THE DEVELOPING PROBLEM OF BROMINATED ORGANICS OF THE PUBLIC DRINKING
WATER SUPPLY IN SOUTH WESTERN PENNSYLVANIA
by
David Karl Schultise
Bachelor of Science, University of Pittsburgh, 2005
Submitted to the Graduate Faculty of
Graduate School of Public Health in partial fulfillment
of the requirements for the degree of
Master of Public Health
University of Pittsburgh
2013
i
UNIVERSITY OF PITTSBURGH
Graduate School of Public Health
This essay is submitted
by
David Karl Schultise
on
April 17, 2013
and approved by
Essay Advisor:
Aaron Barchowsky, PhD
_______________________________________
Professor
Department of Environmental and Occupational Health
Graduate School of Public Health
University of Pittsburgh
Essay Reader:
Leonard Casson, PhD, P.E.
_______________________________________
Associate Professor
Department of Civil and Environmental Engineering
Swanson School of Engineering
University of Pittsburgh
ii
Copyright © by David Karl Schultise
2013
iii
Aaron Barchowsky, PhD
THE DEVELOPING PROBLEM OF BROMINATED ORGANICS OF THE PUBLIC
DRINKING WATER SUPPLY IN SOUTH WESTERN PENNSYLVANIA
David Karl Schultise, MPH
University of Pittsburgh, 2013
ABSTRACT
Shale found in the United States and globally represents a source of energy and economic impact
too enormous to ignore. However, there are potential environmental impacts that have been
discovered utilizing the unconventional drilling methods needed to extract gas from shale. In the
U.S., there are environmental concerns involving to air and water quality as well as other factors
such as impacts on communities.
In Wyoming, where air quality is normally quite good, has seen extremely high levels of ozone
since the gas extraction has begun. In other areas such as Pennsylvania there have been concerns
of shale drilling and the contamination of private drinking water wells. Many research studies
have focused on methane migration in shallow ground water wells. Additionally, in western
Pennsylvania there has been an association with shale gas wastewater and elevated levels of
bromide in rivers which is a major resource for drinking water. Bromide itself is not harmful and
had not been tracked or regulated in Pennsylvania and therefore there are no historical records to
reference.
Bromide is a significant public health risk because bromide reacts with chlorinated organics to
form disinfection by-products called trihalomethanes (THMs) in chlorinated drinking water.
Local water quality experts observed higher than normal levels of brominated species of THMs
iv
since unconventional drilling in the Marcellus shale began in the region. Brominated species of
disinfection by-products have been described by toxicologists as probable carcinogens and are
more toxic then the chlorinated species. The numbers of violations for THMs in South Western
PA correspond with the increases in drilling activity and shale gas waste-water. Additional
research and policies regarding unconventional drilling and waste-water management are
needed.
v
TABLE OF CONTENTS
1.0
INTRODUCTION ........................................................................................................ 1
1.1
MARCELLUS SHALE AND HYDRAULIC FRACTURING ........................ 2
1.2
TRIHALOMETHANE TOXICOLOGY ........................................................... 5
2.0
WATER CHEMISTRY AND BROMIDE CONCERNS ......................................... 7
2.1
PWSA AND UNIVERSITY OF PITTSBURGH STUDY ................................ 8
2.2
SAFE DRINKING WATER COMPLIANCE ISSUES.................................... 9
2.3
CONVENTIONAL TREATMENT INADEQUATE ..................................... 11
3.0
POTENTIAL SOURCES OF BROMIDE AND WATER MANAGEMENT ...... 14
4.0
SUSTAINABILITY ................................................................................................... 17
5.0
POLICY ...................................................................................................................... 18
6.0
SUMMARY AND CONCLUSION........................................................................... 20
APPENDIX: SUPPLEMENTAL INFORMATION ................................................................ 21
BIBLIOGRAPHY ....................................................................................................................... 25
vi
LIST OF TABLES
Table 1. The Maximum Contaminant Levels (MCL) and MCL Goals (MCLG) for Regulated
THMs .............................................................................................................................................. 5
Table 2. Shale Gas Wastewater Bromide Concentrations ............................................................ 10
Table 3. Distribution of Wastewater Disposal Methods ............................................................... 15
vii
LIST OF FIGURES
Figure 1. Shale Plays in the Lower 48 States................................................................................ 21
Figure 2. THM Violations in Pennsylvania by Region................................................................. 22
Figure 3. Bromide Concentration in the Monongahela River....................................................... 22
Figure 4. Number of Treatment Plants by Region Utilizing Surface or GUDI Sources .............. 23
Figure 5. Number of Unconventional Wells Spud in Pennsylvania ............................................. 23
Figure 6. Number of THM Violations in South Western Pennsylvania ....................................... 24
viii
1.0
INTRODUCTION
Shale found in the United States represents a source of energy and economic impact too enormous to
ignore, see Figure 1. Natural gas has become the fossil fuel of choice both environmentally and politically
because it is cleaner burning than other fossil fuels such as coal, it can be produced domestically, and it is
relatively inexpensive (Rozell, 2012). In the US there are many large shale plays; among the largest is the
Marcellus in the northeast. However, there are potential environmental impacts that have been discovered
due to the use of the newly developed unconventional drilling methods needed to extract gas from the
shale. In the US, there are environmental concerns mostly involving to air and water quality, as well as
other factors such as impacts on communities.
