EE&T, INC. 1 OCCURRENCE AND CO NSEQUENCES OF INCREA SED BROMIDE 1 IN DRINKING WATER SO URCES 2 3 Nancy McTigue, Katherine Graf and Richard Brown, EE&T 4

5

ABSTRACT 6
Elevated levels of brominated disinfectant by

- products (DBPs) have been reported 7
recently by some drinking water uti lities. Some of these occurrences have been correlated with 8
upstream discharges of bromide

- containing wastes from coal

- fired power utilities, hydraulic 9
fracturing wastewater discharges and other industrial sources. This paper discusses this problem 10

in te rms of the formation chemistry of disinfectant by

- products when bromide is present, 11
regulatory changes that have resulted in the increased use of bromide by industries and discusses 12
the potential number of water utilities impacted by these discharges. The authors investigated 13
this problem through a review of published and unpublished sources, and through interviews 14

with utilit y personnel and state regulators. 15
Formation of By

- Products During Disinfection 16
The formation of unwanted and possibly carcinogenic by

- products as a result of the 17
disinfection of drinking water was first recognized by researchers in the 1970s. The first 18
regulations to limit the levels of these DBPs, a term used to collectively describe the suite of 19
products resulting from reactions of free chlorine and other oxidants with natural organic matter 20
(NOM) and other substances in the water, were promulgated by the United States Environmental 21
Protection Agency (USEPA) in 1979. Regulations have become more stringent since then as 22
knowledge of the presence, formation and health implications of DBPs has increased since the 23
1970s. Over 500 DBPs have been identified, although just a few have been regulated. 24EE&T, INC. 2

Disinfection of drinking water with free chlorine has made a significant contribution to 25
the reduction in waterborne disease. In spite of the positive benefit, it has also been shown that 26
DBPs can have adverse health effects after prolonged (i.e., lifetime) exposures (AWWA 2004; 27
USEPA 2006). In particular, the DBPs most commonly associated wi th these observed adverse 28
health effects have been halogen substituted organics, typically DBPs containing chlorine or 29
bromine. At present, while there are a large variety of complicated halogen substituted DBP 30
compounds believed to result from chlorinati on of drinking water, the only currently regulated 31
DBPs are total trihalomethanes (TTHM) and haloacetic acids (HAA5). TTHMs are the sum of 32
chloroform (CHCl 3 )
, bromodichloromethane (CHBrCl 2 )
, dibromochloromethane (CHBr 2 Cl) and 33

bromoform (CHBr 3 )

. HAA5 are th e sum of monochloroacetic acid
, (C 2 H 3 ClO 2 ) dichloroacetic 34

acid (C 2 H 2 Cl 2 O 2 )
, trichloroacetic acid (C 2 HCl 3 O 2 )
, bromoacetic acid (C 2 H 3 BrO 2 ) and 35

di bromo acetic acid (C 2 H 2 Br 2 O 2 )

. 36
Chlorine added to drinking water reacts quickly with reduced substances (e.g. red uced 37
iron), plus it also reacts quickly with ammonia, organic compounds containing nitrogen, and the 38
bromide ion. Any chlorine not consumed by these reactions can produce disinfection, but can 39
also produce DBPs if enough DBP precursor material is present a nd if unreacted free chlorine 40
residual remains in water for a long enough time for the DBP formation reactions to occur. 41
Most chlorine in drinking water is consumed in oxidation reactions, including oxidation 42
of organics (Jolley 1975). However, some added chlorine substitutes into organic compounds to 43
produce a chlorine substituted DBP, and some of the added chlorine can transfer its 44
oxidative/disinfecting power to another compound. In the latter case, chlorine can: (a) react with 45
ammonia to produce chlor amines (typically monochloramine or NH 2 Cl), (b) react with nitrogen 46
containing organics to produce organic chloramines, and (c) oxidize bromide to bromine. 47EE&T, INC. 3

Impact of Bromide on DBP Formation 48
If bromide is present, it affects the formation of DBPs in a num ber of ways. Free 49
chlorine reacts with bromide to produce free bromine in water, and the bromine reacts 50
analogously to free chlorine in: (1) oxidation of any reduced metals still present, (2) disinfection, 51
(3) reaction with ammonia to produce bromamines ( typically dibromamine), and (4) formation of 52
bromine substituted DBPs if DBP precursor material is present. 53
Therefore, in water, chlorine can react directly with organic DBP precursors, but can also 54
react first with bromide, and then the resulting bromine can react with organic DBP precursors to 55
produce brominated organic DBPs. This is important for a number of reasons: 56

1. There are reportedly greater health risks attributed to brominated DBPs than 57

chlorinated DBPs 58

Risks from cancer and other adverse human h ealth effects are generally thought to be 59
greater for bromine substituted DBPs than with analogous DBPs containing chlorine instead of 60
bromine (Cantor et al., 2010). For example, the concentration of species that gives a one in a 61
million (1/1,000,000) lif etime cancer risk for dibromochloromethane is 0.6 μg/L on a mass basis. 62
For chloroform it is 6 μg/L. Therefore, on a mass basis it appears that dibromochloromethane 63
has 10 times greater lifetime cancer risk than chloroform. However, when the difference i n 64
molecular weight is taken into account (119.4 μg/μmol for chloroform and 208.3 μg/μmol for 65
dibromochloromethane), the difference on a molar basis is even higher (~17.4 times greater). 66

2. The regulatory limits for drinking water compliance are mass ba sed not molar based 67
Drinking water facilities are currently faced with two regulatory limits for halogen 68
substituted DBPs: TTHM (sum of four compounds listed above) ≤ 80 μg/L and HAA5 (sum of 69
five compounds listed above) ≤ 60 μg/L. The regulatory limit is simply based on taking the 70EE&T, INC. 4

mass concentration of each compound, without correcting for molar weight, and adding each 71
numerical value for the four or five compounds involved. Therefore, a water system with no 72
bromide in the background source water will be in compliance with the TTHM limit if they have 73
60 μg/L of chloroform and no detectable brominated THMs. In this case, about 0.5 μmol/L of 74
TTHMs were produced. However, if nothing else changes but enough bromide is added to 75
produce bromodichloromethane in stead of chloroform, then 0.5 μmol/L of TTHM will produce 76
~82 μg/L which could create compliance difficulties. Therefore, a water system currently in 77
compliance with federal and state requirements may no longer be in compliance if bromide is 78

added to the drinking water source in amounts sufficient to increase the amount of brominated 79
DBPs produced. 80

3. There is increased formation of brominated DBPs due to the greater reactivity of 81

bromide 82
The above suggests that the presence of bromide during chlorinatio n can increase the 83
numerical value of the regulatory compliance value even if the same amount of organic precursor 84
material is present and even if the same molar concentration of DBP is produced. However, 85
since free bromine in drinking water reacts more q uickly than free chlorine, more DBPs (on a 86
molar basis) will be produced since the increased reactivity of bromine will mean more oxidation 87
of organics by bromine, as well as bromine substitution reactions

. 88

A number of factors determine the formation and u ltimate composition of the total THM 89

