Bromate in Drinkin

1
g Water

The bromate ion (BrO
3
-
) may exist in a number of salts, the most common of which
are potassium and sodium bromate.

Identity
Compound CAS No. Molecular formula
Potassium bromate 7758-01-2 KBrO
3

Sodium bromate 7789-38-0 NaBrO
3


Physicochemical properties (Weast, 1986)

Property Potassium bromate Sodium bromate
Boiling point (C) 370 (decomposes) -
Melting point (C) 350 3.81
Density at 20 C 3.27 3.34
Water solubility (g/litre) 133 (40 C) 498 (100 C)
275 (8 C) 909 (100 C)

Major uses and sources in drinking-water
Bromate may be formed in water during ozonation when the bromide ion is present
(Haag & Hoign, 1983). Under certain conditions, bromate may also be formed in
concentrated hypochlorite solutions used to disinfect drinking-water (IPCS, 2000).
This reaction is due to the presence of bromide in the raw materials (chlorine and
sodium hydroxide) used in the manufacture of sodium hypochlorite. Bromide is not
oxidized by chlorine dioxide, so the use of chlorine dioxide will not generate
hypobromous acid, hypobromite ion or bromate (Hoign & Bader, 1994). (Although
bromate can be formed on simultaneous exposure to chlorine dioxide and light [Rice
& Gomez-Taylor, 1986; Gordon & Emmert, 1996], the reaction is thermodynamically
unfavourable, and bromate is unlikely to be formed under water treatment conditions.)
Bromate can also be formed in electrolytically generated hypochlorous acid solutions
when bromide is present in the brine (Fielding & Hutchison, 1993).

Sodium and potassium bromate are powerful oxidizers used mainly in permanent
wave neutralizing solutions and the dying of textiles using sulfur dyes (Mack, 1988).
Potassium bromate is also used as a chemical reagent and as an oxidizer to mature
flour during milling and to condition dough during baking (US FDA, 1994; IARC,
1999). As well, it is used in treating barley in beer making and has been used for the
improvement of the quality of fish paste products in Japan (Ministry of Health and
Welfare, 1979; JECFA, 1995). However, JECFA (1995) concluded that the use of
potassium bromate in food processing was not appropriate and that, as a general
principle, bromate should not be present in food as consumed.



1
Extracted from "Bromate in Drinking-water: Background document for development of WHO
Guidelines for Drinking-water Quality, WHO/SDE/WSH/05.08/78, World Health Organization 2005.
Environmental fate
No information is available on the taste or odour threshold of bromate.
Bromate does not volatilize and is only slightly adsorbed onto soil or sediment.
Because it is a strong oxidant, its most likely fate is reaction with organic matter,
leading to the formation of bromide ion.

Bromate in Water
Bromate is not normally found in water. Conversion of bromide to bromate upon
ozonation may be affected by natural organic matter, pH and temperature, among
other factors. The relative increase of bromate depends on measures used for
comparison (over time or as a function of concentration time, or CT). The use of CT
has been suggested as a more useful indicator to describe the relative rate of bromate
formation because it also gives a simultaneous descriptor for disinfection efficiency
(von Gunten et al., 2001). The rate of formation of bromate ion may increase with
temperature (AWWARF, 1991; Siddiqui & Amy, 1993). In addition, many studies on
the effect of alkalinity on the formation of bromate during ozonation indicate that
increased alkalinity increases bromate formation (Siddiqui et al., 1995). However, the
rate of formation of bromate during ozonation is also affected by ozone
characteristics. Thus, a smaller CT might result because ozone becomes less stable
with increasing temperature and/or alkalinity. All factors being equal, bromide
concentration and ozone dose are the best predictors of bromate formation during
ozonation (IPCS, 2000).

A study of European water utilities found bromate levels ranging from less than the
detection limit (2 g/litre) to 16 g/litre in finished water (IPCS, 2000). Health
Canada (1999) reported an average level of 1.71 g/litre, with a range of 0.554.42
g/litre; in another survey, it reported an average concentration of 3.17 g/litre, with a
range of 0.738.00 g/litre. In ozonated bottled water, the average level of bromate
was 18 g/litre, with a range of 4.337.3 g/litre (Health Canada, 1999). Haag &
Hoign (1983) and McGuire et al. (1990) reported a range of 6090 g/litre in
ozonated water. In IPCS (2000), the range of bromate concentrations reported in
drinking-water with a variety of source water characteristics after ozonation was <2
293 g/litre, depending on bromide ion concentration, ozone dosage, pH, alkalinity
and dissolved organic carbon. AWWA (2000) reported a mean level of bromate in
finished waters of 3.06 g/litre and a median level of 3.64 g/litre. The mean level in
the distribution system was 2.5 g/litre, and the median level was 0.05 g/litre. It
should be noted that some of the studies demonstrating high rates of conversion of
bromide to bromate are pure laboratory studies with very high bromide levels and
thus may not be representative of conversion rates at environmentally relevant doses.

