September 18, 2013 

EE&T Project No. 5327-02 

Subject: Impact of Bromide Discharges into Drinking Water Sources from Coal-Fired 

Power Plants 

BACKGROUND 

In December 2011, the US Environmental Protection Agency (USEPA) approved new 

strict discharge limits targeting oil- and coal-fired electrical power generating facilities. These 

requirements are scheduled to take effect in 2015, though MATS has been revised and 

“reconsidered”, and the comment period has been extended, a number of times since first 

published (USEPA 2012 – USEPA approved in December 2011 but not published in Federal 

Register until February 2012). MATS will target reductions in emissions of metals (mercury, 

arsenic, chromium, nickel), acid gases (hydrochloric and hydrofluoric), particulate matter, sulfur 

dioxide (SO2), and nitrous oxides (NOx). Figure 1 shows a USEPA prepared map of the US 

facilities with coal, oil, or both coal and oil units at the power plant (USEPA 2011). It is 

estimated that 1,100 coal-fired units and 300 oil-fired units at 600 power plants will be impacted 

by the MATS requirements (USEPA 2011). In the remainder of this memorandum, the term 

“coal-fired” power plants will be used, but this will be interpreted to mean coal or oil-fired units 

at electrical power generating facilities with these units. 

This memorandum deals with how these new requirements to control emissions from 

coal-fired power plants may lead to discharges of more bromide into drinking water sources, and 

how these bromide discharges will impact the production of compounds harmful to public health 

and the ability of public water systems to meet federal and state drinking water treatment 

requirements. The discussion below will first discuss how some of the new MATS requirements 

may lead to more bromide discharges into drinking water sources, how this will impact drinking 

water treatment operations and resulting quality of drinking water delivered to customers, and 

some case studies illustrating impact of bromide discharges from coal-fired power plants on 

downstream drinking water systems. 
EE&T, IN

Figure 1

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EE&T, INC. 3

devices. Addition of bromide-containing salts (usually calcium bromide) to the coal combustion 

unit can convert the mercury into the more water soluble Hg2+ form. This soluble mercury is 

better removed by the wet scrubbers used to clean flue gasses. However, while the mercury in 

the wastewater can be removed prior to discharge into a receiving stream, the added bromide is 

not well removed and typically ends up being discharged. Some data regarding the fate of 

bromide in Dutch power plants equipped with selective catalytic reduction (SCR), ESP, and wet 

scrubbers suggests that 82% of the total bromide added is discharged (Meij, 1999). 

In 14 full scale coal-fired power plant tests using calcium bromide (CaBr2) to oxidize 

elemental mercury, greater than 90% of the mercury was oxidized with the addition of 25 to 300 

ppm bromide by weight of coal (Chang et al., 2008). This range is wide due to the coal’s natural 

abundance of chlorine and bromine giving the coal varied natural performance for oxidizing 

mercury. A 1 MW power plant operated 24 hours a day, 365 days a year would produce 

8,760,000 KWh/year. According to the US Energy Information Administration it takes 1.07 lbs 

of coal to produce 1 kWh. This means that for each MW of electrical power plant capacity, a 

coal-fired power plant would require 9,373,200 lbs coal/year or 25,680 lbs coal/day. With the 

range of 25 to 300 ppm for bromide noted in Chang et al. (2008), the amount of bromide added 

to the system each day per MW of power is estimated as follows: 

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If 0.51 to 6.2 lb/day of bromide are added for a 1 MW power plant, and 82% of the 

bromide is discharged as scrubber wastewater, theoretically 0.42 to 5.1 lbs/day of bromide can 

be discharged into receiving streams from a 1 MW plant. 

