica E. Oyster (larvae) 26 2880 LC50 Roberts and Gleeson, 1978
EC50
78. Crassostrea virginica E. Oyster (spat) 23 5760 Roberts et al., 1975
(extrapolated)
79. Crassostrea virginica E. Oyster (adult) 140 36000 LC10 (fall) Scott and Middaugh, 1977
80. Crassostrea virginica E. Oyster (adult) 140 64800 LC10 (winter) Scott and Middaugh, 1977
81. Crassostrea virginica E. Oyster (adult) 650 21600 LC10 (spring) Scott and Middaugh, 1977

WATER QUALITY GUIDELINE SERIES No. WQG-10 46


Concentration Duration
Data Point and Scientific Name Descriptive Name Effect Ref.
(µg/L) (Min.)
82. Crassostrea virginica E. Oyster (spat) 250 120960 LC80 U.S. EPA, 1981
83. Crassostrea virginica E. Oyster (spat) 125 120960 Retarded growth U.S. EPA, 1981
Roosenburg, Rhoderick, Block, Kennedy,
84. Crassostrea virginica E. Oyster (larvae) 300 2880 LC50
Gullans, et al., 1980
Roosenburg, Rhoderick, Block, Kennedy,
84. Crassostrea virginica E. Oyster (larvae) 80 4320 LC50
Gullans, et al., 1980
Roosenburg, Rhoderick, Block, Kennedy,
84. Crassostrea virginica E. Oyster (larvae) 60 5760 LC50
Gullans, et al., 1980
Reduced adductor Hawk and Block, in press, as cited in
85. Crassostrea virginica E. Oyster (adult) 4 5760
muscle glycogen Scott, 1981
86. Crassostrea virginica E. Oyster (larvae) 120 30 LC50 (0°CΔT) Capuzzo, 1979
86. Crassostrea virginica E. Oyster (larvae) 10 30 LC50 (0°CΔT)* Capuzzo, 1979
87. Crassostrea virginica E. Oyster (larvae) 80 30 LC50 (5°CΔT) Capuzzo, 1979
87. Crassostrea virginica E. Oyster (larvae) <10 30 LC50 (5°CΔT)* Capuzzo, 1979
LC50 Roosenburg, Rhoderick, Block, Kennedy,
88. Mya arenaria Soft clam (larvae) 350 720
(approximate) and Vreenegoor, 1980
LC50 Roosenburg, Rhoderick, Block, Kennedy,
88. Mya arenaria Soft clam (larvae) 270 960
(approximate) and Vreenegoor, 1980
LC50 Roosenburg, Rhoderick, Block, Kennedy,
89. Mya arenaria Soft clam (pediveligers) 500 1440
(approximate) and Vreenegoor, 1980
LC50 Roosenburg, Rhoderick, Block, Kennedy,
89. Mya arenaria Soft clam (pediveligers) 250 2880
(approximate) and Vreenegoor, 1980
LC50 Roosenburg, Rhoderick, Block, Kennedy,
89. Mya arenaria Soft clam (pediveligers) 165 4320
(approximate) and Vreenegoor, 1980
LC50 Roosenburg, Rhoderick, Block, Kennedy,
89. Mya arenaria Soft clam (pediveligers) 125 5760
(approximate) and Vreenegoor, 1980
EC50 (retarded
90. Mercenaria mercenaria Hard clam (larvae) 6 2880 Roberts et al., 1975
development)
LC50
91. Mercenaria mercenaria Hard clam (larvae) 1-5 2880 Roberts et al., 1975
(extrapolated)
Inhibition of shell
92. Protothaca staminea Littleneck clam (adult) 25 345600 Hillman et al., 1979
growth
Arthropoda crustacea:
93. Brachionus plicatilis Rotifer 180 30 LC50 (0°CΔT) Capuzzo, 1979
94. Brachionus plicatilis Rotifer 20 30 LC50 (0°CΔT)* Capuzzo, 1979
95. Brachionus plicatilis Rotifer 90 30 LC50 (5°CΔT)* Capuzzo, 1979