In the USA, the annual mean bromate concentration in finished surface water
determined using the EPA methods was 2.9 g/litre, with a range of <0.225 g/litre;
the annual mean concentration of bromate in the same waters determined using the
utility method was 2.1 g/litre, with a range of <550 g/litre. It is difficult to
compare values obtained by the EPA and utility methods because the minimum
reporting level using the utility method is 5 g/litre, while for the EPA method it is
0.2 g/litre. At this time, there are no data for groundwater plants (US EPA, 2001a).


Analytical methods and analytical achievability
Bromate in drinking-water may be measured by ion chromatography using
conductivity detection (EPA Method 300.1), ultraviolet/visible absorbance detection
(EPA Method 317.0) or detection by inductively coupled plasmamass spectrometry
(EPA Method 321.8). For samples with high chloride ion content, a silver cartridge
can be used to remove chloride prior to ion chromatographic analysis to minimize its
interference with bromate measurement (IPCS, 2000). However, it should be noted
that for natural sources and waters with high total organic carbon levels, detection
limits will be slightly different because of the masking effect of natural organic matter
and high concentrations of carbonate/bicarbonate ions that may interfere with bromate
measurement (IPCS, 2000). The method detection limit (MDL) for bromate in EPA
Method 300.1 is <1.5 g/litre, and the practical quantification level (PQL) is
approximately 5 g/litre. The MDLs for bromate in EPA Methods 317.0 and 328.1
are <0.2 g/litre and 0.3 g/litre, respectively, and the PQL for both methods is as low
as 1 g/litre.

Treatment and control methods and technical achievability
There are no practical methods currently available to remove bromate from water.
Advanced treatment processes that have been suggested as warranting further
evaluation include ion exchange and membrane filtration (Kruithof et al., 1992).
Bromate in ozonated drinking-water supplies is best controlled by limiting its
formation, which is influenced by the bromide concentration (0.18 mg/litre)
(Krasner et al., 1993), the source and concentration of organic precursors, pH,
temperature, alkalinity and ozone dose (AWWA, 1993). For example, reductions in
bromate formation can be achieved by lowering the pH to less than 8, adding
ammonia or controlling the ozone reaction time and the ozone/dissolved organic
carbon ratio (Kruithof et al., 1992; von Gunten & Hoign, 1992; Siddiqui & Amy,
1993). These and other measures have both advantages and disadvantages; a low pH,
while reducing bromate formation, increases the formation of bromoform and other
brominated organic by-products, in addition to being undesirable from the point of
view of corrosion control; addition of ammonia results in the conversion of
hypobromous acid to monobromamine, which in turn may be oxidized to nitrate
(Siddiqui & Amy, 1993). Because of the large number of factors that influence
bromate production, it will be necessary to optimize treatment by balancing the
advantages and disadvantages of various measures on an individual basis for each
water supply.