– water quality parameters, residence time, amount of disinfectant, temperature, type and amount 90
of precursor. For any given utility, the relative amount of each of the four THMs can vary 91
during the year because of cha nges in these factors. Until recently, however, except in coastal 92
locations where bromide can be seasonally introduced because of salt water influences, US 93EE&T, INC. 5

utilities have generally seen more chlorinated than brominated species in their distribution 94

TTHM f

ormation. TTHM data collected from 500 water plants during the I nformation 95
Collection Rule (1997

– 1998) showed that chloroform dominated the other three species, and 96
was present at the highest mean concentration (McGuire, et al 2002). 97

SOURCES OF BROMIDE I N RAW WATER 98
Bromide is a trace element in seawater and is rarely observed naturally occurring at 99
significant concentrations in fresh surface waters in the US (Bowen 1979). Typical seawater 100
concentration is about 65,000 μg/L, resulting in some coastal dri nking water supplies having 101

elevated levels of bromide due to seawater intrusion. Bromide from seawater can influence 102
drinking water sources either through intrusion, or through connate seawater (seawater that is 103
trapped in geological formations.) 104

Bromi de in source water can come from seawater, but it can also come from a number of 105
anthropogenic sources. In the past, before leaded gasoline was banned in the US, gasoline 106

emissions were a contributing factor because leaded gasoline contained additives of brominated 107
compounds. Road salt and some fertilizers can also contribute bromide to source waters. 108
Recently, however, there have been reports of increased bromide in source waters due to 109
industrial activities, including hydraulic fracturing, air pollutio n control in coal

- fired power 110
plants and textile production. 111
A possible contributor to bromide in the source water is effluent from coal

- fired power 112
plants. For some of these power plants to produce a clean air effluent they must use wet 113

scrubbers that can introduce bromide into the waste stream, which is then discharged to a surface 114
water body. Another possible contributor is natural gas production. The development of this 115
fuel requires a significant amount of water and if the water is returned to a w ater body it is 116EE&T, INC. 6

typically high in bromide. Although most unconventional oil and natural gas wastewater is 117
disposed of through deep underground injection, wastewater processed through surface treatment 118
plants may have substantially increase d bromide levels . Another possible bromide source is 119
textile mill processes that use brominated compounds to flameproof fabrics. 120
These sources have been studied to some extent but their full impact on the water utility 121
population is not yet well understood, as utilities are just beginning to see the impact of bromide 122
on their DBPs. Some water utilities have recently noticed an increase in the brominated fraction 123
of their DBPs. A number of utilities with no previous violations have experienced DBP MCL 124

violations due to this brominated fraction. Since bromide is unregulated and has no known health 125
impact
, bromide has not historically been monitored in source water , except in research studies. 126

BROMIDE LEVELS IN SOURCE WATERS AND IMPACTS ON DBP SPECIATION 127
As reported by A my and colleagues, in 1994 a source water bromide survey of 100 128

utilities over 18 months was conducted, showing bromide levels for large and small random ly 129
selected utilities ranged from <5 to 429 μg/L

. A t targeted utilities where the researchers 130

suspecte d that high levels of bromide existed
, the average bromide level was 210 μg/L. When 131

all data were considered, the overall average of all data from the 100 utilities was about 100 132
μg/L

. Lower bromide levels were found in lake sources. The median (50

- perc ent) value for 133
river and groundwater sources was approximately 60 μ g/L, whereas
, that for lakes the median 134
was approximately 30 μg/L . The 90 percent values for river and groundwater sources were 135

ap proximately 300 μ g/L (Amy 1994). 136
During the Information Col lection Rule, all large utilities serving more than 100,000 137

customers were required to sample a number of water quality parameters, including source water 138
bromide and distribution system THMs and HAAs. Samples were analyzed from 500 water 139EE&T, INC. 7

plants during an 18 month period in 1997

– 1998. A shift in speciation toward more brominated 140
DBPs as bromide in the source water increased was noted in the analysis of the database. 141
(McGuire et al 2002). However, the range of speciation within each category of bromide 142
concentration was quite large. About 80 percent of the samples analyzed for bromide in source 143
water were less than 100 μg/L of bromide. 144
The USEPA reported on the results of an extensive nationwide survey of DBP 145
occurrences in drinking water. They found t hat bromide levels in source water above 400 μg/L 146
were associated with increased levels of DBPs in the finished water (Weinberg 2002). 147
Preliminary data from an extensive monitoring effort taking place in North Carolina 148

indicate that the bromide levels in some watersheds are elevated, especially during periods of 149

low stream flow . In one river, bromide levels as high as 1 mg/L were measured (Greune 2013). 150
The percentage of chloroform in the TTHM collected in the distribution system of a drinking 151

water utili ty on that river decreased significantly with increased bromide levels. At the highest 152
bromide source concentration, nearly all of the TTHM was composed of brominated species

. 153
Other recent studies have reported on the same trend. 154

COAL FIRED POWER PLANT DI SCHARGE POTENTIAL IMPACT ON WATER 155
QUALITY 156
Recently finalized air regulations for power plant emissions may result in more 157
brominated compounds being used by these power plants, and ultimately more bromide wastes 158
being discharged to receiving streams. In D ecember 2011, the USEPA approved new strict air 159
discharge limits, referred to as the Mercury and Air Toxics Standards (MATS), targeting oil

- and 160

coal

- fired electrical power generating facilities. These requirements are scheduled to take effect 161
in 2015 (US EPA 2012). MATS will target reductions in emissions of metals (mercury, arsenic, 162EE&T, INC. 8

chromium, nickel), acid gases (hydrochloric and hydrofluoric), particulate matter, sulfur dioxide 163
(SO 2 ), and nitrous oxides (NO x ). Figure 1 shows a USEPA prepared map of the US facilities 164
with coal, oil, or both coal and oil units at the power plant and their relative capacities in 165
megawatts (MW) (USEPA 2011). 166

It is estimated that 1,100 coal

- fired units and 300 oil

- fired units at 600 power plants will 167
be impacted by the MATS requirements (USEPA 2011). P ower plants that use coal as a fuel are 168

most likely to install wet scrubbers and are the focus of this report. 169

The Flue Gas Desulfurization (FGD) process, also known as air scrubbers, is the 170
preferred air pollution control tec hnology for controlling SO 2 and sometimes mercury. The new 171

MATS SO 2 and mercury requirements could result in installation of more wet or dry scrubbers. 172
Economic analysis will dictate which is selected, but wet scrubber technology is generally 173

favored when coal with higher sulfur content is used, as is the case in much of Eastern US. 174
Mercury is present in flue gas in varying percentages, depending on the origin of coal, in 175
three basic forms (Kellie et al, 2005): particulate

- bound, elemental (Hg 0 ), and oxid ized mercury 176
in gas form (Hg 2+ ). The particulate

- bound mercury can be easily removed by electrostatic 177
precipitators (ESP) or fabric filters (Bustard et al. 2003). The oxidized mercury has a tendency 178
to stick to particulate matter and is water soluble (Bl ythe et al. 2002). Consequently, it can be 179
captured by the ESP, fabric filters, or wet/dry scrubbers. However, Hg 0 is highly volatile and 180
insoluble in water and is thus not readily removed by typical air pollution control devices. The 181

relative concentra tion of chloride and bromide that naturally occurs in the coal dictates the form 182
of mercury that is present. In general bromide is lower in lignite and sub

