Applied Geochemistry 71 (2016) 73e85

Contents lists available at ScienceDirect

Applied Geochemistry
journal homepage: www.elsevier.com/locate/apgeochem

Chemical and isotope compositions of shallow groundwater in areas

impacted by hydraulic fracturing and surface mining in the Central
Appalachian Basin, Eastern United States
St. Thomas M. LeDoux a, *, Anna Szynkiewicz a, **, Anthony M. Faiia a, Melanie A. Mayes b,
Michael L. McKinney a, William G. Dean a
a
The University of Tennessee, Dept. of Earth and Planetary Sciences, 1412 Circle Drive, Knoxville, TN, 37996, USA
b
The Climate Change Institute and the Environmental Science Division, Oak Ridge National Laboratory, P.O. Box 2008, Oak Ridge, TN, 37831, USA

a r t i c l e i n f o a b s t r a c t

Article history: Hydraulic fracturing of shale deposits has greatly increased the productivity of the natural gas industry
Received 8 August 2015 by allowing it to exploit previously inaccessible reservoirs. Previous research has demonstrated that this
Received in revised form practice has the potential to contaminate shallow aquifers with methane (CH4) from deeper formations.
13 May 2016
This study compares concentrations and isotopic compositions of CH4 sampled from domestic ground-
Accepted 14 May 2016
Available online 17 May 2016
water wells in Letcher County, Eastern Kentucky in order to characterize its occurrence and origins in
relation to both neighboring hydraulically fractured natural gas wells and surface coal mines. The studied
groundwater showed concentrations of CH4 ranging from 0.05 mg/L to 10 mg/L, thus, no immediate
Keywords:
Methane
remediation is required. The d13C values of CH4 ranged from
66‰ to
16‰, and d2H values ranged from
Groundwater
286‰ to
86‰, suggesting an immature thermogenic and mixed biogenic/thermogenic origin. The
Isotopes occurrence of CH4 was not correlated with proximity to hydraulically fractured natural gas wells.
Hydraulic fracturing Generally, CH4 occurrence corresponded with groundwater abundant in Naþ, Cl
, and HCO
3 , and with
Surface mining low concentrations of SO2
2

4 . The CH4 and SO4 concentrations were best predicted by the oxidation/
reduction potential of the studied groundwater. CH4 was abundant in more reducing waters, and SO2
4
was abundant in more oxidizing waters. Additionally, groundwater in greater proximity to surface
mining was more likely to be oxidized. This, in turn, might have increased the likelihood of CH4 oxidation
in shallow groundwater.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction integrity, migration of saline fluids (e.g., flowback water) associated

Hydraulic fracturing e the process of fracturing rocks with
pressurized fluid to release hydrocarbons trapped in their pore
spaces e has garnered a great deal of controversy over the past
decade due to its potential to contaminate shallow groundwater.
This may include contamination by stray gas migration (e.g.
methane) and/or mixing with deeper saline fluids of anthropogenic
and natural origins (Osborn et al., 2011; Warner et al., 2012; Jackson
et al., 2013; Vengosh et al., 2014). There are several causes by which
hydraulic fracturing can contaminate groundwater: poor well
* Corresponding author.
** Corresponding author.
E-mail addresses: stthomasledoux@gmail.com (St.T.M. LeDoux), aszynkie@utk.
edu (A. Szynkiewicz).
with drilling, and natural migration of deep formation waters
through permeable geologic formations (Osborn et al., 2011;
Warner et al., 2012, 2013a, b; Vengosh et al., 2014). Nevertheless,
the effect of hydraulic fracturing upon groundwater differs greatly
between areas and may also depend on local geology, fracture
system, and bedrock composition (Osborn and McIntosh, 2010;
Warner et al., 2013a; Molofsky et al., 2013; McIntosh et al., 2014;
Siegel et al., 2015). Additionally, leakage of hydrocarbons through
abandoned oil and gas wells can be locally important (Kang et al.,
2014). Therefore, more site-specific investigations are needed to
determine possible effects of shale gas drilling and hydraulic frac-
turing on the quality of water resources (Warner et al., 2013b). To
date, only a few geochemical studies exist targeting this problem in
the United States. Most of them are focused on groundwater
contamination in the northern Appalachian Basin, related to shale
gas extraction from the Marcellus Shale (Osborn and McIntosh,

http://dx.doi.org/10.1016/j.apgeochem.2016.05.007
0883-2927/© 2016 Elsevier Ltd. All rights reserved.
74 St.T.M. LeDoux et al. / Applied Geochemistry 71 (2016) 73e85