WATER QUALITY GUIDELINE SERIES No. WQG-10 47


Concentration Duration
Data Point and Scientific Name Descriptive Name Effect Ref.
(µg/L) (Min.)
96. Brachionus plicatilis Rotifer <10 30 LC50 (5°CΔT)* Capuzzo, 1979
97. Acartia tonsa Copepod <50 1440 LC50* Roberts et al., 1975
97. Acartia tonsa Copepod <50 2880 LC50* Roberts et al., 1975
98. Acartia tonsa Copepod 29 2880 LC50 Roberts and Gleeson, 1978
98. Acartia tonsa Copepod 67 2880 LC50 Roberts and Gleeson, 1978
99. Acartia tonsa Copepod 820 30 LC50 (0°CΔT) Capuzzo, 1979
100. Acartia tonsa Copepod 320 30 LC50 (0°CΔT)* Capuzzo, 1979
101. Acartia tonsa Copepod 860 30 LC50 (5°CΔT) Capuzzo, 1979
102. Acartia tonsa Copepod 320 30 LC50 (5°CΔT)* Capuzzo, 1979
103. Palaemonetes pugio Glass shrimp 380 1440 LC50* Roberts et al., 1975
103. Palaemonetes pugio Glass shrimp 220 5760 LC50* Roberts et al., 1975
104. Crangon nigricauda Shrimp (adult) 134 5760 LC50 Thatcher, 1977
105. Pandalus goniurus Shrimp (adult) 90 5760 LC50 Thatcher, 1977
106. Pandalus danae Shrimp (juv. & adult) 178 5760 LC50 Thatcher, 1977
107. Anonyx sp. Amphipod (adult) 145 5760 LC50 Thatcher, 1977
108. Pontogeneia sp. Amphipod (juv.) 687 5760 LC50 Thatcher, 1977
109. Neomysis sp. Mysid (adult) 162 5760 LC50 Thatcher, 1977
110. Panopeus herbstii Crab (larvae) 24 5760 LC50 Roberts, 1977
111. Pagurus longicarpus Crab (larvae) <400 1440 LC50 Roberts, 1977
111. Pagurus longicarpus Crab (larvae) 160 2880 LC50 Roberts, 1977
111. Pagurus longicarpus Crab (larvae) 62 5760 LC50 Roberts, 1977
111. Pagurus longicarpus Crab (larvae) 54 7200 LC50 Roberts, 1977
112. Hemigrapsus nudus Crab (juv. & adult) 1418 5760 LC50 Thatcher, 1977
113. Hemigrapsus oregonsis Crab (juv. & adult) 1418 5760 LC50 Thatcher, 1977
Disruption of Mg
114. Cancer productus Crab (adult) 690 5760 Roesijadi et al., 1979
regulation
115. Hornarus americanus Lobster (larvae) 300 30 LC50* Capuzzo, 1977
116. Hornarus americanus Lobster (larvae) 2900 30 LC50 Capuzzo, 1977
EC50 reduced
117. Hornarus americanus Lobster (larvae) 30 60 Capuzzo, 1977
respiration rate*
EC50 reduced
118. Hornarus americanus Lobster (larvae) 80 60 Capuzzo, 1977
respiration rate
119. Homarus americanus Lobster (larvae) 2900 60 LC50 Goldman et al., 1977