- bituminous coal, 3 ppm 183

and 1

– 2 ppm, respectively, than in bituminous coal, 20 ppm (Buschmann 2005 ). Therefore, the 184

addition of bromide

- containing salts (usually calcium bromide) to the coal combustion unit can 185EE&T, INC. 9

convert the mercury into the more water soluble Hg 2+ form. This soluble mercury is better 186
removed by the wet scrubbers used to clean flue gas ses. 187
However, while the mercury in the wastewater can be removed prior to discharge into a 188
receiving stream, the added bromide is not typically removed and ends up being discharged. A 189
US Department of Energy (USDOE) National Energy Technology Laboratory (NETL) report 190
(Benson et al. 2007) documented the correlation between bromide in or added to the coal and the 191
concentration of bromide in the FGD wastewater, referred to as liquor in their study. The US 192
DOE NETL results in Figure 2 show that after a coup le weeks the FGD liquor concentration of 193
bromide is equal to the concentration that is added to the coal. 194

In 14 full

- scale coal

- fired power plant tests using calcium bromide (CaBr 2 ) to oxidize 195
elemental mercury, greater than 90

- percent of the mercury was oxidized with the addition of 25 196
to 300 ppm bromide by weight of coal (Chang et al. 2008). This range is wide due to the coal’s 197
natural abundance of chlorine and bromine giving the coal varied natural performance for 198
oxidizing mercury. Using this informa tion, it is possible to calculate the amount of bromide that 199
could be discharged as a function of the amount of energy produced by the power plant as 200

described below. 201
A power plant with a 1 MW capacity operated 24 hours a day, 365 days a year would 202
produce 8,760,000 KWh/year. According to the US Energy Information Administration (US 203
EIA) (2013a) it takes 1.07 lbs of coal to produce 1 kWh. This means that for each MW of 204
electrical power plant capacity, a coal

- fired power plant would require 9,373,200 lbs co al/year or 205
25,680 lbs coal/day. With the range of 25 to 300 ppm for bromide noted in Chang et al. (2008), 206
the amount of bromide added to the system each day per MW of power is estimated as follows: 207

208EE&T, INC. 10 209

210 Therefore, depending on the amount of bromide presen t or added to the coal, the 211
production of 1 MW of power would result in the addition of 0.51 to 6.2 lb/day of bromide. 212
Further, according to the DOE NETL report (Benson et al. 2007) all of the bromide added to the 213
power plant is discharged into receiving s treams; these calculations indicate that between 0.51 214
and 6.2 pounds per day of bromide per MW of power produced will be discharged into receiving 215

streams. 216
Currently, there are no bromide discharge standards . However, the new MATS 217
requirements may increase bromide discharges from coal

- fired power plants in a couple of ways. 218

First, coal

- fired power plants have already or are going to be adding wet scrubbers in response to 219

SO 2 removal requirements of MATS. Even if the coal source used has a low bromide conte nt, 220

the increased use of wet scrubbers to remove SO 2 as a consequence of the MATS requirements 221
will result in more bromide releases, even in situations where bromide is not added to improve 222
mercury removal. If the coal source is high in bromide, these wet scrubber discharges will 223
include even greater amounts of bromide. Furthermore, the increased need to remove mercury 224

in coal

- fired power plants may cause bromide to be added, unless the coal is already naturally 225
high in bromide. In either case the amount of bromide released to receiving waters will be 226
greater than before the wet scrubber was added. 227
Figure 3 was prepared by the US EPA (2011) and illustrates the projected improvement in 228
mercury releases in different states as a consequence of the MATs mercu ry requirements. A 229
large portion of these improved mercury releases are expected to be due to increased use of 230
bromide and/or wet scrubber technology. Power plants that have installed scrubbers in response 231EE&T, INC. 11

to the MATS may move to a higher sulfur coal con tent since they already have control 232
technology in place. It is generally less expensive than the low sulfur coal ( USEIA 201 3 b ) and 233
has a higher BTU value (Bowen 2008). Bituminous coal has higher sulfur content and also, as 234
previously discussed, has highe r bromide content. The lower cost of bituminous coal alone 235

could increase scrubber use, wastewater volume and bromide concentrations. 236
According to USEPA (20 1 3 ) 85 percent of the FGD systems installed in the US are wet 237
systems. Generally, it is more cost effective to install a wet scrubber rather than a dry scrubber 238
for a power plant burning a higher sulfur content in the coal, >2% by weight. Also, dry and 239
spray dry scrubbers are applied to smaller uni ts, less than 300 MW (USEPA 20 13 ). Figure 4 is 240

from a USDOE NETL report (Miller et al. 2006), showing that flue gas desulfurization capacity 241

is projected to increase to 231 GW by year 2020. If 90 percent of the FGD processes installed 242
continue to be wet scrubbers, then 208 GW of the electrical power generat ing capacity in 2020 243
will employ wet scrubbers. One vendor promoting the use of bromide injection for mercury 244
control claims a combined total of 8,000 MW of US utility coal

- fired boilers use their technology 245
(Mcilvaine Company 2012). 246
As discussed previou sly, bromide is present in the coal burned, and is often added as 247
calcium bromide in the FGD process. As the use of FGD increases, the amount of bromide that 248
is ultimately released to receiving waters may increase dramatically, resulting in adverse impact s 249
on downstream drinking water plants. 250
Consequently, the new, stringent air emissions regulation designed to lower mercury 251
emissions may result in increased bromide discharges to drinking water sources as power plants 252
change technology or coal sources in efforts to meet the requirements. Public drinking water 253
sources may, in turn, experience difficulty in meeting regulatory requirements and may see an 254EE&T, INC. 12

increase in the production of more brominated DBPs with greater health risks than analogous 255

chlorinated DBPs to drinking water consumers, as previously discussed. 256

Bromine disinfectants, also referred to as bromine biocides, are also used as an 257
alternative to chlorine for cooling tower disinfection. Regulations have made it particularly 258

difficult to use chlo rine to control cooling tower biological fouling. However, power plant 259
cooling water discharges containing bromine are controlled by the NPDES permits which restrict 260
discharge of bromine compounds to not more than two hours per day. This could possibly r esult 261
in a bromide spike and therefore a TTHM spike at a downstream water treatment plant. 262

HYDRAULIC FRACTURING POTENTIAL IMPACT ON WATER QUALITY 263
Unconventional natural gas development (UNGD), also known as hydraulic fracturing or 264
“fracking”, which made up 23 percent of natural gas production in 2010 in the United States, is 265
increasing each year and is expected to grow to 49 percent by 2035 ( USDOE 2012). Hydraulic 266
fracturing introduces water to the shale formation (millions of gallons per well) in order to 267
increase permeability through fracture generation, and thus this water has the potential to return 268
to the surface with gas. Anywhere from 10 to 80 percent of the injected volume may return to 269

the surface as wastewater. The wastewater from this entire pro cess includes both “flowback” 270
and “produced water.” Flowback is the fracturing fluid that quickly returns to the surface, and 271
produced water is the fracturing fluid that takes longer to return to the surface (Robart 2012; US 272

EPA 2010). 273

Both flowback and p roduced waters are enriched with materials from the shale formation, 274

such as minerals, brines, hydrocarbons, and naturally occurring radioactive materials