2010; Osborn et al., 2011; Warner et al., 2012, 2013a; Molofsky et al.,
2013; Darrah et al., 2014; Harkness et al., 2015; Siegel et al., 2015),
one of the largest shale basins in the United States. Significantly less
information is available for Central and Southern Appalachian ba-
sins where hydraulic fracturing takes place in shallower Paleozoic
formations (Warner et al., 2013b).
In this study, we investigated the effects of hydraulic fracturing
upon groundwater from domestic wells in eastern Kentucky, an
area that has been a hotbed of recent natural gas development in
the Central Appalachian Basin of the Eastern United States (Fig. 1).
Since the 1980’s, oil and gas companies have been utilizing hy-
draulic fracturing to increase production of methane (CH4) from
conventional, shallow deposits in this area (KGS, 2014). Vertical
fracturing of more unconventional deposits, such as the Chatta-
nooga Shale of Devonian age, began in 1990, and horizontal dril-
ling/fracturing was not introduced to the studied area until 2006
(Nuttall, 2013). Hydraulic fracturing in the Chattanooga Shale is
different than its northern counterpart, the Marcellus Shale since it
resides at shallower depths: ~1000e1500 m for the Chattanooga
(KGS, 2014) and ~2000e3000 m for the Marcellus (Jackson et al.,
2013). Due to the excessive depth and overbearing weight of the
Marcellus shale, immense amounts of fresh water have to be
pumped under high pressure in order for these formations to
fracture. Conversely, the shallower Chattanooga Shale requires far
less pressure to be fractured, and liquid nitrogen foam is routinely
used to induce hydraulic fracturing. The latter is less hydraulically
intensive and generates considerably less wastewater. Similar to
other fracturing fluid mixtures, the specific chemical content of
nitrogen foam is largely proprietary and unknown to the public. As
a result, little is known about how this process may affect
groundwater quality. By focusing on the shallower Chattanooga
Shale, this study seeks to provide a much needed point of com-
parison between different regional, technical, and commercial
contexts of hydraulic fracturing across Appalachia.
The major goal of this study was to determine whether CH4
detectable in domestic drinking wells in eastern Kentucky occurs as
a result of stray gas migration from hydraulically fractured natural
gas wells drilled into the Chattanooga Shale, or is a natural occur-
rence. In 2014, we collected 59 groundwater samples with varying
proximity to neighboring hydraulically fractured natural gas wells
and surface coalmines for chemical and isotopic analysis of dis-
solved CH4. Additionally, major water chemistry, the sulfur (S) and
oxygen (O) isotope composition of dissolved sulfate (SO4), and the
hydrogen (H) and oxygen (O) isotope composition of groundwater
were used to characterize groundwater in the study area.
2. Geologic setting
Our study area covers 878 km2 and is located in and around
Letcher County, Kentucky (Fig. 1). The area is dominated by the
rolling Appalachian Mountains and sits at elevations between 360
and 670 m. The geology of Letcher County is uniformly composed of
five major rock units: 1) the Chattanooga Shale, 2) the Pennington
Formation, 3) the Lee Formation, 4) the Lower Breathitt Formation,
and 5) the Middle Breathitt Formation (Suppl. Fig. S1). These strata
are Devonian to Pennsylvanian in age, respectively, and reflect a
waxing/waning fluvial depositional history of the Appalachian
basin prior to its upheaval during the Paleozoic (Rice et al., 1979).
The Middle and Lower Breathitt formations, dominate the surface
geology of Letcher County, and are composed of rapidly inter-
bedded siltstone, shale, sandstone, and coal (Suppl. Fig. S2).
Conversely, the Chattanooga, Pennington and Lee formations are
only exposed at the Pine Mountain Thrust Fault along the northern
base of the Pine Mountain Ridge, located along Kentucky’s south-
eastern border with Virginia.
Letcher County is divided between the greater Kentucky River
and Upper Cumberland River watersheds. The geologic and topo-
graphic heterogeneity of the area’s mountainous terrain dictates