Wyoming, where air quality is normally quite good, has seen extremely high levels of ozone since the gas
extraction has begun. Gas well sites have been known to increase ozone precursors such as NOx and
VOCs, which contributed to ozone levels exceeding the national ambient air quality standard (NAAQS)
(Fields, 2010). In Pennsylvania, there is increased alarm of shale drilling and contamination of private
drinking water wells from methane migration. Many studies have been conducted to determine the fate
and transport of the methane, but less attention has been on surface waters and water resource
management. In Southwestern Pennsylvania there has been an association with drilling wastewater and
increased levels of bromide in rivers which is a major source of drinking water.
Bromide is a significant public health risk because bromide reacts with chlorinated organics to form
disinfection by-products called trihalomethanes. Water quality experts at Pittsburgh Water and Sewer
1
Authority, University of Pittsburgh, Pennsylvania American Water Company, and Carnegie Mellon
University have found higher than normal levels of brominated species in the local rivers since
unconventional drilling started in Southwestern Pennsylvania.
1.1
MARCELLUS SHALE AND HYDRAULIC FRACTURING
The Marcellus play occurs in Ohio, New York, West Virginia, Pennsylvania, and parts of Maryland
(Kappel, 2009). The Marcellus shale is a Devonian age layer of sedimentary rock located in the
Appalachian Basin (Kappel, 2009). This relatively thin layer of black shale formed from an ancient
seabed, which over time and high pressure caused this layer to be abundant in hydrocarbons. Marcellus
shale covers approximately 31 million acres and ranges from 4,000-7,000 feet below the Earth’s surface
(Kappel, 2009).
The Marcellus formation consists of wet and dry gases. Wet gas has greater value in the petrochemical
industry than the energy industry. Some of the components of wet gas include ethane, benzene, tolulene,
ethylbenzene, and xylene (a group called BTEX), hydrogen sulfide (H2S) and others which can be broken
down or “cracked” into smaller chemical building blocks. Shell Chemical intends to build an ethane
cracker in Beaver County Pennsylvania as a result of the abundant source of raw chemical materials. The
chemical cracking and other spin-off jobs extend the economic impacts of this formation. Dry gas is
predominantly methane, used as a fuel source for home heating, electrical power generation, and
transportation among other uses.
This resource has become significant recently and was estimated in 2008 to have recoverable natural gas
of 363 trillion cubic feet (TCF) (Kappel, 2009). The total annual US consumption of natural gas is about
25 TCF (US Energy Information Administration, 2013). The oil and gas industry is not new to
Pennsylvania, in fact, oil exploration began in Venango County, PA in 1859. Since then, over 350,000
2
wells have been drilled in PA (Boyer, 2012). Increased interest in the Marcellus shale began in the 1990s
is a result of two factors. First, wellhead prices increased from $2.00 per million cubic feet (MCF) in the
1980s to a peak of $10.82 per MCF in 2008. Second, is due to the advent of directional drilling which is
now used in conjunction with hydraulic fracturing (Kappel, 2009).
Directional drilling allows for drillers to drill down to the shale layer and then turn to follow the
horizontal shale seam. The existing technique of hydraulic fracturing is incorporated to fracture the shale
which then allows for the gas to flow to the surface. The hydraulic fracturing process requires large
volumes of water (3-5 million gallons), high pressure, proppant, about 0.5% chemicals, many of which
are toxic to humans and wildlife (Colborn, 2011). Proppant is a material that holds open fractures in the
formation to allow for the gas to flow freely, this is usually sand.
The Pennsylvania Department of Environmental Protection has defined this new hydraulic fracturing
process as such: Unconventional Drilling – “An unconventional gas well is a well that is drilled into an
unconventional formation, which is defined as a geologic shale formation below the base of the Elk
Sandstone or its geologic equivalent where natural gas generally cannot be produced except by horizontal
or vertical well bores stimulated by hydraulic fracturing” (PA DEP).
Some of the water from this process (10-25%) returns to the surface is called “flowback” and occurs after
10-14 days, over time up to 80% of water returns to the surface (Hayes, 2009; Kirby, 2010). Once
production begins, produced water that returns to the surface contains chemicals from the Marcellus
formation itself in addition to the chemicals in the slick water. Some of the chemicals returning to the
surface are total dissolved solids (TDS), sodium, calcium, chloride, bromide, potassium, barium,
strontium, radium, uranium, and hydrocarbons such as benzene (Kirby, 2010; Kappel, 2009; Vanbriesen,
2012). The concentrations of these chemicals in the produced water generally increase over time spent in
3
the formation (Hayes, 2009). TDS ranges from 3,010-261,000mg/L, bromide ranges from 1851,600mg/L, chloride ranges from 1,670-181,000mg/L, sulfate ranges from 10-89.3mg/L (VanBriesen,
2012).