. T he 275
longer the fluid takes to return to the surface
, the greater the concentratio n of formation mat erials 276
(Hayes 2009). Flowback water management is usually done onsite through minimization, 277EE&T, INC. 13

recycling and reuse within operations. Produced water management may also include treatment 278
followed by surface water discharge, such as at publicly owned wastew ater treatment plants 279
(POTWs) or centralized brine treatment plants (CWTs). Existing CWTs are exempt from the 280
regulations passed in 2008 that included re striction to TDS discharges . This could result in the 281

elevated TDS concentrations , including elevated bromide and chloride found in flowback and 282
produced water being released in the effluent. 283

Table 1 shows the ranges of b romide concentration, the average wastewater flow for the 284
facility, and the receiving watershed for a number of treatment facilities in Pennsylvania that 285

treat hydraulic fracturing wastewater and discharge to surface water bodies . Clearly, significant 286
quantities of bromide are being introduced to receiving waters by these facilities. The West 287
Virginia Department of Environmental Protect ion (WVDEP) also collected 13 produced water 288
samples with bromide levels ranging from 1,290 to 525,000 μg/L, with an average concentration 289
of 185,000 μg/L. 290
For example as shown in Table 1 , the Josephine Brine Facility, located on the 291
Conemaugh River within the Allegheny watershed, typically discharging 155,000 gal/day with 292
an effluent bromide concentration range from 601,000 to 8,290,000 μg/L. However, to fully 293
understand the magnitude of this effluent flow and concentration, the receiving stream flow must 294
be known. The closest USGS gauge station (USGS 03041500) to the brine facility’s discharge 295
on the Conemaugh River measured an average flow of 1,629 ft 3 /s (cfs). This means that the 296
brine effluent flow makes up 0.015 percent of the total river flow, dilut ing the bromide 297
concentration by the same fraction. With that dilution factor, the bromide concentration added to 298
the river at the discharge location is approximately 88 to 1,220 μg/L. As discussed previously, 299
concentrations seen in US rivers by Amy et al . in 1994 averaged around 60 μg/L. Since 1994 300EE&T, INC. 14

pre

- dates the ongoing shale gas development boom, those concentrations could be considered the 301
background concentration. This means that the lower limit of Josephine Brine Facility’s bromide 302

effluent concentra tion is more than double background and the upper limit increase d bromide 20 303

fold. 304

Other Industries 305

Other industries could have wastewater effluents with elevated bromide. Any industry 306
with mercury and SOx emissions could also have or will have wet scrub ber installations as well. 307
Therefore, their effluent streams could be a new source of bromide to receiving streams. 308
Brominated flame retardants are used in a variety of consumer products and several of 309
those are produced in large quantities. The use of flame retardant has grown dramatically over 310
the past 30 years in response to concerns about the increasing use of flammable plastics and 311
textiles. Many concerns surrounding these compounds focus on their persistence in the 312

environment and bioaccumulation. While the flame retardants themselves are unlikely to form 313
DBPs due to their inherent environmental persistence, effluent streams of the facilities that 314
produce and use these compounds (i.e. textile mills) could be a possible source. 315

ANALYSIS OF POTENTIA L IMPACT ON DRINKING WATER 316
Currently there are no standards for drinking water or receiving waters for bromide, since 317

in its unreacted form, bromide has no known health effects associated with ingesting it. 318
Drinking water utilities have not traditionally monitored for bromide in their sources, and in 319
most cases, industries are not required to report levels of bromide discharged to receiving waters. 320
In order to determine the potential number of drinking water utilities that could be 321
impacted by the bromid e resulting from wet scrubber installations at coal fired plants, a number 322

of databases and tools were used. 323EE&T, INC. 15

According to the U. S. Energy Information Administration, there were 332 electric 324

utilities that use d coal from 2002 to 201 1 (USEIA 2011). This n umber only includes the electric 325
production for the public entities and not the independent power producers or the commercial 326
and industrial sectors. These sectors operated an additional 257 coal fired units during 2011, 327
although they are much smaller in general, than those owned by the electric utilities. 328
Of the 332 public entities identified , 302 have NPDES permits. 329
Using the latitude and longitude information provided in the NPDES permits for these 330
plants, a map was created in ArcMap, as shown in Fig ure 5. Along with the latitude and 331
longitude the database for these power plants also contains plant nameplate capacity ( USEIA 332
2011), NPDES permit number ( USEP 2013 ), HUC code ( USEPA 2013 ), FGD type and install 333
year ( USEIA 2011 ) and current coal sulfur co ntent ( USEIA 2013 c ). This information was used 334
to identify water bodies potentially at risk for bromide contamination

. 335
As shown, most of the power plants using coal are east of t he Mississippi River. They 336

are typically located on or near a large surface water body. Also, a high density of coal

- fired 337
power plants is located on the borders of Ohio, West Virginia, Kentucky, and Indiana where the 338

Ohio River is located. 339

Out of the 302 coal

- fired electric utility power plants with NPDES permits identified , 1 18 340
had wet scrubber installations (shown in Figure 5 , part A ), 39 had dry scrubber installations and 341
eight used a high sulfur content coal (>2%) which, as previously discussed are good candidates 342

for a wet scrubber installation. 343
SDWIS (Safe Drinking Wate r Information System) was then used to map community 344
water systems (CWS) that use surface water. The SDWIS database contains information on all 345
community surface drinking water treatment plants in the US including location, Public Water 346EE&T, INC. 16

System Identificat ion (PWS ID) number, population se rved, and contact information. This 347
database included 8,370 surface water treatment plants which serve a population larger than 500. 348
The surface drinking water treatment plant database and the 118 coal

- fired power plan ts 349
with wet scrubbers were plotted in ArcMap, shown in Figure 5 part B with streams/canals, rivers, 350
and water bodies layers. This was done to display power plants that could have bromide in their 351
wastewater effluent. Then with the understanding of stream flow direction, NPDES HUC codes 352
for the power plants, and visual confirmation of drinking water treatment plant locations, 96 353
surface drinking water treatment plans were identified as being downstream from 57 wet 354

scrubber coal

- fired power plants. One powe r plant effluent could impact multiple water 355
treatment plant intakes. These water treatment plants and power plants are shown in Figure 6

. 356
An example of how potentially impacted facilities were identified using the power plant 357
and water treatment plant l ocation databases is shown in Figure 7

. Figure 7 includes locations of 358
a power plant, rivers, streams, and drinking water treatment facilities using surface water. All of 359
the facilities shown in Figure 7 use the same source whether it is influent (WTP) o r effluent 360
(power plant). 361
Through SDWIS it was determined whether these 96 downstream utilities had a reported 362

MCL violation of TTHM or HAA5. Out of the 96 water treatment plant s identified, 25 had DBP 363

MCL violations and 17 of those had violations occurred after wet scrubber installations. Of 364

those 17
, six water treatment plants had violations occur within a year of the install

. These 365
numbers suggest that there may be a correlation between the installation of the wet scrubber and 366

increased DBP formatio n at downstream water plants, although many factors impact the 367
formation of DBPs. To determine if these increases could be due to power plant effluents, state 368
regulators and utility personnel at these water plants were contacted for further information. 369EE&T, INC. 17