WATER QUALITY GUIDELINE SERIES No. WQG-10 48


Concentration Duration
Data Point and Scientific Name Descriptive Name Effect Ref.
(µg/L) (Min.)
119. Homarus americanus Lobster (larvae) 3950 60 LC50 Goldman et al., 1977
120. Homarus americanus Lobster (larvae) 300 60 LC50* Goldman et al., 1977
120. Homarus americanus Lobster (larvae) 1300 60 LC50* Goldman et al., 1977
Echinodermata:
EC50 (egg
121. Dendraster excentricus Sand dollar 2 5 fertilization Dinnel et al., 1981
success)
EC50 (egg
121. Dendraster excentricus Sand dollar 13 5 fertilization Dinnel et al., 1981
success)
EC50 (egg
122. Strongylocentrotus droebachiensis Sea urchin 5 5 fertilization Dinnel et al., 1981
success)
Vertebrates:
Fish:
Pleuronectidae:
123. Pseudopleuronectes americanus Winter flounder (juv.) 550 30 100% mortality Capuzzo, Davidson, et al., 1977
124. Pseudopleuronectes americanus Winter flounder (juv.) 2550 30 100% mortality* Capuzzo, Davidson, et al., 1977
125. Pseudopleuronectes americanus Winter flounder (juv.) 200 30 Stress Capuzzo, Davidson, et al., 1977
126. Pseudopleuronectes americanus Winter flounder (juv.) 1500 30 Stress* Capuzzo, Davidson, et al., 1977
127. Parophrys vetulus English sole. (juv.) 73 5760 LC50 Thatcher, 1977
Salmonidae:
128. Oncorhynchus kisutch Coho salmon (juv.) 70 5760 LC50* Buckley, 1976a
Maximum safe
129. Oncorhynchus kisutch Coho salmon (juv.) 3-9 120960 Buckley et al., 1976
concentration*
130. Oncorhynchus kisutch Coho salmon (smolts) 270 7.5 LC50 (7.3°CΔT) Stober et al., 1980
130. Oncorhynchus kisutch Coho salmon (smolts) 179 15 LC50 (7.3°CΔT) Stober et al., 1980
130. Oncorhynchus kisutch Coho salmon (smolts) 129 30 LC50 (7.3°CΔT) Stober et al., 1980
130. Oncorhynchus kisutch Coho salmon (smolts) 130 60 LC50 (7.3°CΔT) Stober et al., 1980
Avoidance
- Oncorhynchus kisutch Coho salmon (smolts) 2 N.G. Stober et al., 1980
threshold
131. Oncorhynchus kisutch Coho salmon (juv.) 32 5760 LC50 (5°CΔT) Thatcher, 1977
132. Oncorhynchus gorbuscha Pink salmon (juv.) >23 5760 LC50 Thatcher, 1977
133. Oncorhynchus tshawytscha Chinook salmon (juv.) >38 5760 LC50 Thatcher, 1977

WATER QUALITY GUIDELINE SERIES No. WQG-10 49


Concentration Duration
Data Point and Scientific Name Descriptive Name Effect Ref.
(µg/L) (Min.)
Antherinidae:
134. Menidia menidia Atlantic silverside 95 1440 LC50 Roberts et al., 1975
134. Menidia menidia Atlantic silverside 38 2880 LC50 Roberts et al., 1975
134. Menidia menidia Atlantic silverside 37 5760 LC50 Roberts et al., 1975
135. Menidia menidia Atlantic silversides (egg) 120 1440 LC5 Morgan and Prince, 1977
135. Menidia menidia Atlantic silversides (egg) 160 2880 LC5 Morgan and Prince, 1977
136. Menidia menidia Atlantic silversides (egg) 380 1440 LC50 Morgan and Prince, 1977
136. Menidia menidia Atlantic silversides (egg) 300 2880 LC50 Morgan and Prince, 1977
137. Menida beryllina Tidewater silversides (egg) 150 1440 LC5 Morgan and Prince, 1977
137. Menida beryllina Tidewater silversides (egg) 140 2880 LC5 Morgan and Prince, 1977
138. Menida beryllina Tidewater silversides (egg) 230 1440 LC50 Morgan and Prince, 1977
138. Menida beryllina Tidewater silversides (egg) 250 2880 LC50 Morgan and Prince, 1977
Percichthyidae:
Middaugh et al., 1977, as cited in U.S.
139. Morone saxatilis Striped bass (larvae) 40 2880 Incipient LC50
EPA, 1985
Middaugh et al., 1977, as cited in U.S.
139. Morone saxatilis Striped bass (larvae) 70 2880 Incipient LC50
EPA, 1985
140. Morone saxatilis Striped bass (eggs) 270 120 LC50 Burton et al., 1979
141. Morone saxatilis Striped bass (prolarvae) 160 5 LC50 Burton et al., 1979
141. Morone saxatilis Striped bass (prolarvae) 190 240 LC50 Burton et al., 1979
141. Morone saxatilis Striped bass (prolarvae) 120 120 LC50 Burton et al., 1979
142. Morone saxatilis Striped bass (egg) 48 2880 LC50 Morgan and Prince, 1977
142. Morone saxatilis Striped bass (egg) 60 1440 LC50 Morgan and Prince, 1977
143. Morone saxatilis Striped bass (egg) 220 2880 LC50 Morgan and Prince, 1977
144. Morone saxatilis Striped bass (larvae) 68 1440 LC50 Morgan and Prince, 1977
145. Morone americana White perch (egg) 150 4560 LC50 Morgan and Prince, 1977
146. Morone americana White perch (larvae) 200 1440 LC50 Morgan and Prince, 1977
147. Morone americana White perch (egg) 270 4560 LC50 Morgan and Prince, 1977
148. Morone americana White perch (larvae) 310 1440 LC50 Morgan and Prince, 1977
Clupeidae:
149. Alosa aestivalis Blueback herring (egg) 150 4800 LC50 Morgan and Prince, 1977
150. Alosa aestivalis Blueback herring (egg) 330 4800 LC50 Morgan and Prince, 1977