Despite all the benefits of the energy and chemical components, it is not hard to see there may be health
and environmental consequences to this method of exploration. Surface water treatment plants in the
South Western Region of Pennsylvania have experienced challenging source water conditions, possibly
from shale wastewater, that have increased the brominated species of trihalomethanes (THMs) in drinking
water. Many treatment works are failing or struggled to meet the disinfection by-products (DBPs)
regulatory requirements that EPA establishes for public health. The Stage 1 and 2 Disinfectants and
Disinfection By-products Rules are the regulatory framework, which is designed to maintain safe drinking
water. Figure 2 illustrates most violations are in the South West compared to other regions in
Pennsylvania. Stage 2 was implemented on April 1, 2012 for water systems serving a population greater
than 100,000 and is more stringent than Stage 1. Stage 2 required samples to be collected in the
distribution system and compliance calculated on a locational running annual average (LRAA) rather than
averaging all sites so additional violations could be expected as more systems comply with the Stage 2
rule. This paper’s primary focus is on the trihalomethane (THM) class of disinfection by-products as a
result of chlorinated drinking water. Haloacetic Acids are also a by-product of chlorinated water but
remain low in South Western Pennsylvania.
4
Table 1. The Maximum Contaminant Levels (MCL) and MCL Goals (MCLG) for Regulated THMs
Species of THM
MCL
Bromodichloromethane
Bromoform
Dibromochloromethane
Chloroform
1.2
MCLG
80µg/L (Sum of the
Zero
concentrations all four
Zero
trihalomethanes) as an
60µg/L
annual average
70µg/L
TRIHALOMETHANE TOXICOLOGY
DBPs were first discovered in chlorinated drinking water in the 1970s (Bellar, 1974 and Rook, 1974).
THMs are a class of regulated disinfection by-products comprising of four species which are listed above.
The EPA Integrated Risk Information System (IRIS) has classified these THMs as being B2, probable
human carcinogens with the exception of dibromochloromethane, which is a C, possible human
carcinogen, over a lifetime exposure. The brominated species (bromoform and dibromochlormethane)
were found to develop cancers of the bladder, rectal, or colon in mice or rats. The chlorinated species
(chloroform and bromodichloromethane) were found to cause liver and kidney tumors in mice or rats.
There was inadequate support for humans but there was a positive correlation between drinking
chlorinated water and several human cancers. This information lacked control for risk factors such as diet,
smoking, and alcohol consumption. Toxicologists have described the brominated species of haloacetic
acids to be more toxic than chlorinated species (Plewa, 2004). Richardson also describes brominated
DBPs as having a greater toxicological effect than chlorinated (Richardson, 2007). Humans are exposed
to THMs when they use chlorinated municipal water. According to the EPA, a family of four uses an
average of 400 gallons of water per day, 70% of this is used indoors for activities such as cooking,
5
bathing, drinking. Routes of exposure include ingestion, dermal absorption, and inhalation (EPA). Due to
multiple routes of exposure drinking bottled water may not have a significant reduction in exposure. As a
result of THM toxicity and exposure it is important to find methods to reduce the levels of long term
exposure and risk of cancer.
6
2.0
WATER CHEMISTRY AND BROMIDE CONCERNS
The first unconventional hydraulically fractured well was drilled in 2006, since then surface water
treatment works began to see an increase in DBP formation. Historically, many of the DBPs were
predominantly chlorinated species of trihalomethanes, but have shifted more to the brominated species. In
2008-09 the PA DEP conducted a study of water systems whose source is the Monongahela and Ohio
Rivers. These rivers had unusually high levels of sulfate and total dissolved solids (TDS) (Handke, 2009).
DEP concluded that water systems in the DEP study were found to have THM concentrations that were
impacted by bromide in the source water at varying times of the year (Handke, 2009). Two years later,
Pittsburgh Water and Sewer Authority (PWSA) documented higher brominated species as a result of
increased bromide levels in the neighboring Allegheny River (States, 2012).
Natural Organic Matter (NOM) + Cl2 + Br- ----- Trihalomethanes: (CHCl3), (CHCl2Br), (CHClBr2), (CHBr3)
Components of NOM include humic and fulvic acids from decaying plants and are identified as DBP
precursors. A 2002 EPA study has shown that increases in bromide concentration in source water
increases THMs and causes a shift in speciation (EPA, 2002). Even at low bromide concentrations mixed
bromochloro and brominated species increased (Chang, 2001). Hypobromous acid and hypobromite are
generated by the reaction with chlorine and bromide. Hypobromous acid reacts with NOM more quickly
than hypochlorous acid. Therefore, when bromide is present increased brominated species of DBPs are
expected (Chang, 2001). The observed shift within the THMs to more brominated species is partially due
to the molecular mass being greater in the brominated than chlorinated species (Handke, 2009). Bromide
7
is common in seawater and the brominated DBPs predominate as expected. Known sources of bromide in
South Western Pennsylvania may include, but are not limited to coal fired power plant air scrubbers, steel
mills, publically owned treatment works (POTWs), and industrial waste water facilities. Because bromide
by itself is not harmful, there is not a regulatory discharge limit and therefore is not measured or reported.
However, it can be concluded that the increased presence of brominated THMs demonstrates an increase
of bromide in the source water.