Fig. 1. Location map showing groundwater sampling sites (yellow circles) and hydraulically fractured natural gas wells (red dots e ALL permitted after 1980; blue dots e DEVIATED
permitted between 2006 and 2012; green dots e ACTIVE permitted since 2011) in the studied area of Letcher County, Kentucky. The size of yellow circles shows proportional
concentration of CH4 (0.05e10 mg/L) measured at a given sampling site. Topographic image and gas well locations were provided by the Kentucky Geological Survey (KGS, 2014).
(For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
 St.T.M. LeDoux et al. / Applied Geochemistry 71 (2016) 73e85
depth to the water table, which can be extremely variable within a
few square kilometers and range from less than 10 m near
streambeds to as high as 500 m atop nearby ridges. Major aquifers
are primarily composed of sandstone at depths of 10e100 m within
the Lower Breathitt Formation. These aquifers are usually less than
10 m thick and are horizontally discontinuous. The hydraulic con-
ductivity of these aquifers is variable within several orders of
magnitude, ranging from 5  10
8 cm/s to 1  10
4 cm/s,
depending on the extent of fracturing within conducting bedrock
(Minns, 1993).
Groundwater flow within this region is differentiated between
two primary zones. The first zone is composed of more heavily
fractured bedrock (~0 me20 m), and has generally high hydraulic
conductivity. Flow direction within this shallow fracture zone has
been shown to mirror topography towards first order streams
(Minns, 1993). The second zone (below ~ 20 m) is considerably less
fractured and has generally lower hydraulic conductivity. At these
depths, groundwater flow is directed towards third order streams
(Minns, 1993). Uncased domestic wells drilled into either hydro-
logical zone commonly intersect multiple conducting strata to in-
crease their longevity, often passing through multiple adjacent coal
and shale seams (KGS, 2014).
There are a number of geologic and anthropogenic processes
affecting water quality in the studied area, mostly tied to fossil fuel
extraction (e.g., coal mining, gas and oil drilling, etc.). Over the past
century, coal mining (Suppl. Fig. S3) has a documented history of
impacting the surface and groundwater quality in Letcher County
as a result of acid mine drainage (e.g., stream acidification) from
sulfide oxidation of excavated coal beds (Carey et al., 1993). How-
ever, the effects of more recent oil and gas drilling on groundwater
quality in this area are not yet well understood.
3. Methods
3.1. Field sampling
Groundwater samples were collected from domestic wells
across Letcher County (Fig. 1, Suppl. Figs. S1, S3). Based on verbal
reports from homeowners, most of these wells were drilled into the
Lower Breathitt Formation at depths ranging from ~10 m to 100 m.
The water sampling took place at regular, bi-weekly intervals over
two seasons (winter and summer of 2014), alternating between
areas of high and low natural gas well density (Fig. 1). 20 ground-
water samples were collected between January 18 and March 1 of
2014, and an additional 39 samples were collected between June 10
and August 1 of 2014. The sampled groundwater was kept on ice
during transport, and afterward stored at 4  C in the laboratory.
At each household, groundwater was sampled directly from an
outside faucet upstream of any filtration and/or treatment system.
Water was run from the faucet through a hose, which was sub-
merged into a collection bucket, until temperature, pH, and con-
ductivity stabilized. The EC, temperature, pH, TDS, dissolved oxygen
(DO), and oxidation/reduction potential (ORP) were measured in
situ using an YSI 556 Multiprobe. Additionally, the concentration of
dissolved hydrogen sulfide (H2S) was measured in situ using a Hach
DR900 Colorimeter and alkalinity was measured using a LaMotte
field titration kit.
For analyses of bulk concentration, d13C and d2H of CH4,
groundwater was sampled using methods adopted from Kampbell
and Vandegrift (1998) and Bastviken et al. (2004). For bulk con-
centration, groundwater was collected into a 50 mL septum-sealed,
evacuated glass bottle using a full 60 mL syringe. The syringe was
injected into the bottle and allowed to reach equilibrium with the
surrounding pressure, at which point the needle was removed and
CH4 was allowed to degas into the remaining headspace in the
75
bottle. CH4 concentrations in the headspace were analyzed within
14 days of collection using a Gas Chromatograph. Separately,
groundwater was bottled without headspace and acidified to
pH < 2 using 20% w/v HCl for C and H isotopic analysis of CH4 (see
section 3.3 for more details).
Additionally, 60 mL of sampled groundwater was filtered in the
field with a 0.45 mm nylon filter into two plastic bottles. One bottle
was acidified with 3 drops of concentrated HNO3 for cation analysis.
The second bottle was left untreated for anion analysis. Also,
unfiltered groundwater samples were collected in 1.0 L plastic
bottles and were processed the day after sampling and analyzed for
the S and O isotope compositions of dissolved sulfate (SO4).
3.2. Chemical analysis
Major cation concentrations (Ca2þ, Kþ, Mg2þ, Naþ) were
measured using a Perkin Elmer Optima 8000 Inductively Coupled
Plasma-Optical Emission Spectrometer (ICP-OES) in the Center for
Mass Spectrometry of the Department of Chemistry at the Uni-
versity of Tennessee, Knoxville (UTK). Samples (diluted with de-
ionized water to 1:10, 1:100 or 1:1000) were analyzed using
multi-element atomic adsorption standards (diluted from
10.00 mg/L stock solutions). Reported analytical error was ±6%,
with a minimum detection limit of 0.5 mg/L.
Anion concentrations (Cl
, SO2