UTILITY IMPACTS BY COAL FIRED PLANTS 370

Personnel at fourteen utilities and eight states were contacted. Of those, some reported 371
no increase in DBPs. Four drinking water utilities were identi fied, WTP A through D in Table 2
, 372
as having documented increase s in brominated DBPs along with increased bromide in their 373

source water believed to be from the wet scrubber installation at coal

- fired power plants. All of 374
these increases followed a wet scrubber installation at an upstream power treatment plant. The 375

dat a from each of these four plants is described below. 376

Water T reatment P lant A 377

As shown in Table 2 , WTP A has not had a DBP violation. But THM and HAA data 378
indicated that increases in brominated DBPs were noted during the same time periods elevated 379

bromide w as noted in the source water. The increased bromide in the plant’s source water 380
appears to have occurred shortly after the wet scrubber installation at the power plant in 2009. 381
The TTHM compound impacted most from the increase in bromide in the source wa ter 382
was bromoform. Bromoform in the finished water increased by a factor of 10 to 20. Levels of 383

bromodichloromethane, bromodichloromethane and bromochloroacetic also increased. Other 384
water treatment plants in the area made similar observations, however they declined to provide 385

these data. 386

Water T reatment P lant B 387

Two water treatment plants
, WTP B and WTP C were identified in the NPDES permit of 388

a coal fired power plant that installed a wet scrubber in 2008 were contacted

. WTP B shared 389
quarterly complian ce data. WTP B did not have a violation but utility personnel stated that 390
bromide was observed in their source water in 2008 and was not present before this time. In 391

response to the elevated bromide levels, the utility took samples from the source water, went 392EE&T, INC. 18

several miles upstream and collected samples at each effluent water source. They concluded that 393
the upstream power plant was the bromide source. 394

WTP B uses free chlorine for disinfection but intends to switch to chloramines to avoid 395

DBP exceedances. Figure 8 part A shows WTP B’s average quarterly TTHM speciation for all 396
sampling locations over time. The black line on the figure represents the TTHM MCL level and 397
the vertical red line shows the year that the upstream power plant installed a wet scrubb er. For a 398
TTHM MCL violation to occur the running annual average must exceed 80 μg/L. Exceeding the 399
MCL for one quarter may not result in a violation if the last three quarters were far enough below 400
the MCL to result in the average of the four quarters t o be below the MCL. Prior to 2008, the 401
year of the wet scrubber installation, WTP B had rel atively low TTHM concentration made up of 402
mostly chloroform. After the wet scrubber installation the TTHM not only increased but the 403
speciation was dominated by br ominated THMs. 404
The speciation change is better illustrated when comparing two of the same quarters but 405
from different years, one preceding the wet scrubber installation and one following. For WTP B 406
the second and fourth quarters before and after the in st allation are shown in Figure 8 part B 407
where chloroform is shown in blue. Before the wet scrubber, 2008, less than 25 percent of the 408
TTHM was from brominated compounds, after the installation more than 80 percent of the 409
TTHM was from brominated compounds. 410

Water T reatment P lant C 411
When WTP B started to monitor bromide they contacted WTP C. In response
, WTP C 412
also began to monitor bromide at their intake. WTP C is approximately eight miles from the 413
power plant discharge location while WTP B is about 20 miles away from the source. As shown 414
in Figure 9 part A , after the wet scrubber installation, the red line, the speciation change d and the 415EE&T, INC. 19

concentrations increase d . Bromide monitoring data is also shown in Figure 9 part A . WTP C has 416
had three quarters of THM vio lations. All violations occurred after the wet scrubber installation 417

in 2008, one in 2009 and two in 2011. As shown in Figure 9 part B
, for the same quarter before 418
the scrubber installation the TTHM is almost entirely comprised of chloroform and for the 419
quarters with violations, after the wet scrubber installation, over 90 percent of the TTHM is from 420
brominated compounds. In response to the violations the utility initiated a flushing program in 421

the distribution system and they have installed an aeration system to remove DBPs. 422

Water T reatment P lant D 423
WTP D was identified using the power plant and water treatment plant location databases 424
and is located downstream from a wet scrubber power plant’s discharge location. The upstream 425
power plant had two wet sc rubbers installed, one in 2006 and one in 2007, indicated by the red 426
lines in Figure 1 0 part A . Although the change is not as dramatic as WTP B the majority of 427
THM speciation is brominated after the wet scrubber installations. The change is m ore easily 428

o bserved in Figure 10 part B , where brominated species make up less than 20 percent of TTHM 429
before 2006, when the first wet scrubber was installed and more than 50 percent after 2007, 430

when the second wet scrubber was installed. 431

UTILIT IES IMPACTS BY OTHER INDUSTRIES 432
Other potential sources of bromide such as hydraulic fracturing and textile production, 433
have been reported. 434
Wilson and VanBriesen (2012 ) reported bromide concentrations in excess of 500 μg/L 435
during low stream flow periods in 2008 and 2009 on t he Allegheny River . The authors correlated 436

these increases with increased DBP violations. Between 2008 and 2011, 33 different Western 437
Pennsylvania drinking water systems exceeded THM MCLs ( Frazier and Murray 2011). 438EE&T, INC. 20

States et al. (2012) reported during 201 0
, seven water treatment plants using the 439
Allegheny River as a source had 19 to 110 μg/L TTHMs in their effluent with 12 to 55 percent of 440

those from b romoform

. 441

Water T reatment P lant E 442
WTP E was initially identified and contacted using the coal

- fired power plant and surface 443
water treatment plants database. Utility personnel contacted believe that hydraulic fracturing was 444
the main cause for WTP E’s bromide and subsequent TTHM increase. Since 2008, WTP E’s 445

source water had high TDS , and so was diluted with gro undwater from backup wells. The utility 446
personnel stated that this occurred around the time that hydraulic fracturing began in that area of 447
the country and they believe that fracturing has caused this change. Nearby plants in the area 448

have also violated the T THM MCLs since 2008. Another city that received its water from WTP 449
E exceeded THMs in the water supply in May 2013

. 450
Figure 11 part A shows the average quarterly TTHM speciation for all sampling 451

locations for WTP E from 1999 to 2013, where each color represents a different compound that 452
makes up TTHM and the black line represents the TTHM MCL. According to the utility, the 453
hydraulic fracturing wastewater discharges in the area started in 2008. It is clear that the 454
chlorinated portion (blue) decrease s after 2008 and the brominated portion increases (all other 455
colors). This comparison is better shown in Figure 1 1 part B , where the first column represents 456
samples before hydraulic fracturing impacts and the second represents after. Before hydraulic 457

fra cturing the brominated compounds made up 50 percent or less of TTHM and after they made 458
up more than 80 percent TTHM. 459