2.1
PWSA AND UNIVERSITY OF PITTSBURGH STUDY
Due to limited or no data, the natural levels of bromide in Western Pennsylvania rivers systems are not
clear. PWSA and the University of Pittsburgh studied the raw water in the Allegheny River and its
tributaries and estimated the natural concentration to be less than 50µg/L. Their study found bromide
levels at the water treatment plant intakes in Pittsburgh tend to vary by season and rainfall, but were often
measured around 150-175µg/L in dryer months during 2010 and 2011. Peak levels have been measured as
high as 241µg/L in 2010 and 299µg/L in 2011. In a 2002 EPA study which included all regions in the
United States found source water bromide concentration ranges of 400µg/L, 150µg/L, and 20µg/L which
were classified as high, moderate, and low concentrations, respectively. The source water that was
400µg/L was influenced by seawater intrusion (EPA, 2002).
The PWSA study focused on several factors including the sources of bromide, effectiveness of bromide
removal by the PWSA plant, and the natural levels of bromide in the Allegheny system. Known
contributors of bromide on the Allegheny River system are coal power plants, POTWs receiving shale
waste-water, steel mills, and industrial treatment facilities treating shale waste water. Data indicates
industrial plants treating Marcellus shale waste-water has the most significant impact on water quality.
For example, industrial waste plant C contributed a 21 fold increase (116 to 2,400µg/L) in bromide
8
concentration in July 2011 (States, 2012). A mass balance analysis in 2011 found that the industrial sites
contributed to -30-130% mass contribution of bromide. Six of the twelve months in 2011 were more than
50% bromide contribution by mass (States, 2012). Coal fired power plants and POTWs treating Marcellus
waste water also contributed to increases in bromide, particularly, power plants in the summer months
(States, 2012). Overall, bromide levels increase downstream. There is a seasonal effect which can be seen
in the bromide data from the Monongahela River in Figure 3. The drier seasons result in low river flows
and thus increase the concentration of bromides.
The Monongahela River was also researched by Dr. VanBriesen of CMU. Unfortunately, data from her
studies have not been published. However, Dr. Vanbriesen has indicated to the media that shale waste
water and new smokestack scrubbers at coal-fired power plants are likely sources of bromide on the
Monongahela River (Hopey, 2011).
2.2
SAFE DRINKING WATER COMPLIANCE ISSUES
Many surface water treatment plants are or have been in violation of the Stage 1 DBP rule. The water
systems seem to believe the Marcellus Shale produced water causes the high DBPs in their water because
it is the only new potential pollution source in the area. The general manager for the Beaver Falls Water
Authority (BFWA) reported high THMs and cites Marcellus shale waste-water as a possible cause.
BFWA was one the first water systems to be in violation for THMs. On January 31, 2013 a man was
charged with dumping an estimated quarter million gallons of brine and drilling mud into a storm drain
that empties into the Mahoning River in Youngstown, Ohio and then flows into the Beaver River, which
the source for BFWA (Morgan, 2013). Brackenridge Water Authority was also out of compliance for
THMs. Fawn-Frazier Water Authority, which purchases bulk water from Brackenridge Water Authority
9
on the Allegheny, has been out of compliance for THMs for 5 of 8 quarters in 2011-12. Carmichaels
Municipal Water Authority, source is the Monongahela, also failed to meet regulatory compliance for
THMs in late 2010, early 2011 (Niedbala, 2013). West View Water Authority exceeded the lead action
level after switching to chloramines to help maintain compliance for THMs in 2010. Chloramines are an
alternative disinfectant that slows THM formation, but can be corrosive to household plumbing. In
addition to the potential health effects of THMs, there is increased stress and fear as well as reduced
consumer confidence when the public is informed their water is failing standards for safe water.
The cause for this problem that is unique to South Western Pennsylvania is unknown. The North Central
region of Pennsylvania where drilling activities are also flourishing does not appear to have water quality
problems related to THM formation as seen in Figure 2. The bromide concentration in produced water
from both regions is equivalent, Table 2. There is twice as many water treatment plants (Figure 4) in the
South Western region than the North Central region, but there are 97% more THM violations.
Table 2. Shale Gas Wastewater Bromide Concentrations
County
No. of Samples
North Central
Bradford
Tioga
Susquehanna
Lycoming
Cammeron
Centre
South West
Butler
Washington
Greene
Westmoreland
Fayette
Avg. [Br-] mg/l
St. Dev.
13
7
5
6
3
3
37
476
460
411
382
716
520
494
269
322
422
199
417
187
7
7
8
11
2
35
347
945
515
719
183
542
255
434
487
608
70
Source: Data obtained from PA DEP.
10
2.3
CONVENTIONAL TREATMENT INADEQUATE
Through the conventional treatment process of surface water through flocculation, coagulation,
sedimentation, and filtration, organic matter and chlorine react to form disinfection by-products (DBPs),
trihalomethanes and haloacetic acids, as well as unregulated DBPs. As the bromide levels increase in the
source water so do the brominated species of DBPs (Chang, 2001). Chlorine is widely used as a primary
disinfectant because it is effective and relatively inexpensive therefore, removing chlorination is not a
practical solution for water systems. Water systems are challenged with meeting all of the regulatory
requirements and must balance acute and chronic health risks. Compliance with the Stage 1 and Stage 2
D/DBPR is difficult to achieve while also complying with the following regulations: Surface Water
Treatment Rule (SWTR), Interim Enhanced Surface Water Treatment Rule (IESWTR), Long Term 1
Enhanced Surface Water Treatment Rule (LT1), Long Term 2 Enhanced Surface Water Treatment Rule
(LT2), Lead and Copper Rule (LCR), and Total Coliform Rule (TCR). For example, reducing the level of
chlorine disinfectant will decrease DBP formation but it also increases microbial risk that results in an
acute waterborne disease outbreak. LeChevallier recommends a free chlorine residual of 0.2-0.5 mg/l in
all areas of the distribution system to maintain a safe barrier to protect public health. Each rule has stature
in law and requires simultaneous compliance, so the goal of one rule cannot be undermined in favor of the
goal of another.