4 ) were measured using a Dionex
ICS-2000 ion chromatograph in the Aqueous Geochemistry and
Microbiology Laboratory of the Department of Earth and Planetary
Sciences (EPS) at UTK. Samples (diluted with deionized water to
1:10 or 1:100) were analyzed using multi-element ion standards
(diluted from 100 mg/L stock solutions). Reported analytical error
was ±4%, with a detection limit of 0.5 mg/L. In the same laboratory,
the concentration of dissolved CH4 was measured using an Agilent
GC-MS system for separation and identification of organic com-
pounds. Samples were analyzed without dilution using a multi-
component gas standard (diluted from 15 mg/L stock solution).
Reported analytical error was ±3%, with a detection limit of 0.1 mg/
L.
3.3. Isotopic analysis
The d13C and d2H of CH4 were determined within 6 months of
collection in the Stable Isotope Facility of the Department of Plant
Sciences at the University of California, Davis using a Gas Bench
interfaced with a Delta V Plus isotope ratio mass spectrometer
(IRMS) following the method of Yarnes (2013). Isotope values were
reported in units of per mil (‰) with respect to Vienna Pee Dee
Belemnite (VPBD) for d13C and Vienna Standard Mean Ocean Water
(VSMOW) for d2H. Reported analytical error was ±0.2‰ for d13C and
±2.0‰ for d2H.
All groundwater samples were processed for analysis of S and O
isotope composition of dissolved SO2
4 . The day after field sampling,
each water sample was filtered and acidified to a pH < 2 using 20%
w/v HCl. Afterward, 10 mL of 10% w/v BaCl2 was added to the
sample to precipitate BaSO4. Prior to drying, the BaSO4 precipitate
was rinsed several times with DI-water. The d34S of SO2
4 was
determined using a Costech elemental analyzer (EA) interfaced
with a Delta V IRMS in the Stable Isotope Research Facility of the
Department of Geological Sciences at Indiana University, Bloo-
mington. The d18O of SO2
4 was determined in a continuous flow
system using a high temperature conversion elemental analyzer
(TC/EA) interfaced with a Delta Plus XL isotope ratio mass spec-
trometer in the Stable Isotope Laboratory at UTK. Isotope values
were reported in ‰ with respect to Vienna Can ~ on Diablo Troilite
(VCDT) for d34S and VSMOW for d18O, with a reported analytical
error of ±0.3‰ for both.
76 St.T.M. LeDoux et al. / Applied Geochemistry 71 (2016) 73e85
The d2H and d18O of groundwater were determined using a Los
Gatos liquid isotope analyzer in the Stable Isotope Laboratory at
UTK. Isotope values for both d2H and d18O were reported in ‰ with
respect to VSMOW, with a reported analytical error of ±0.7‰ for
d2H and ±0.2‰ for d18O.
3.4. Bedrock samples
Each of the major geologic units (the Middle/Lower Breathitt
Formations, Lee Formation, Pennington Formation, and Chatta-
nooga Shale; Suppl. Fig. 1) was sampled for S isotope analysis of
bedrock S-bearing minerals (e.g., sulfides, sulfates) using the
method of S sequential extraction adopted from Szynkiewicz et al.
(2009). In short, bedrock samples were ground into a fine sediment
and used for extraction of elemental sulfur with dichloromethane
(DCM) in a Soxhlet apparatus. Activated copper (Cu) granules were
added to the sample flask to recover elemental sulfur as CuS and
then treated with 15 mL of hot deoxygenated 6 M HCl while
flushing the solution with N2 gas. H2S was evolved from reduction
of elemental sulfur bound to the copper granules and precipitated
as Ag2S. After DCM extraction, the residual sediment was treated
with 30 mL of 6 M HCl in the same way as the previously mentioned
copper granules. Evolved H2S from the decomposition of acid-
