BC Env Chlorine Waterqualityguideline Technical
BC Env Chlorine Waterqualityguideline Technical
BC Env Chlorine Waterqualityguideline Technical
Technical Appendix
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.
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.
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
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).
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:
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:
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:
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.
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.
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).
4.7.4 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.
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)
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.
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
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)