The concentration of DBP precursors (NOM), chlorine dose and residual, time, temperature and pH affect
the formation of DBPs (Handke, 2009). Temperature is easily identified because higher THM levels are
observed during the warmer months because of faster reaction rates. Water age is identified as a factor
because the samples collected from the distal locations in a distribution system are generally greater than
fresher water. Chlorine influences THM formation, as chlorine reacts with organics, the concentration of
THMs increase while chlorine decreases. Decreasing NOM during the treatment process also decreased
THM formation (Teksoy, Alkan, 2008).
11
Researchers at Pittsburgh Water and Sewer Authority and University of Pittsburgh began to study the
overall impact of bromide on DBP formation, identify sources of bromide, and the ability of the plant to
remove bromide. They have identified several sources of bromide in the Allegheny River watershed.
PWSA and other researchers have demonstrated there is a correlation between increased bromide and
increased THM formation, brominated species of THMs also increased with bromide concentration
(Chang and States). Dr. States of PWSA determined in October 2010 their treatment plant was only able
to remove about 28.7% of the bromide. Unfortunately, conventional filtration is not efficient in reducing
salts such as bromide. There are a few chemical or operational changes that can help to reduce the amount
of THMs in the drinking water supply:
1. Change treatment plant operations ie: decrease pre-oxidant chlorine and increase post-oxidant
chlorine. Oxidation of metals can be achieved by feeding potassium permanganate in lieu of prechlorine. However, these process changes will need to consider the Surface Water Treatment
Rule which requires 1 log inactivation of Giardia cysts by chlorination.
2. Enhanced coagulation, which increases total organic carbon (TOC) removal and therefore reduces
DBP precursors. Enhanced coagulation is a process of obtaining increased removal of DBP
precursors by conventional treatment. This requires a certain percentage reduction in NOM using
TOC as a surrogate for NOM. This treatment technique removes additional NOM measured as
TOC. Since the removal is dependent on alkalinity there are “easy to treat” and “difficult to treat”
waters. Step one measures TOC removal performance and step 2 requires an alternative removal
protocol if the water is “difficult to treat”.
3. Changing from free chlorine to chloramines as a secondary disinfectant. Chlorine combined with
ammonia yields a less reactive disinfectant which slows DBP formation. Chloramines do have
DBPs as well and are being evaluated for regulatory change. Nitrosamines are currently under
review under EPAs Unregulated Contaminant Monitoring Rule 3 (UCMR3).
12
4. Membrane filtration is ideal for removing salts and DBP precursors. However, membrane
technology is maintenance intensive and has high energy demands.
5. Since DBPs form with increasing water age, DBPs can also increase throughout the distribution
system. Distribution system optimization is being studied by the USEPA in the twelve area wide
optimization program (AWOP) states. Optimization includes methods to increased water storage
tank turnover, looping dead end lines, water quality sampling to identify areas of poor water
quality. Parameters include chlorine concentration, pH, temperature, and DBPs.
6. Water storage facility mixing or aeration systems can also be effective. Mixing systems prevent
stratification of water temperature gradients which can lead to poor water quality. Some aeration
systems involve fans that strip off the DBPs which improves water quality. These systems can be
expensive and may have energy needs.
Given these potential solutions there is no guarantee these methods will always work. There is also a
consequence to each method. Therefore, the most viable solution to this environmental problem is to
minimize impacts of source water bromide through produced water management.
13
3.0
POTENTIAL SOURCES OF BROMIDE AND WATER MANAGEMENT
Bromide concentration in source water has been correlated to brominated THMs at PWSA (States, 2012)
There has also been an association with produced water and high levels of TDS and elevated levels of
bromide when compared to other waters and wastewaters in Pennsylvania (VanBriesen, 2012).
Unconventional wells require considerably more water for fracturing than conventional. Since 2005, the
number of wells spud has increased exponentially with a slight decrease in 2012 largely due to
oversaturation of supply of natural gas, Figure 5. There has been a marked increase in produced water in
Pennsylvania from 2006-11 from this rapidly expanding industry. For example, from 2001-2006 there
were 6.3 million barrels a year of produced water which increased dramatically in 2008-2011 to 26
million barrels (VanBriesen, 2012). This increase and the lack of adequate waste-water facilities in the
region raise questions about where all this salty water is going. Increased produced water discharges seem
to be increasing the salinity of fresh water resources. TDS in produced water from oil and gas wells in
Pennsylvania is about 68,000-354,000mg/L (VanBriesen, 2012). The Marcellus formation TDS is about
3,010-261,000mg/L (Hayes, 2009). Freshwater should be less than 1,500mg/L TDS (Vanbriesen, 2012).
The following are five methods for this waste-water; reuse, injection wells, brine treatment plants (CWT),
municipal sewerage treatment works (POTW), other such as road application.