In 2006 about 100 gigawatts (GW) of coal-fired power plant capacity in the United States 

was equipped with flue gas desulfurization (FGD) technology, 90 GW of which are wet 

scrubbers (Miller et al, 2006). Figure 2 is from a National Energy Technology Laboratory report, 

projecting the flue gas desulfurization capacity to increase to 231 GW by year 2020. If 90 

percent of the FGD processes installed continue to be wet scrubbers, then 208 GW of the 
EE&T, IN

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EE&T, IN

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EE&T, INC. 6

2006). These adverse health effects have mostly been attributed to disinfection by-products 

(“DBPs”), the term used to collectively describe the suite of products resulting from reactions of 

free chlorine and other oxidants with natural organic matter (NOM) and other substances in the 

water. In particular, the DBPs most commonly associated with these observed adverse health 

effects have been halogen substituted organics, typically DBPs containing chlorine or bromine. 

At present, while there are a large variety of complicated halogen substituted DBP compounds 

believed to result from chlorination of drinking water, the only currently regulated DBPs are 

TTHM (the sum of chloroform, bromodichloromethane, dibromochloromethane, and 

bromoform) and HAA5 (mono-, di-, and tri-chloro acetic acid and mono- and di-bromo acetic 

acid). 

Chlorine added to drinking water reacts quickly with reduced substances (e.g., reduced 

iron), as noted above, plus it also reacts quickly with ammonia, organic compounds containing 

nitrogen, and the bromide ion (Br -). Any chlorine not consumed by these reactions can produce 

disinfection, but can also produce DBPs if enough DBP precursor material is present and if 

unreacted free chlorine residual remains in water for a long enough time for the DBP formation 

reactions to occur. 

Most chlorine in drinking water is consumed in oxidation reactions, including oxidation 

of organics (Jolley 1975). However, some added chlorine substitutes into organic compounds to 

produce a chlorine substituted DBP, and some of the added chlorine can transfer its 

oxidative/disinfecting power to another compound. In the latter case, chlorine can: a) react with 

ammonia to produce chloramines (typically monochloramine or NH2Cl), b) react with nitrogen 

containing organics to produce organic chloramines, and c) oxidize bromide to bromine. When 

free chlorine reacts with bromide to produce free bromine in water, the bromine reacts 

analogously to free chlorine in: i) oxidation of any reduced metals still present, ii) disinfection, 

iii) reaction with ammonia to produce bromamines1

 (typically dibromamine), and iv) formation 

of bromine substituted DBPs if DBP precursor material is present. 

 

1

 Chloramines can also react with bromide to produce bromamines 
EE&T, INC. 7

Therefore, in water chlorine can react directly with organic DBP precursors, but can also 

react first with bromide, then the resulting bromine can react with organic DBP precursors to 

produce brominated organic DBPs2

. This is important for a number of reasons: 

1. Greater health risks attributed to brominated DBPs than chlorinated DBPs = Risks 

from cancer and other adverse human health effects are generally thought to be 

greater for bromine substituted DBPs than with analogous DBPs containing chlorine 

instead of bromine (Cantor et al. 2010). For example, the concentration of species that 

gives one in a million (1/1,000,000) lifetime cancer risk for dibromochloromethane 

(ChBr2Cl) is 0.6 μg/L on a mass basis. For chloroform (CHCl3) it is 6 μg/L. 

Therefore, on a mass basis it appears that CHBr2Cl has 10 times greater lifetime 

cancer risk than CHCl3. However, when you take into account the different in 

molecular weight (119.4 μg/μmol for CHCl3 and 208.3 μg/μmol for CHBr2Cl), the 

difference on a molar basis is even higher (~17.4 times greater). 