WATER QUALITY GUIDELINE SERIES No. WQG-10 50


Concentration Duration
Data Point and Scientific Name Descriptive Name Effect Ref.
(µg/L) (Min.)
151. Alosa aestivalis Blueback herring (larvae) 75 2880 LC50 Morgan and Prince, 1977
152. Alosa aestivalis Blueback herring (larvae) 250 2880 LC50 Morgan and Prince, 1977
153. Clupea harengus Pacific herring (juv) 65 5760 LC50 Thatcher, 1977
Embiotocidae:
154. Cymatogaster aggregata Shiner perch (juv.) 664 7.5 LC50 (7.5°CΔT) Stober et al., 1980
154. Cymatogaster aggregata Shiner perch (juv.) 220 60 LC50 (7.5°CΔT) Stober et al., 1980
155. Cymatogaster aggregata Shiner perch (juv.) 410 15 LC50 (3.2°CΔT) Stober et al., 1980
155. Cymatogaster aggregata Shiner perch (juv.) 302 30 LC50 (3.2°CΔT) Stober et al., 1980
Avoidance
- Cymatogaster aggregata Shiner perch (juv.) 175 N.G. Stober et al., 1980
threshold
156. Cymatogaster aggregata Shiner perch (juv & adult) 71 5760 LC50 Thatcher, 1977
Gobiidae:
157. Gobiosoma bosci Naked gody 640 120 LC50 Roberts et al., 1975
157. Gobiosoma bosci Naked goby 80 1440 LC50 Roberts et al., 1975
157. Gobiosoma bosci Naked goby 80 2880 LC50 Roberts et al., 1975
157. Gobiosoma bosci Naked goby 80 5760 LC50 Roberts et al., 1975
Syngnathidae:
158. Syngnathus fuscus N. pipefish 280 1440 LC50 Roberts et al., 1975
158. Syngnathus fuscus N. pipefish 270 2880 LC50 Roberts et al., 1975
158. Syngnathus fuscus N. pipefish 270 5760 LC50 Roberts et al., 1975
Sciaenidae:
159. Leiostanus xanthurus Spot (juv.) 180 30 Avoidance Middaugh et al., 1977
159. Leiostomus xanthurus Spot (juv.) 50 30 Avoidance Middaugh et al., 1977
160. Leiostomus xanthurus Spot (juv.) 140 1440 LC50 Bellanca and Bailey, 1977
160. Leiostomus xanthurus Spot (juv.) 90 5760 LC50 Bellanca and Bailey, 1977
Cyprinodontidae:
100% mortality,
161. Fundulus heteroclitus Mummichog 650 30 Capuzzo, Davidson, et al., 1977
25°c
100% mortality
162. Fundulus heteroclitus Mummichog 1200 30 Capuzzo, Davidson, et al., 1977
25°C*
100% mortality
163. Fundulus heteroclitus Mummichog 250 30 Capuzzo, Davidson, et al., 1977
30°c

WATER QUALITY GUIDELINE SERIES No. WQG-10 51


Concentration Duration
Data Point and Scientific Name Descriptive Name Effect Ref.
(µg/L) (Min.)
100% mortality
164. Fundulus heteroclitus Mummichog 850 30 Capuzzo, Davidson, et al., 1977
30°C*
100% mortality
165. Fundulus heteroclitus Mummichog 400 30 Capuzzo, Goldman, et al., 1977
25°C
100% mortality
166. Fundulus heteroclitus Mummichog 300 30 Capuzzo, Goldman, et al., 1977
25°C*
Initial respiratory
167. Fundulus heteroclitus Mummichog 300 30 Capuzzo, Goldman, et al., 1977
stress*
Sparidae:
168. Stenotomus versicolor Scup 650 30 100% mortality Capuzzo, Davidson, et al., 1977
169. Stenotomus versicolor Scup 3100 30 100% mortality* Capuzzo, Davidson, et al., 1977
170. Stenotomus versicolor Scup 500 30 Stress Capuzzo, Davidson, et al., 1977
171. Stenotomus versicolor Scup 2200 30 Stress* Capuzzo, Davidson, et al., 1977
Gasterosteidae:
3-spine Stickleback (juv.&
172. Gasterosteus aculeatus 167 5760 LC50 Thatcher, 1977
adult)
Ammodytidae:
173. Ammodytes hexapterus Pac. sand lance (juv. & adult) 82 5760 LC50 Thatcher, 1977
N.G. Not Given
* Chloramines tested or suspected
juv. Juvenile
Δ Temperature change