14
Table 3. Distribution of Wastewater Disposal Methods
Disposal Method
Percent of Total Disposed
Industrial Water Water Treatment
77.5%
Reuse in Other Wells
16%
Municipal Waste Water Treatment Facilities(POTW)
5%
Unknown Disposal
1%
Injection Wells
0.5%
Road Spreading
0.007%
(Rozell, 2012)
In the fall of 2008, the Monongahela River exceeded the drinking water standards for total dissolved
solids (TDS), 500mg/L, and sulfate, 250mg/L (VanBriesen, 2012). Significant increases of TDS, sulfate,
and increases of brominated THMs prompted the Pennsylvania Department of Environmental Protection
(PA DEP) to request POTWs to stop accepting shale gas wastewater for treatment in May 19, 2011.
However, industrial waste water plants are still permitted to accept the waste water despite high bromide,
TDS and other chemicals in the effluent. In November 2012 Dr. Vanbriesen reported that “Bromide
concentrations have declined (In the Monongahela), and there are reduced loads entering the river. We
don’t know why, but the decline corresponds to the DEP’s request that treatment plants stop accepting
drilling waste-water” (Hopey, 2012). As of November 2012, the bromide levels in the Allegheny
remained elevated.
A probability bounds analysis, which is well suited for when data is sparse and parameters are highly
uncertain analyzed five pathways for the contamination of water from shale gas operations. The five
pathways identified in the study were; transportation spills, well casing leaks, leaks through fractured
rock, drilling site discharge, and waste-water disposal. Overwhelmingly, waste-water disposal was
identified to be the most important area for additional research (Rozell et al., 2012). This conclusion and
15
other work support the need to eliminate surface waste-water discharges to protect the environment and
drinking water sources.
Several other areas in the United States where unconventional drilling is occurring are Texas, Colorado,
and Wyoming. These locations do not appear to have the same problems with surface water treatment and
disinfection by-products. Produced water management disposal methods can vary as a result of geology,
climate, location, or other factors. In arid climates evaporation can be used. Wet and humid weather does
not lend to efficient evaporation in Pennsylvania. Evaporation reduces the need to haul water to treatment
plants which reduces the likelihood of spills. Some of the solids left behind like Barium may be at
hazardous waste levels (Keister, 2010). EPA class II injection wells can be used in locations where the
geology permits such as Texas and Ohio, but the geology in Pennsylvania does not allow for this disposal
method. In Youngstown, OH a 4.0 magnitude earthquakes epicenter was near a 9,000 foot injection well
where produced water was disposed. This and a series of smaller earthquakes in the area have been
attributed to shale gas produced water injection as the probable cause. In Ohio, Senate Bill 315 was
passed on June 11, 2012, which requires electronic submission of quarterly brine reports and a host of
additional environmental health and safety measures (ODNR).
16
4.0
SUSTAINABILITY
Water resources are limited. 2012 was the 3rd hottest summer on record in the continental U.S. resulting in
strong winds, devastating storms, and wildfires. The Palmer Drought Index indicated 55.1% of the lower
48 states were moderate to extreme drought, with 39% experiencing severe to extreme drought (The
Aquifer, 2012). With this in mind it simply does not make sense to use fresh water resources for hydraulic
fracturing, because much of this water is unrecoverable especially when disposed via injection wells. PA
DEP has proposed to utilize mine influenced water (MIW) or partially treated MIW for hydraulic
fracturing operations. DEP produced a white paper outlining the process for the voluntary use of MIW
which obviously reduces the impact of water resources for consumption, recreation, and the environment.
This process also helps to reduce widespread legacy pollution, MIW (PA DEP). Overall, reusing,
recycling and treating the waste-water seem to be the only sustainable methods to waste water disposal in
the north eastern region of the United States. The pollution of water resources is expensive. The American
Water Works Association reports the average cost of tap water to be $0.0048/gallon, pollution and
unsustainable use of this resource is likely to increase the cost of water to each consumer (AWWA,
2012). Removal of salts and other constituents is important prior to discharging into streams, rivers, lakes,
etc. because it can affect aquatic life and alter the ecosystem (VanBriesen, 2012). Alternative methods for
hydraulic fracturing may have less environmental consequences such as using nitrogen gas, nitrogen
based foams, carbon dioxide which could help carbon sequestering, and liquefied petroleum gas (LPG)
(Rozell, 2012).
17
5.0
POLICY
There is a need for national policies regarding oil and gas produced water management. The incidence of
increased brominated THMs may become widespread throughout the country if produced water from
shale gas operations continues to be unregulated. There are several potential policy solutions to consider.
1. A system for documenting water withdrawals, flowback, and produced water will be necessary to
help prevent drillers or rogue water haulers from illegally dumping waste water into streams or
sewers. A cradle to grave system similar to the Resource Conservation and Recovery Act
(RCRA) would need to be developed in order to assure illegal dumping and falsification of
records is greatly reduced.
2. Develop a plan to build infrastructure for brine water treatment for this expanding industry like
stationary or mobile membrane plants or other proven technologies. Additional research is
necessary to determine if there are acceptable levels of bromide and other chemicals that can be
discharged to surface waters. Subsequently, changes to the national pollutant discharge
elimination system (NPDES) requirements could be recommended.