2. Regulatory limits for drinking water compliance are mass based not molar based = 

Drinking water facilities are currently faced with two regulatory limits for halogen 

substituted DBPs: TTHM (sum of four compounds listed above) ≤ 0.080 mg/L and 

HAA5 (sum of five compounds listed above) ≤0.060 mg/L. Consequently, the 

regulatory limit is simply based on taking the mass concentration of each compound, 

without correcting for molar weight, and adding each numerical value for the four or 

five compounds involved. Therefore, a water system with no bromide in background 

source water will be in compliance with TTHM limit if they have 60 μg/L of 

chloroform and no detectable brominated THMs. In this case, about 0.5 μmol/L of 

TTHMs were produced. However, if nothing else changes but enough bromide is 

added to produce bromodichloromethane instead of chloroform, then 0.5 μmol/L of 

TTHM will produce ~82 μg/L which could create compliance difficulties3

. Therefore, 

a water system currently in compliance with federal and state requirements may no 

 

2

 Furthermore, although free chlorine cannot react with bromine in drinking water to produce bromate, a 

stronger oxidant like ozone can reach with bromide in drinking water to produce bromate, which is a regulated 

inorganic DBP in drinking water. 

3

 Compliance is based on annual average at each compliance location in a water system, as required in Stage 

2 DBPR. Therefore, a single TTHM value above 0.080 mg/L (80 μg/L) will not mean the water system is out of 

compliance, as long as the average TTHM for four samples at this location during a one year period is ≤0.080 mg/L. 
EE&T, INC. 8

longer be in compliance if bromide is added to the drinking water source in amounts 

sufficient to increase the amount of brominated DBPs produced. 

3. Increased formation of brominated DBPs due to greater reactivity of bromide = The 

above note suggests that the presence of bromide during chlorination can increase the 

numerical value of the regulatory compliance value even if the same amount of 

organic precursor material is present and even if the same molar concentration of 

DBP is produced. However, since free bromine in drinking water reacts more quickly 

than free chlorine, more DBPs (on a molar basis) will be produced (the increased 

reactivity of bromine will mean more oxidation of organics by bromine, as well as 

bromine substitution reactions). 

Therefore, releases of bromide into drinking water sources can potentially impact public 

health for consumers of treated drinking water, and can substantially complicate treatment at 

drinking water facilities in order to meet regulatory requirements. Water systems have typically 

already completed their studies to evaluate source water quality in order to develop DBP control 

strategies. New bromide releases from coal-fired power plants have not been evaluated by water 

plants beforehand. If these bromide releases occur, the drinking water systems may not detect the 

changing conditions until they start noting elevated DBP levels, particularly brominated species, 

in compliance monitoring locations. Then all water systems in the watershed will have to do an 

immediate re-evaluation of treatment to meet the regulatory limits under the new conditions. 

Unfortunately, there is little the water systems can do once the bromide gets into the source 

water. They could try drastically increasing removal of organic DBP precursors, but that will not 

be easy or affordable. Removing the bromide once it is in the water will be even more 

problematic. The best solution would be to find a way to keep the bromide from getting into the 

drinking water sources, either by: a) not using bromide to remove mercury at coal-fired power 

plants, b) using coal with lower mercury content, or c) trying to remove bromide from 

wastewater streams prior to discharge (this will not be easy either, but will at least be easier to do 

in a concentrated stream than in a more dilute stream at the water plant). 
EE&T, INC. 9

CASE STUDIES 

While many US water systems do not have source water bromide levels as high as some 

overseas locations, there has become a new concern associated with bromide discharges into 

potable water sources. There is some information available in the literature where drinking water 

facilities have detected an increase in brominated DBPs and they have traced bromide discharges 

from coal-fired power plants as potential sources (States et al. 2013 and Hopkins 2013). These 

references also cite other potential bromide sources, including hydrofracking, treated wastewater 

effluents, and industrial discharges. 

Figure 1 indicated the USEPA identified coal- and oil-fired electrical generating facilities 

in the US. Except for a large number of generating facilities in TX, most of the power plants 

indentified are east of the Mississippi River, especially in TN, GA, AL, SC, NC, VA, eastern 

OH, western PA, and several locations along the Ohio River (IL, IN, OH, KY, and WV). 