Water T reatment P lant F 460EE&T, INC. 21

WTP F was identified through contacts made in the project. The WTP had a THM 461
violation in August of 2012 that resu lted in the utility calling state personnel. The state worked 462
with two point sources, both textile mills located about 100 miles upstream where bromide was 463
discharged from a chemical manufacturing process. This impact was initially noticed by the 464

water t reatment plant during the fourth quarter of 2011, which agrees with the TTHM rise above 465
the TTHM MCL in the third quarter in 2011, shown in Figure 12 part A . Also, the speciation 466
shown in Figure 1 2 part B shows a shift from 30 percent to 80 percent bromin ated THMs before 467
and after the textile mill impact, respectively. In response to the bromide levels, the WTP 468
changed its treatment process. This included increasing the permanganate dose in their reservoir, 469
moving their pow d ered activated carbon feed to allow for longer contact time, decreasing the 470
chlorine dose used in pre

- chlorination, and decreasing the chlorine dose in the distribution 471
system. The state also worked with the textile mills to reduce their discharge. 472

POSSIBLE WAYS TO LIMIT BROMIDE IN SO URCE WATER 473
In order to limit the discharge of toxics to a receiving body, states must develop water 474
quality standard as regulated by the Clean Water Act. Water quality standards are provisions of 475
State or Federal law which consist of a designated use or u ses for the receiving waters and water 476
quality criteria for such waters based upon such uses. 477

T he US EPA website describes the methods that can be used by states to develop these 478

standards

. http://water.epa.gov/scitech/swguidance/standards/wqsregs.cfm 479
As discussed previously, some states have attempted to limit the discharge of bromide 480
through NPDES permits. But, since bromide has not been defined as a “toxic pollutant” 481
according t o the list contained in the CWA (section 307.a), or as a “pollutant” it has been 482
difficult to include bromide limits in discharge permits. However, as the CWA was designed to 483EE&T, INC. 22

“protect the designated use,” states may be able to develop a water quality stan dard for bromide 484
that recognizes that the transformation of bromide within the drinking water plant into by

485
products with human health implications justifies limiting its discharge into a receiving water. 486

While s ome states are not able to get effluent conc entration restrictions
, some have been 487

able to write in e ffluent monitoring requirements power plant’s National Pollutant Discharge 488
Elimination System (NPDES) permits. For example, a power plant in North Carolina that 489

installed a wet scrubber in 2008 is r equired by its NPDES permit to take monthly grab samples 490
that are analyzed for bromide. The permit also requires that the plant submit a semi

- annual 491
status report on the effort they undertake to reduce bromide at the source of downstream water 492

treatment p lants. In the event of a TTHM MCL violation at two named water treatment plants 493
that are located downstream or any wholesale customers of those systems, the power plant is 494
required within 14 days of the request to provide the latest available bromide moni toring data so 495
that it can be incorporated into required public notices issued by the water treatment plant(s)

. 496

CONCLUSIONS 497
With new bromide sources being introduced into drinking water sources it is important 498
for the downstream impacts to be considered. Water utilities need to be made aware of the 499
potential impact of bromide on their distribution system TTHMs and HAAs. This report 500
highlighted a number of occurrences of utilities exceeding MCLs because of the shift to 501
brominated species. However, it is s uspected that many utilities have experienced elevated 502
levels of DBPs without MCL exceedances but are unaware of the cause for this change. 503
Further, State agencies should closely evaluate the discharge permits of industries that 504
use bromide in their proces ses such as coal fire plants and determine if monitoring and bromide 505
limits are appropriate. Because it is so difficult for water plants to remove bromide from their 506EE&T, INC. 23

source water, the best course of action will be to prevent bromide from entering the sour ce of any 507
drinking water plant. 508

REFERENCES 509
Amy, G., Siddiqui, M., Zhai, W., DeBroux, J., Odem, W. 1994. Survey of Bromide in Drinking 510 Water and Impacts on DBP Formation. AWWA Research Foundation and American 511 Water Works Association, Denver, CO, Project #82 5. 512 513 AWWA

. 2004. Formal Comments of the American Water Works Association on the Stage 2 514 Disinfectants and Disinfection By

- Products Proposed Rule, Water Docket OW

- 2002

- 515 0043 . Washington, DC: AWWA. 516 517 Benson, S.A., Holmes, M.J., McCollor, D.P., Mackenzie, J.M., Crocker, C.R., Kong, L., 518 Galbreath, K.C., Dombrowski, K., Richardson, C. 2007. Large

- Scale Mercury Control 519 Technology Testing for Lignite

- Fired Utilities

– Oxidation Systems for Wet FGD. US 520 DOE, NETL. 2007

- EERC

- 03

- 12. 521 522 Blythe, G., Richardson, C., Rhudy, R. 2002. Pilot Evaluation of the Catalytic Oxidation of 523 Mercury for enhanced Removal in Wet FGD Systems. In Proceedings of Air Quality III: 524 Mercury, Trace Elements and Particulate Matter Conference, Arlington, VA, September 525 9

- 12, 2002. Energy and Environment al Research Center, University of Dakota, Grand 526 Fork, North Dakota, September 2002. 527 528 Bowen, B.H., Irwin, M.W. October 2008. Coal Characteristics: Center for Coal Technology 529 Research Basics Facts File #8. The Energy Center at Discover Park, Perdue Universit y. 530 http://www.purdue.edu/discoverypark/energy/assets/pdfs/cctr/outreach/Basics8

- 531 CoalCharacteristics

- Oct08.pdf 532 533 Bowen, H.J.M. 1979. Environmental Chemistry of Elements. London: Academic Press. 534 535 Buschmann, J., Lindau, L., Vosteen, B.W. 2005. The KNX Coal Ad ditive Technology: A Simple 536 Solution for Mercury Emissions Control. ALSTOM Power Inc. h ttp://www.vosteen

537

c onsulting.de/downloads/2005_12_Vosteen_Consulting_KNX_TM_Coal_Additive_Tech 538 nology_PowerGen_USA.pdf 539 540 Bustard, J. , Renninger, S., Chang, R., Miller, R., Monroe, L., Sjostrom, S. 2003. Results of 541 Activated Carbon Injection for Mercury Control Upstream of COHPAC Fabric Filter. 542 Presented at the A&WMA/EPA/DOE/EPRI Combined Power Plant Air Pollutant Control 543 Mega Symposium, Washington, DC, May 19

- 22, 2003. 544 545 Can tor, K.P., Villanueva, C.M., Silverman, D.T., Figueroa, J.D., Real, F.S., Garcia

- Closas, M., 546 Malats, N., Chanock, S., Yeager, M., Tardon, A., Garcia

- Closas, R., Serra, C., Carrato, 547 A., Castano

- Vinyals G., Samanic, C., Rothman, N., and Kogevinas, M. 2010. 548EE&T, INC. 24

P olymorphisms in GSTT21, GSTZ1, and CYP2E1, disinfection by

- products, and risk of 549 bladder cancer in Spain. Environmental Health Perspective, 118, 1545

- 1550. 550 551 Chang, R. et al. 2008. Near and Long Term Options for Controlling Mercury Emissions from 552 Power Plan ts. Proceedings of the Power Plant Air Pollutant Control “Mega” Symposium, 553 Baltimore, MD, August 25

- 28, 2008. 554 555 Environmental Law Clinic, University of Pittsburgh School of Law. 2009. Wastewater 556 Treatment Facilities. Clean Water Action, 2009, July 15. http://www.pennfuture.org/ 557 UserFiles/File/Marcellus_WaterTreatment_20090715.xls 558 559 Ferrar et al. 2013. Assessment of Effluent Contaminants from Three Facilities Discharging 560 Marcellus Shale Wastewater to Surface Waters in Pennsylvania. Environ. Sci. Technol., 561 47, 3472