volatile sulfides (e.g., monosulfides) was precipitated as Ag2S. Af-
terward, the acid leachate was separated from the sediment using a
centrifuge. Dissolved Fe2þ was removed from the acid leachate by
precipitation as iron oxides following the addition of NaOH to
adjust the pH of the solution to 9. After treatment with NaOH, the
acid-dissolved SO2
4 was precipitated from the remaining solution
as BaSO4. Finally, the remaining sediment was treated with a
mixture of 20 mL 12 M HCl and 20 mL of 1 M CrCl2$6H2O under N2
gas to dissolve chromium-reducible sulfides (e.g., disulfides). The
obtained BaSO4 and Ag2S precipitates were then measured for their
S isotope composition by the method outlined in section 3.3.
3.5. Spatial (proximity) and statistical analyses
For spatial analysis, the locations of each sampling site were
related to various features in the studied area of Letcher County
(e.g., the locations of gas wells, coal mines, etc.) using ArcGIS
Software. Locational data for all natural gas wells and surface mines
permitted within Letcher County since 1900 were obtained from
the Kentucky Geological Survey (KGS). Generally, three different
gas well classifications were used for spatial analyses (Fig. 1): 1) all
hydraulically fractured natural gas wells permitted after 1980
(referred to as ALL), 2) all deviated hydraulically fractured natural
gas wells permitted between 2006 and 2012 (referred to as DEVI-
ATED), and 3) all active hydraulically fractured natural gas wells
permitted after 2011 (referred to as ACTIVE). Consequently,
chemical and isotope results were compared to: 1) the distance
from each sampling site to the nearest hydraulically fractured
natural gas well (a metric adopted from Jackson et al., 2013) for
each major gas well category, and 2) the percentage of area covered
by surface mining (past and present) within a 1 km radius of each
sampling site.
The observed relationships between various measured param-
eters for each site and their corresponding proximity metrics were
tested primarily using linear regression (Suppl. Table S1). All the
measured values that were not normally distributed were trans-
formed to meet the assumption of normality necessary for linear
regression. In cases where such transformations were not possible,
the observed relationships were alternatively tested using Spear-
man’s rank-order correlation (Suppl. Table S1). Additionally, any
statistical relationships that involved discrete/categorical predictor
variables (i.e., treatment versus control categories, non-continuous
measurements, etc.) were tested using an analysis of variance test
(ANOVA) (Suppl. Table S1).
4. Results
4.1. Concentrations and isotope composition of CH4
The measured CH4 concentrations in groundwater ranged from
<0.05 mg/L to ~10 mg/L. These data were bimodally distributed
between sites with CH4 concentrations <1 mg/L and sites with CH4
concentrations >1 mg/L. Approximately half of the households
sampled showed higher CH4 concentrations in groundwater
(>1 mg/L). According to Spearman’s rank-order correlation, there
was no relationship between CH4 concentrations and proximity to
hydraulically fractured natural gas wells of any category (i.e., ALL:
r ¼
0.06; ACTIVE: r ¼
0.07; or DEVIATED: r ¼ 0.26; Fig. 2).
We have divided our groundwater into two types based upon
the CH4 concentration. Type 1 groundwater had higher concen-
trations of CH4, ranging from 1 mg/L to 9 mg/L (Suppl. Table S4).
Type 2 groundwater showed lower concentrations of CH4, ranging
from <0.1 to 1 mg/L (Suppl. Table S4). The d13C and d2H values of
CH4 in groundwater samples ranged from
66‰ to
16‰ and from