Locations with fossil fuel powered electrical generating facilities in US generally use coal,, 

though oil-fired facilities can be found at some locations along either Atlantic or Pacific coasts 

(CA, NY, NJ, MA, CT, FL) and in some important oil producing areas (TX, OK, LA). 

Figure 4 includes locations of three power plants, rivers, streams, and a drinking water 

treatment facility using surface water located upstream of Charleston SC. This situation is an 

example of a water system directly impacted by bromide discharges from a power plant. As 

shown in Figure 4, the City of Charleston surface water treatment plant, called Hanahan Water 

Treatment Plant, uses the Cooper River as their water source and their intake is downstream from 

three coal fired power plants. The power plant that is furthest upstream has a capacity of 2,390 

MW and is located at the north shore of Lake Moultrie. The next power plant south of this power 

plant has a capacity of 346 MW and is located on the south shore of Lake Moultrie. The power 

plant closest to Charleston’s intake has a capacity of 633 MW and installed a wet scrubber in 

2009. The power plant’s website indicates that the new wet scrubber eliminates 60-90% of the 

former mercury emissions. 
EE&T, IN

Figure 4

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EE&T, INC. 11

Figure 5 shows bromide levels at the finished water tap (blue line) and in the source 

water reservoir (red line) from 8/1/2008 to 9/13/2013. For the most part the bromide level from 

August 2008 to August 2010 stays around 0.1 mg/L and only exceeded 0.15 mg/L on a couple of 

days during this period. After August 2010 the bromide concentrations rise and peak around 0.35 

mg/L in December 2010. Another rise occurred in October 2011, this time with peaks at 0.45 and 

0.55 mg/L in March and June 2012, respectively. The increased bromide in the plant’s source 

water appears to occur shortly after the wet scrubber installation at the power plant in 2009. 

Figure 6 shows concentrations (μg/L) of three specific DBPs, bromoform (blue), 

bromodichloromethane (red), and bromochloroacetic acid (green) analyzed from the WTPs 

finished water tap from 8/1/2008 to 9/13/2013 (note DBP formation would be even greater at in 

distribution system due to longer reaction time for DBP formation). The constituent impacted 

most during this period was bromoform. From August 2008 to June 2010 bromoform had a 

concentration around 1 μg/L but clearly increases by a factor of 10 to 20, reaching levels of 17 to 

25 μg/L Bromodichloromethane had peaks at 13 and 15 μg/L in June 2009 and August 2009. 

After that, the concentrations stayed below 5 μg/L until early 2013 when concentrations began to 

increase again to 10 μg/L. Bromochloroacetic acid concentrations remained consistently below 

10 μg/L except for one spike at 40 μg/L on March 2013. Many other water treatment plants in 

South Carolina made similar observations, however they declined to provide these data. 

The water system evaluated whether drought/climate change could have caused the 

increased bromide levels but drought was ruled out as a direct or indirect contributor to the 

observed bromide and DBP results. 

 
EE&T, IN

Figure 4

Figure 

C. 

. Bromide 

8/1/2008 

5. Bromof

(green) c

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to 9/13/2013

form (blue)

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EE&T, INC. 13

SUMMARY 

New requirements for increased SO2 removal at coal-fired power plants should increase 

releases of bromide discharges drinking water sources. Because of the mercury content of some 

coal sources used at US coal-fired power plants, and new requirements to improve mercury 

removal, coal-fired power plants may increase the use of bromide to oxidize and remove 

mercury in wet scrubber processes. However, adding the bromide to increase mercury removal 

will further increase bromide releases in wastewater discharges from these facilities. This can 

have substantial impacts on the amount and type of DBPs produced during drinking water 

treatment at downstream facilities, particularly the increased production of brominated DBPs. 

These brominated DBPs have potential for greater health effects for drinking water consumers 

and may cause drinking water facilities currently in compliance with DBP requirements to be out 

of compliance if a greater proportion of the DBPs present are brominated. 