REFERENCES
AWWA (1993) Brominated DBPs [editorial]. Journal of the American Water
Works Association, 85(1):41.
AWWA (2000) American Water Works Association committee report:
Disinfection at large and medium-size systems. Journal of the American Water
Works Association, 92(5):3243.
AWWARF (1991) Disinfection by-products database and model project. Denver,
CO, American Water Works Association Research Foundation.
Fielding M, Hutchison J (1993) Formation of bromate and other ozonation by-
products in water treatment. In: Proceedings of the IWSA International Workshop
on Bromate and Water Treatment, Paris 1993. London, International Water Supply
Association, pp. 8184.
Health Canada (1999) Bromate. Guidelines for Canadian drinking water quality
supporting document. Ottawa, Ontario, Health Canada, Environmental Health
Directorate, Health Protection Branch.
Hoign J, Bader H (1994) Kinetics of reactions of chlorine dioxide (OClO) in
water I. Rate constants for inorganic and organic compounds. Water Research,
28(1):4555.
IARC (1999) Some chemicals that cause tumours of the kidney or urinary bladder
in rodents and some other substances. Lyon, International Agency for Research on
Cancer, pp. 481496 (IARC Monographs on the Evaluation of Carcinogenic Risks
to Humans, Vol. 73).
IPCS (2000) Disinfectants and disinfectant by-products. Geneva, World Health
Organization,
JECFA (1995) Evaluation of certain food additives and contaminants. Geneva,
World Health Organization, Joint FAO/WHO Expert Committee on Food
Additives (WHO Technical Report Series No. 859).
Krasner SW et al. (1993) Formation and control of bromate during ozonation of
waters containing bromide. Journal of the American Water Works Association,
85(1):7183.
Kruithof JC et al. (1992) Formation of bromate by ozonation and application of
other chemical disinfectants. Nieuwegein, The Netherlands Waterworks Testing
and Research Institute (KIWA).
Mack RB (1988) Round up the usual suspects. Potassium bromate poisoning.
North Carolina Medical Journal, 49:243245.
McGuire MJ, Krasner SW, Gramith JT (1990) Comments on bromide levels in
state project water and impacts on control of disinfectant by-products. Los
Angeles, CA, Metropolitan Water District of Southern California.
Ministry of Health and Welfare (1979) The Japanese standards of food additives,
4th ed. Tokyo. p. 367. Nakajima M et al. (1989) Effect of route of administration
in the micronucleus test with potassium bromate. Mutation Research, 223:399
402.
Rice RG, Gomez-Taylor M (1986) Occurrence of by-products of strong oxidants
reacting with drinking water contaminants scope of the problem. Environmental
Health Perspectives, 69:3144.
Siddiqui MS, Amy G (1993) Factors affecting DBP formation during ozone
bromide reactions. Journal of the American Water Works Association, 85(1):63
72.
Siddiqui MS, Amy GL, Rice RG (1995) Bromate ion formation: a critical review.
Journal of the American Water Works Association, 87(10):5870.
US EPA (2001a) Stage 2 occurrence and exposure assessment for disinfectants and
disinfection byproducts (D/DBPs). Washington, DC, US Environmental Protection
Agency.
US FDA (1994) Code of Federal Regulations. Vol. 21. Food and Drugs, 1994, Part
136, 137 and 172.730. Washington, DC, US Food and Drug Administration; Office
of the Federal Register, National Archives and Records Administration.
von Gunten U et al. (2001) By-products formation during drinking water
disinfection: a tool to assess disinfection efficiency? Water Research, 35:2095
2099.
Weast RC, ed. (1986) CRC handbook of chemistry and physics, 67th ed. Boca
Raton, FL, CRC Press.


Methods of Measurement of Bromate in Drinking-Water

EPA Method 300.1: Determination of Inorganic Anions in Drinking Water by Ion
Chromatography;
http://water.epa.gov/scitech/drinkingwater/labcert/upload/met300.pdf
The U.S.EPA Method 300.1 employs conductivity as the means of detection which works well for
most anions. However, the method is nonspecific and coeluting interferences cannot be identified. The
more recent U.S.EPA Method 317.0 utilizes a Bromate specific reagent in a post-column reaction. This
allows for a very specific and sensitive assay for Bromate in complex matrices.

EPA Method 317.0: Determination Of Inorganic Oxyhalide Disinfection By-
Products In Drinking Water Using Ion Chromatography With The Addition Of A
Postcolumn Reagent For Trace Bromate Analysis
http://www.caslab.com/EPA-Methods/PDF/EPA-Method-317.pdf

EPA Method 321.8: Determination of Bromate in Drinking Waters by Ion
Chromatography Inductively Coupled Plasma Mass Spectrometry.
http://www.epa.gov/microbes/m_321_8.pdf

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Published paper shows low concentration of bromate in municipal waters as
compared to bottled drinking waters:

Brian M. De Borba, Jeff S. Rohrer, Chris A. Pohl, Charanjit Saini, "Determination of
trace concentrations of bromate in municipal and bottled drinking waters using a
hydroxide-selective column with ion chromatography", Journal of Chromatography
A1085 (1), 23-32, 2005.

Chlorination has been commonly used for more than a century to disinfect public
drinking waters. However, chlorination of drinking water can produce
trihalomethanes and other suspected carcinogenic DBPs that can endanger human
health.

The data in these tables demonstrate acceptable levels for most inorganic DBP anions
and bromide using either EPA methods.