3. Communicating accidental spills to the appropriate authorities is pertinent for source water
protection and to assuring safe drinking water. The water systems already use communication
networks, such as the River Alert Information Network (RAIN) and the Ohio River Water Basin
Sanitation Commission (ORSANCO), to alert downstream water suppliers of chemical spills. The
intentional spill in Youngstown, OH was never communicated to the public water systems and
18
later entered the BFWA water system. A communication plan could have prevented this
exposure.
4. Research is needed to address human and ecological effects when developing new regulations
regarding oil and gas waste-water management.
5. Developing a surrogate for bromide levels would be a useful tool for water systems. Conductivity
varies by flow so it is not a good indicator of bromide (Kirby, 2010). TDS seemed to be a good
indicator on the Monongahela River but not Allegheny River (States, VanBriesen).
6. Abandoning wells afterwards will need to be considered to prevent a legacy pollution problem.
Currently underway are two EPA studies. The first is “EPA’s Study of Hydraulic Fracturing and its
Potential Impact on Drinking Water”, a final draft is due in 2014. The second is a two-year study that will
help to understand DBP formation in water treatment plants with a goal of producing a predictive model
of DBP formation based on a set of measurable parameters.
It is essential that policies need to be easily amended, due to an evolving industry. The Pittsburgh
Tribune-Review reported that oil drillers have begun to hydraulic fracture on shallow oil formations
between 1,000-3,000 feet, which already makes the new PA DEP regulations obsolete (Puko, 2013).
19
6.0
SUMMARY AND CONCLUSION
The Marcellus Shale formation is a significant economic resource for the petrochemical industry and an
abundant energy source, but it is important to use as much information that is available to make the
necessary regulatory framework to ensure a safe environment and to protect public health. Although the
connection between shale gas waste-water and the increase of brominated species of THMs has not been
confirmed, there is information that suggests a cause and effect relationship. Increased gas well drilling
(Figure. 5) and shale gas production water both correspond to the number of water system violations for
THMs in Southwestern PA, Figure 6.
Gas well drilling in Pennsylvania has been around for more than 150 years, but the elevated bromide
levels have not been a noticeable problem for public water systems until the use of unconventional
methods began. It is unclear why the bromide appears to have such a significant impact on the South
Western region. The North Central region, also a hot spot for unconventional drilling in the Marcellus
formation, does not seem to experience the same water quality consequences. There is a need to identify
the source of the bromide and take action to prevent pollution of surface water sources. Poor water quality
has negative impacts on the environment and public health. Rigorous national standards regulations and
significant penalties for bad operators and rouge haulers are necessary to ensure uniformity throughout
the industry. Fresh water sources are becoming increasingly limited and just might emerge as having
more value than the gas it is used to extract.
20
APPENDIX
SUPPLEMENTAL INFORMATION
Figure 1. Shale Plays in the Lower 48 States
Source: Provided by U.S. Energy Information Administration
21
Figure 2. THM Violations in Pennsylvania by Region
Source: Data obtained from PA DEP
Figure 3. Bromide Concentration in the Monongahela River
Source: Pennsylvania American Water Company, January 2013
22
Figure 4. Number of Treatment Plants by Region Utilizing Surface or GUDI Sources
Source: Data obtained from PA DEP
Figure 5. Number of Unconventional Wells Spud in Pennsylvania
Source: Data obtained from PA DEP
23
Figure 6. Number of THM Violations in South Western Pennsylvania
Source: Data obtained from PA DEP
24
BIBLIOGRAPHY
Bellar, T.A., Lichtenberg, J.J., Kroner, R.C., 1974. “The Occurrence of Organohalides inChlorinated
Drinking Water.” Jour. AWWA, 66:12:703.
Boyer, E.W., Swistock, B.R., Clark, J., Madden, M., Rizzo D. 2012. “The Impact of Marcellus Gas
Drilling on Rural Drinking Water Supplies.” The Center for Rural Pennsylvania. March 2012. P.
5.
Chang, E.E., Lin, Y.P., Chiang, P.C. (2001). "Effects of bromide on the formation of THMs and HAAs."
Chemosphere 43(8): 1029-1034.
Colborn, T., Kwiatkowski,C., Schultz, K., Bachran, M. (2011). "Natural Gas Operations from a Public
Health Perspective." Human and Ecological Risk Assessment 17(5): 1039-1056.
Environmental Protection Agency (EPA) "The Occurance of Disinfection By-Products (DBPs) of Health
Concern in Drinking Water: Results of a Nationwide Occuance Study." (2002)
Fields, R. "Air Monitoring Strategies." Presentation at the University of Pittsburgh Graduate School of
Pubic Health: Health Effects of Shale Gas Extraction Conference, November 19, 2010,
Pittsburgh, PA.
Handke, P. 2009. "Trihalomethane Speciation and the Relationship to Elevated Total DissolvedSolids
Concentrations Affecting Drinking Water Quality at Systems Utilizing the MonongahelaRiver as
a Primary Source During the 3rd and 4th Quarters of 2008." Pennsylvania Department
ofEnvironmental Protection. pp1-18.
Hayes, T. 2009. "Sampling and Analysis of Water Streams Associated with the Development of
Marcellus Shale Gas." Final Report to the Marcellus Shale Coalition. Gas Technology Institute,
Des Plaines, IL.