Removing the bromide at the drinking water plant is not economically sound. Water 

systems are left without options to reduce DBPs and comply with USEPA drinking water 

regulations, absent installing combinations of drinking water treatment unit operations (e.g., 

reverse osmosis (RO), granular activated carbon in combination with split-stream RO, etc.). 

Installing such advanced treatment will dramatically increase treatment costs and water rates in 

the communities served, as well as potentially creating other unintended consequences (e.g., 

disposal of membrane residuals, disposal or regeneration of spent carbon, disposal of anionic 

exchange regeneration brine wastes, etc.). Removing bromide at the discharge source is less 

expensive and more proactive than to remove diluted bromide at multiple downstream water 

treatment facilities. It is also more equitable for the discharger to remove the bromide rather than 

forcing downstream water users to have to address this precursor to cancer causing contaminants. 

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AWWA 2004. Formal Comments of the American Water Works Association on the Stage 2 

Disinfectants and Disinfection By-Products Proposed Rule, Water Docket OW-2002-

0043. Washington, DC: AWWA. 

Blythe, G.; Richardson, C.; Rhudy, R. 2002. Pilot Evaluation of the Catalytic Oxidation of 

Mercury for enhanced Removal in Wet FGD Systems. In Proceedings of Air Quality III: 

Mercury, Trace Elements and Particulate Matter Conference, Arlington, VA, September 

9-12, 2002. Energy and Environmental Research Center, University of Dakota, Grand 

Fork, North Dakota, September 2002. 
EE&T, INC. 14

Bustard, J.; Renninger, S.; Chang, R.; Miller, R.; Monroe, L.; Sjostrom, S. 2003. Results of 

Activated Carbon Injection for Mercury Control Upstream of COHPAC Fabric Filter. 

Presented at the A&WMA/EPA/DOE/EPRI Combined Power Plant Air Pollutant Control 

Mega Symposium, Washington, DC, May 19-22, 2003.

Chang, R. et al. 2008. Near and Long Term Options for Controlling Mercury Emissions from 

Power Plants. Proceedings of the Power Plant Air Pollutant Control “Mega” 

Symposium, Baltimore, MD, August 25-28, 2008. 

Hopkins, D. 2013. Bromide – an unsuspected culprit assessing impacts on Stage 2 DBPR 

compliance. Presented at VA-AWWA/VWEA Joint Annual Meeting, September 8-12, 

2013. Richmond, VA. 

Jolley, R. 1975. Chlorine-containing organic constituents in chlorinated effluents. Jour WPCF. 

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Kellie, S.; Cao, Y.; Duan, Y.; Li, L.; Chu, P.; Mehta, A.; Carty, R.; Riley, J.T.; Pan, W.P., 2005. 

Factors Affecting Mercury Speciation in a 100-MW Coal-Fired Boiler with Low-NOx 

Burners. Energy Fuels, 19:3:800-806. 

Mcilvaine Company, 2012. Big Market for Chemicals to Capture Mercury. 

www.pollutionsolutions-online.com 

Meij, R., 1999. Mass Balance Study.... presented at IEA Trace Element Workshop, University 

of Warwick. 

Miller, C., T. Feeley, W. Aljoe, B. Lani, K. Schroeder, C. Kairies, A. McNemar, A. Jones, J. 

Murphy. 2006. Mercury Capture and Fate Using Wet FGD at Coal-Fired Power Plants. 

DOE/NETL Mercury and Wet FGD R&D. August 2006. 

States, S., et al. 2013. Marcellus Shale drilling and brominated THMs in Pittsburgh, PA, drinking 

water. Jour AWWA. 105:8:E432-E448. 

US Energy Information Administration. 2013. How Much Coal, Natural Gas, or Petroleum Is 

Used to Generate a Kilowatt-hour of Electricity? Web. 

<http://www.eia.gov/tools/faqs/faq.cfm?id=667&t=2>. 

USEPA. 2006. Stage 2 Disinfectants and Disinfection Byproducts Rule: National Primary and 

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