- 3481. 562 563 Frazier, R.R., Murray, A. 2011. Salts from drilling, a drinking water danger, still showing up in 564 rivers. The Allegheny Front. December 2, 2011. 565 566 Greune, A., Knappe, D. (2013.) Bromide Occurrence in No rth Carolina Surface Waters. NC 567 State University. 568 569 Hayes, T. 2009. Sampling and Analysis of Water Streams Associated with the Development of 570 Marcellus Shale Gas; Report for the Marcellus Shale Coalition; Gas Technology Institute 571 572 Jolley, R. 1975. Chlorine

- containing organic constituents in chlorinated effluents. Jour WPCF. 573 47:3:601. 574 575 Kellie, S.
, Cao, Y. , Duan, Y., Li, L., Chu, P., Mehta, A., Carty, R., Riley, J.T., Pan, W.P. 2005. 576 Factors Affecting Mercury Speciation in a 100

- MW Coal

- Fired Boiler with Low

- N Ox 577 Burners. Energy Fuels, 19:3:800

- 806. 578 579 Mcilvaine Company, 2012. Big Market for Chemicals to Capture Mercury. 580 www.pollutionsolutions

- online.com 581 582 McGuire, M., McLain, J., Obelensky, A. 2002. Informati on Collection Rule Data Analysis. 583 WaterRF, Denver, CO. 584 585 Robart, C. J. 2012. Water Management Economics in the Development and Production of Shale 586 Resources; International Association for Energy Economics; http://www.goog le.com/ 587 url?sa=t&rct=j&q=&esrc=s&source=web&cd=3&ved=0CFYQFjAC&url=http%3A%2F 588 %2Fwww.iaee.org%2Fen%2Fpublications%2Fnewsletterdl.aspx%3Fid%3D157&ei=KX 589 18T6fiKMX00gGRqN3oCw&usg=AFQjCNE1P6_9r6UvkXfecb8RQPRMMI5jpg&sig2 590 =ftRnZeUjOamktVCa8pK5gg. 591 592 States, S., Cypr ych, G., Stoner, M., Wyndra, F., Kuchta, J., Casson, L., Monnell, J., 2012. 593 Bromide in the Allegheny River and THMs in Pittsburgh Drinking Water: A Link with 594EE&T, INC. 25

Marcellus Shale Drilling. Ohio AWWA; http://www .ohiowater.org/oawwa/oawwa/ 595 state%20conventions/ARCHIVES/2012/Presentations/Bromide%20in%20the%20Allegh 596 eny%20River%20and%20THMs.pdf 597 598 US DOE . 2012. Annual Energy Outlook 2012: Early Release Overview; Energy Information 599 Administration. Energy Information Ag ency; http://www.eia.gov/forecasts/aeo/er/pdf/ 600 0383er%282012%29.pdf. 601 602 US EIA. 2011. Form EIA

- 860. US DOE, Washington, DC. http://www.eia.gov/electricity/ 603 d ata/eia860/

. 604 605 US EIA . 2013 a . How Much Coal, Natural Gas, or Petroleum Is Used to Generate a Kilowatt

606 hour of Electricity? Web. http://www.eia.gov/tools/faqs/faq.cfm?id=667&t=2. 607 608 US EIA. 2013b. 2012 Brief: Coal Prices and Production in Most Basins Down in 2012. U.S. 609 Energy Information Administration. www.eia.gov/todayinenergy/detail.cfm?id=9570 610 611 US EIA. 2013c . Form EIA

- 923 . US DOE, Washington, DC. http://www.eia.gov/ 612 electricity/data/eia923/ .US EPA. 2003. Air Pollution Cont rol Technology Fact Sheet: 613 Flue Gas Desulfurization (FGD)

– Wet, Spray Dry, and Dry Scrubbers. Washington, DC: 614 US EPA. 615 616 USEPA. 2006. Stage 2 Disinfectants and Disinfection Byproducts Rule: National Primary and 617 Secondary Drinking Water Regulations: Final Ru le. Federal Register 71:2:388

- 493, 618 January 4, 2006. 619 620 USEPA. 2011. Regulatory Impact Analysis for the Final Mercury and Air Toxics Standards 621 (EPA

- 452/R

- 11

- 011). Washington, DC: US EPA. 622 623 US EPA . 2012. National Emissions Standards for Hazardous Air Pollutants from Coal

- and Oil

624 fired Electrical Generating Units (40 CFR 60 and 63). Federal Register . 77:32:9304

- 625 9513. 626 627 US EPA. 2013. Facility Registry Service (FRS) Query. US EPA, Washington, DC. 628 http://www.epa.gov/enviro/html/fii/fii_query_java.html. 629 630 Weinberg, H.S ., Krasner, S.W., Richardson, S.D., Thruston, A.D. 2002. The Occurrence of 631 Disinfection By

- Products (DBPs) of Health Concern in Drinking Water: Results of a 632 Nationwide DBP Occurrence Study. National Exposure Research Laboratory. Office of 633 Rese arch and Development, United States Environmental Protection Agency, Athens, 634 GA. EPA/600/R

- 02/068 635 636 Wilson, J.M., VanBriesen, J.M. 2012. Oil and Gas Produced Water Management and Surface 637 Drinking Water Sources in Pennsylvania. Environmental Practice, 14 (4) 288

- 300. 638 639 640EE&T, INC. 1 Table 1 Bromide Concentrations in CWTs and POTWs in PA Treating Marcellus Shale Wastewater

Name Treatment facility type Br concentration (μg/L) a,b Date Plant flow (gal/day) c Receiving

watershed c minimum maximum minimum maximum PA Brine Josephine Facility CWT 601,000 8,290,000 5/25/2011 12/21/2011 155,000 Allegheny PA Brine Franklin Facility CWT 364,000 770,000 8/2/2011 5/9/2011 300,000 Allegheny
Minard Oil Dent Treatment Facility CWT 606,000 657,000 10/6/2011 2/9/2012 16,000 Monongahela
Brockwa y Sewer Authority POTW 2,320 19,200 12/7/2011 11/21/2011 1,500,000 Allegheny Ridgway Borough POTW 2,880 11,500 9/8/2011 7/21/2011 2,20,000 Allegheny City of McKeeport POTW 119 600 10/20/2010 10/19/2010 11,500,000 Monongahela
Franklin TWP of Greene Count y POTW <0.016 20,910 11/7/2011 11/10/2010 1,250,000 Monongahela

a US EPA.2013. Key Documents About Mid

- Atlantic Oil and Gas Extraction. http://www.epa.gov/region03/marcellus_shale

b Ferrar et al. 2013. Assessment of Effluent Contaminants from Three Fac ilities Discharging Marcellus Shale Wastewater to Surface Waters in Pennsylvania. Environ. Sci. Technol., 47, 3472