Hopey, Don. 2012. "Study Finds Lower Bromide Levels in Mon, but Not in Allegheny." Pittsburgh Post
Gazette. http://www.post-gazette.com/stories/local/region/study-finds-lower-bromide-levels-inmon-but-not-in-allegheny-661870/. March 3, 2013.
Hopey, Don. 2011. "Bromide: A Concern in Drilling Wastewater." Pittsburgh Post-Gazette.
http://www.post-gazette.com/stories/news/environment/bromide-a-concern-in-drillingwastewater-212188/ February 20, 2012.
Kappel, W.M., Soeder, D.J. (2009). "Water Resources and Natural Gas Production from the Marcellus
Shale." United States Geological Survey Fact Sheet
25
Keister, Timothy. "Marcellus Hydrofracture Flowback and Production Wastewater Treatment, Recycle,
and Disposal Technologies." The Science of Marcellus Shale Lycoming College in Williamsport,
PA. January 29,2010.
Kirby, C. "Inorganic Geochemistry of Marcellus Shale Hydrofracturing Waters." Presentation at the
University of Pittsburgh Graduate School of Pubic Health: Health Effects of Shale Gas Extraction
Conference, November 19, 2010, Pittsburgh, PA.
LeChevallier, M.W., Welch, N.J., and Smith, D.B. (1996), Full-Scale Studies of Factors Related to
Coliform Regrowth in Drinking Water, Applied and Environmental Microbiology, 62 (7), 22012211.
Morgan, Rachel. "Marcellus 'Gold Rush' Leads to Unsafe Practices." Times Online.
http://www.timesonline.com/news/local_news/youngstown-brine-dumping-cleanupongoing/article_cef55385-78ff-5e3e-a2a4-c002f450cc2f.html March 7, 2013.
Morgan, Rachel. "Beaver Falls Water Autority Never of Illegal Dumping." Ellwood City Ledger.
http://www.ellwoodcityledger.com/news/local_news/beaver-falls-water-authority-never-notifiedof-illegal-dumping/article_09d32034-d36e-5891-a9f1-dab4c22bbe9b.html March 1, 2013
Niedbala, Bob. "Carmichaels Water Authority Report on THM Study." Observer-Reporter.
http://www.observer-reporter.com/article/20130115/NEWS02/130119511/1/News#.UWsnEEpv6dw January 15, 2013.
Ohio Department of Natural Resources Senate Bill 315http://oilandgas.ohiodnr.gov/LawsRegulations/Senate-Bill-315.aspx/. March 12, 2013
Pennsylvania Department of Environmental Protection (PA DEP) Wells Spudded Data
http://www.depreportingservices.state.pa.us/ReportServer/Pages/ReportViewer.aspx?/Oil_Gas/Sp
ud_External_Data. March 10, 2013.
Pennsylvania Department of Environmental Protection (PA DEP). "White Paper: Utilization of Mine
Influenced Water for Natural Gas Extraction Activities."
http://www.bipc.com/files/media/misc/6c8353f92ee6a9c7b973a78c1edd462f.pdf
Plewa M.J., Wagner E.D., Richardson S.D., Thurston A.D., Woo Y.T., McKague A.B. 2004. "Chemical
and Biological Characterization of Newly Discovered Iodoacid Drinking Water Disinfection
Byproducts." Environmental Science and Technology. 38(18):4713-4722.
Puko, T. "Drillers Explore 'Groundbreaking' Fracking Technique." Pittsburgh Tribune-Review. January
21, 2013.
Richardson, S.D., Plewa, M.J., Wagner, E.D., Schoeny R., DeMarini, D.M.. 2007. "Occurrence,
Genotoxicity, and Carcinogenicity of Regulated and Emerging Disinfection By-Products in
Drinking Water: A Review and Roadmap for Research." Mutation Research-Reviews in Mutation
Research. 636(1-3):178-242.
Rook, J.J., 1974. Formation of Haloforms During Chlorination of Natural Water. Jour WaterTreatment &
Examination., 23:3:234.
26
States, S., Georgina, C., Stoner, M., Wydra, F., Kuchta, J., Monnell, J., Casson, L. (2012). "Bromide in
the Allegheny River: A Possible Link with Marcellus Shale Operations." Presentation at the
University of Pittsburgh Graduate School of Public Health: Health Effects of Shale Gas
Extraction Conference, November 9, 2012, Pittsburgh, PA.
Teksoy, A., U. Alkan, et al. (2008). "Influence of the treatment process combinations on the formation of
THM species in water." Separation and Purification Technology 61(3): 447-454.
Rozell, D. J. and S. J. Reaven (2012). "Water Pollution Risk Associated with Natural Gas Extraction from
the Marcellus Shale." Risk Analysis 32(8): 1382-1393.
U.S. Energy Information Administration, 2013. "Natural Gas Consumption by End Use."
http://www.eia.gov/dnav/ng/ng_cons_sum_dcu_nus_a.htm. April 17, 2013.
VanBriesen, J.M., Wilson, J.M. (2012). "Oil and Gas Produced Water Management and Surface Drinking
Water Sources in Pennsylvania." Environmental Practice 14 (4): 288-300.
27