WATER QUALITY GUIDELINE SERIES No. WQG-10 52


Table 4. Chlorine Criteria for Freshwater Aquatic Life
Jurisdiction or
Criteria Statements Criteria Values Date
Author

Aquatic life should be protected where the concentration


of residual chlorine in the receiving system does not
exceed 3 µg/L at any time or place. Aquatic organisms will
tolerate short-term exposure to high levels of chlorine. 3-50 µg/L U.S. EPA 1973
Until more is known about the short-term effects, it is
recommended that total chlorine should not exceed 50
µg/L for a period up to 30-minutes in any 24-hour period.

Concentration of total residual chlorine not to exceed 10


µg/L when discharged continuously. This concentration
would not protect trout and salmon and some important 10 µg/L Brungs 1973
fish-food organisms; it could be partially lethal to
sensitive life stages of sensitive fish species.

Concentration of total residual chlorine not to exceed 2


µg/L when discharged continuously. This concentration 2 µg/L Brungs 1973
should protect most aquatic organisms.

Concentration of total residual chlorine not to exceed 200


µg/L when discharged intermittently for a period of 2 200 µg/L for
Brungs 1973
h/day. This concentration would not protect trout and 2h/day
salmon.
Concentration of total residual chlorine not to exceed 40
µg/L when discharged intermittently for a period of 2 40 µg/L for 2h/
Brungs 1973
h/day. This concentration should protect most species of day
fish.

An upper limit of 4 µg/L HOCl should afford sufficient EIFAC 1973


4 µg/L HOCL
protection of fish stocks and other aquatic organisms. Alabaster and Lloyd 1984

Safe values for continuous exposure are 5 µg/L and 20


5 µg/L and 10
µg/L TRC for coldwater and warmwater intolerant fish, Basch and Truchan 1974
µg/L
respectively.

Safe values for intermittent exposure to chlorine are 40


µg/L and 200 µg/L for coldwater and warmwater
intolerant fish, respectively. These intermittent safe
40 µg/L and 200
concentrations are to apply to a 30-minute exposure Basch and Truchan 1974
µg/L
period with a number of 30-minute exposures
allowable/day to be determined on a case-by-case basis
for each plant.

Total residual chlorine should not exceed (a) 2.0 µg/L for
2.0 µg/L and U.S. EPA 1976
the protection of salmonid fish; and (b) should not
10.0 µg/L Alaska 1979
exceed 1 O. 0 µg/L for other freshwater organisms.

WATER QUALITY GUIDELINE SERIES No. WQG-10 53


Jurisdiction or
Criteria Statements Criteria Values Date
Author
A single criterion for total residual chlorine of 3 µg/L for
fresh water aquatic life continuously exposed to total 3 µg/L Brungs 1976
residual chlorine.

Criteria for intermittent exposure of aquatic organisms to


total residual chlorine should be time-related as Time-related Brungs 1976
proposed by Mattice and Zittel (1976).

The chronic (>5 days) toxicity threshold for freshwater


1. 5 µg/L Mattice and Zittel 1976
aquatic life is 1.5µg/L total residual chlorine.

The acute (<5 days) toxicity threshold for freshwater


aquatic life exposed to intermittent discharges is 1 000
Time-related Mattice and Zittel 1976
µg/L for 1 minute. time-related and ranges from 1.5 µg/L
total residual chlorine for 5 days to

1977
Objective for residual chlorine in receiving waters outside
Below 1979
the initial dilution zone is below detectable limits as British Columbia
detection 1980
measured by amperometric method.
1980

1978
Total residual chlorine, as measured by the amperometric
International Joint
(or equivalent) method, should not exceed 2 µg/L to 2 µg/L
Commission Ontario
protect aquatic life.
1984

A single criterion of 3 to 5 µg/L total residual chlorine


(measured by amperometric titration in conjunction with
3 to 5 µg/L American Fisheries
a polarograph). Separate criteria should be established 1979
Time-related Society
for intermittent discharges based on an exposure time
versus chlorine concentration curve.