- 3481. c Environmental Law Clinic, University of Pittsburgh School of Law. 2009. Wastewater Treatment Facilities. Clean Water Action , 2009, J uly 15. http://www.pennfuture.org/UserFiles/File/Marcellus_WaterTreatment_20090715.xlsEE&T, INC. 2 Table 2 Water Treatment Plants impacted by bromide sources with the population they serve, the wet scrubber installation years of the upstream wet scrubbers, and th e years the water

treatment plant had TTHM or HAA5 MCL violations.
Water treatment plant Bromide

source Population

served Wet scrubber

installation year TTHM

violation
year HAA5

violation year A Power plant 227,000 2006, 2007, 2009

- - B Power plant 16,000 2008

- - C Power plant 3,000 2008 2008, 2009

- D Power plant 24,000 2006, 2007

- 2003

E Shale gas

wastewater discharge 22,000

- 2008, 2009

-

F Textile mill 18,000

- 2012

-EE&T, INC. 1

Figure 1 Location of US Power Plants impacted by new air quality regulations (US EPA 2011)EE&T, INC. 2

Figure 2 Measured bromide c oncentration in the FGD liquor with respect to bromide

concentration in coal (Benson et al

. 2007)

Figure 3 Projected State

- by

- State mercury (Hg) emissions from US Coal

- Fired Power

Plants with and without improvements in response to MATS requirements (USEPA 2011)EE&T, INC. 3

Figure 4 Projected increase in US Coal

- Fired Wet FGD Capacity (Miller et al

. 2006)EE&T, INC. 4

a ) C oal

- fired power plants with NPDES Permits (302) and those with wet

scrubbers (118) in the U.S.

b ) S urface water treatment plants and coal

- fired power plants with and without

wet scrubbers
Figure 5 Locations of surface water plants and coal fired power plantsEE&T, INC. 5

Figure 6 C oal

- fired power plants with wet scrubbers and downstream surface drinking water treatment plants Note, there

are 96 WTPs identified with several hidden in the mapEE&T, INC. 6

Figure 7 A coal

- fired power plant and five downstream surface water treatment plants

for drinking waterEE&T, INC. 7

a ) Average quarterly T THM concentrations for WTP B from Quarter 2 of 2006 to Quarter 3 of

2013
Before Upstream Wet Scrubber

Installation After Upstream Wet Scrubber Installation

b ) THM Speciation for WTP B for the same quarters preceding and following the wet s crubber

installation year, 2008
Figure 8 THM Data from Water Plant B 0.0000 0.0200 0.0400 0.0600 0.0800 0.1000 0.1200 0.1400

5/3/2006 8/1/2006 11/8/2006 2/6/2007 5/1/2007 8/7/2007 11/20/2007 2/12/2008 5/20/2008 8/12/2008 11/18/2008 2/24/2009 5/12/2009 8/18/2009 11/9/2009 2/17/2010 5/12/2010 8/18/2010 11/1/2010 2/1/2011 5/2/2011 8/1/2011 11/1/2011 2/1/2012 4/2/2012 7/3/2012 8/2/2012 11/28/2012 2/5/2013 4/2/2013 7/1/2013 THM (mg/L)

Chloroform Bromoform Bromodichloromethane
Dibromochloromethane TTHM MCL Wet Scrubber Installation

Chloroform Bromoform Bromodichloromethane Dibromochloromethane 

## Q4 2006 Q4 2012

Q2 2007 Q2 2013EE&T, INC. 8

a ) TTHM concentrations for WTP C from Quarter 1 of 2006 to Quarter 4 of 2012

Before Upstream Wet Scrubber

Installation After Upstream Wet Scrubber Installation

b ) THM Speciation for WTP C for the same quarters preceding and following the wet

s crubber installation year, 2008 Figure 9 THM Data from Water Plant C 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

0.0000 0.0200 0.0400 0.0600 0.0800 0.1000 0.1200 0.1400 0.1600 0.1800

02/23/06 09/20/06 02/14/07 09/19/07 02/20/08 09/18/08 02/18/09 09/24/09 02/25/10 09/08/10 03/10/11 09/07/11 7/31/2012 8/13/2012 8/28/2012 9/10/2012 9/24/2012 10/8/2012 10/23/2012 11/5/2012 11/19/2012 12/3/2012 12/17/2012

Bromide (mg/L) THM (mg/L)

Chloroform Bromoform Bromodichloromethane
Dibromochloromethane TTHM MCL Bromide

Wet Scrubber Installation

Chloroform Bromoform Bromodichloromethane Dibromochloromethane 

## Q2 2008 Q2 2011

Q3 2006 Q3 2011EE&T, INC. 9

a ) Average quarterly TTHM concentrations for WTP D from Quarter 2 2005 to Quarter 4

2012
Before Upstream Wet Scrubber

Installation After Upstream Wet Scrubber Installation

b ) THM s peciation for WTP D for the same quarters preceding and following the wet scrubber

i nstallation year, 2006 and 2007
Figure 10 THM Data from Water Plant D

0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 THM (mg/L)

Chloroform Bromoform Bromodichloromethane
Chlorodibromomethane TTHM MCL Wet Scrubber Installations

Chloroform Bromoform Bromodichloromethane Dibromochloromethane 

## Q1 2005 Q1 2008

Q4 2005 Q4 2008EE&T, INC. 10

a ) Average quarterly TTHM concentrations for WTP E from Quarter 2 1999 to Quarter 3 2013

Before Hydraulic Fracturing Activity After Hydraulic Fracturing Activity

b ) THM Speciation for WTP E for the same quarters preceding and followin g hydraulic fracturing

activity Figure11. THM Data from Water Plant E

0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18

5/4/1999 12/7/1999 4/30/2000 12/13/2000 4/4/2001 12/5/2001 4/24/2002 12/10/2002 4/2/2003 12/11/2003 4/6/2004 12/9/2004 4/6/2005 12/7/2005 4/6/2006 12/6/2006 4/11/2007 12/11/2007 4/16/2008 8/28/2008 1/11/2009 7/8/2009 1/14/2010 7/14/2010 1/11/2011 7/13/2011 1/18/2012 7/9/2012 1/9/2013 7/9/2013 THM (mg/L)

Chloroform Bromoform Bromodichloromethane
Dibromochloromethane TTHM MCL

Chloroform Bromoform Bromodichloromethane Dibromochloromethane 

## Q3 2006 Q3 2008

Q1 2007 Q1 2009EE&T, INC. 11

a ) Average quarterly TTHM concentrations for WTP F from Q uarter 1 2007 to Quarter 3 2012

Before Textile Mill Impacts After Textile Mill Impacts

b ) THM Speciation for WTP F for the same quarters preceding and following the wet scrubber

i nstallation year, 2006 and 2007 Figure12 THM Data from Water Plant F

0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1

2/21/2007 5/24/2007 8/28/2007 10/16/2007 1/23/2008 4/23/2008 7/22/2008 10/22/2008 1/21/2009 4/22/2009 7/22/2009 11/2/2009 3/16/2010 4/21/2010 7/22/2010 10/20/2010 1/19/2011 4/20/2011 7/21/2011 10/20/2011 1/18/2012 5/16/2012 8/16/2012 TTHM (mg/L)

Chloroform Bromoform Bromodichloromethane
Dibromochloromethane TTHM MCL



## TTHM Q2 2007

Chloroform Bromoform 

## TTHM Q2 2012

TTHM Q3 2009 TTHM Q3 2012