Total residual chlorine must not exceed 2 µg/L for cold 2 µg/L and 10
Idaho 1980
water biota and 1 0 µg/L for warm water biota. µg/L
Canada Dept. of
For continuous exposure, the total residual chlorine
2 µg/L Fisheries and 1983
should be less than 2 µg/L.
Oceans
Canada Dept.
For intermittent exposure, the total residual chlorine
40 µg/L Fisheries and 1983
should be less than 40 µg/L for 2 hours/day.
Oceans
Maximum acceptable concentration of total residual
2 µg/L Manitoba 1983
chlorine for cold water aquatic life is 2 µg/L.
Maximum acceptable concentration of total residual
10 µg/L Manitoba 1983
chlorine for cool water aquatic life is 10 µg/L
To protect freshwater aquatic life and its uses, in each 30 1983
8.3 and 14 µg/L U.S. EPA
consecutive days: (a) the average concentration of total (Draft)

WATER QUALITY GUIDELINE SERIES No. WQG-10 54


Jurisdiction or
Criteria Statements Criteria Values Date
Author
residual chlorine should not exceed 8.3 µg/L; (b) the
maximum concentration should not exceed 14 µg/L; and
(c) the concentration may be between 0.3 and 14 µg/L for
up to 96 hours.
Freshwater aquatic organisms and their uses should not
be affected unacceptably if the -day average
concentration of total residual chlorine does not exceed 11 and
U.S. EPA 1985
11 µg/L more than once every 3 years on the average and 19 µg/L
if the 1-hour average concentration does not exceed 19
µg/L more than once every 3 years on the average.
The concentration of residual chlorine, as measured by
the amperometric (or equivalent) method, should not 2 µg/L CCREM 1987
exceed 2.0 µg/L.

WATER QUALITY GUIDELINE SERIES No. WQG-10 55


Table 5. Chlorine Criteria for Marine Aquatic Life
Jurisdiction
Criteria Statements Criteria Values Date
or Author
It is recommended that an application factor of 0.1 be
used with 96-h LC50 data from seawater bioassays for 0.1 of 96-h LC50 U.S. EPA 1972
the most sensitive species to be protected.
However, it is suggested that free residual chlorine in
seawater in excess of 10 µg/L can be hazardous to marine 10 µg/L U.S. EPA 1972
life.
Total residual chlorine concentration of 10 µg/L for
10 µg/L U.S. EPA 1976
marine organisms.
The chronic toxicity threshold for saltwater is 20 µg/L. 20 µg/L Mattice and Zittel 1976
The acute toxicity threshold for marine aquatic life
exposed to intermittent discharges is time-related and
Time-related Mattice and Zittel 1976
ranges from 20 µg/L total residual chlorine for 2 hours to
300 µg/L for 10 seconds.

Objective for residual chlorine in receiving waters outside 1977


the initial dilution zone is below detectable limits as British Columbia 1979
measured by amperometric method. 1980

The best criterion available for marine organisms at American Fisheries


20 µg/L 1979
present is 20 µg/L (as oxidant species). Society
Total residual chlorine shall not exceed 2.0 µg/L for
salmonid fish, or 10.0 µg/L for other organisms. For 2 and 10 µg/L
harvesting for consumption of raw mollusks or other raw Alaska 1979
aquatic life, total residual chlorine shall not exceed 1 000 1 000 µg/L
µg/L at any time.
To protect saltwater aquatic life and its uses, in each 30
consecutive days: (a) the average concentration of
chlorine-produced oxidants should not exceed 7.4 µg/L; 7.4 and 1983
U.S. EPA
(b) the maximum should not exceed 13 µg/L; and (c) the 1 3 µg/L (Draft)
concentration may be between 7.4 and
13 µg/L for up to 96 hours.
Saltwater aquatic organisms and their uses should not be
affected unacceptably if the 4-day average concentration
of chlorine-produced oxidants does not exceed 7.5 µg/L 7.5 and
U.S. EPA 1985
more than once every 3 years on the average and if the 1- 13 µg/L
hour average concentration does not exceed 13 µg/L
more than once every 3 years on the average.

WATER QUALITY GUIDELINE SERIES No. WQG-10 56


Figure 1. Toxicity of Chlorine to Freshwater Organisms

WATER QUALITY GUIDELINE SERIES No. WQG-10 57


Figure 2. Toxicity of Chlorine to Marine Organisms

WATER QUALITY GUIDELINE SERIES No. WQG-10 58


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