286‰ to
86‰, respectively (Fig. 3).
4.2. Chemical composition of groundwater
The Piper diagram shows two distinctive groundwater types in
the studied area (Suppl. Fig. S 4) which coincide with the bimodal
distribution of samples based upon CH4 concentrations. Type 1
groundwater with higher CH4 concentration (1e10 mg/L) had low
concentrations of SO2

4 or below detection. In addition, Type 1
groundwater can be classified as NaeHCO3eCl-rich water. Type 2
groundwater with low CH4 concentrations (<1 mg/L) had higher


concentrations of SO2

4 and lower concentrations of Cl , and can be
e e
classified as predominantly Ca HCO3 SO4-rich water.
In Type 1 groundwater, the Naþ concentrations ranged from
12 mg/L to 268 mg/L, and Cl
concentrations from 3 mg/L to
310 mg/L. Conversely, the SO2
4 concentrations ranged from 1 mg/L
to 34 mg/L and Ca2þ concentrations from <0.5 mg/L to 87 mg/L. In
Type 2 groundwater, the Naþ concentrations ranged from 3 mg/L to
123 mg/L and Cl
concentrations from 1 mg/L to 69 mg/L. In
contrast, the SO2

4 concentrations ranged from 1 to 289 mg/L and
Ca2þ concentrations from <0.5 mg/L to 406 mg/L. Both water types
showed similar concentrations of HCO


3 , although the HCO3 made
up a smaller proportion of the overall ionic content for Type 1
groundwater than it did for Type 2. The HCO
3 concentrations in
Type 1 groundwater ranged from 124 mg/L to 368 mg/L and in Type
2 groundwater from 28 mg/L to 492 mg/L (Suppl. Table S4).
4.3. Isotope composition of groundwater
The measured d18O and d2H of groundwater sampled ranged
from
8‰ to
6‰ and from
49‰ to
37‰, respectively
(Suppl. Table S.5). The slope and intercept corresponding to these
values were statistically indistinguishable to that of the Kentucky
meteoric water line (Kendall and Coplen, 2001; Suppl. Fig. S.5)
when compared using a T-test (T57 ¼ 0.67, P > 0.05). Both d18O and
d2H values were normally distributed and characteristic of a single
sample population.
In groundwater samples with SO2
4 concentrations >1 mg/L, the
d S and d18O of SO2

34
4 varied greatly from
1‰ to þ59‰ and
from þ2‰ to þ19‰, respectively (Suppl. Table S5), and were
positively correlated (R2 ¼ 0.47, P < 0.0001, Fig. 4). In contrast, the
d34S values of S-bearing bedrock minerals (e.g., sulfates, sulfides)
varied within a smaller range, from
3‰ to þ26‰ (Fig. 4,
 St.T.M. LeDoux et al. / Applied Geochemistry 71 (2016) 73e85 77

Suppl. Table S3).

10 A
4.4. Oxidation-reduction potential (ORP) and dissolved oxygen
(DO)
8

The measured ORP values were normally distributed, ranging

[CH4] (mg/L)

from
353.6 mV to þ232.8 mV. The ORP appeared to be a reliable

6

predictor of CH4 and SO2
4 concentrations (Fig. 5A). Generally, CH4

was more abundant in more reducing groundwater (R2 ¼ 0.40,
P < 0.0001), and SO4 was more abundant in more oxidizing
4

groundwater (R2 ¼ 0.21, P < 0.001). Additionally, the CH4 and

SO2

4 concentrations were inversely correlated to one another
(r ¼
0.74; Fig. 5B), implying that CH4 concentrations were highest
in samples with low concentrations of SO2
2

2

4 (<10 mg/L), and SO4

concentrations were highest in samples with very low concentra-
tions of CH4 (<1 mg/L).
0

Given that coal mining is a prominent surface feature in the

studied area (Suppl. Fig. S.3), the measured ORP values were
0 500 1000 1500 2000 compared with the proximity to surface mining defined here as the
Distance (m) percentage of area within a 1 km radius of each sampling site
covered by surface mining. The mean ORP values for sampling sites
with <30% area within a 1 km radius covered by surface mining
10

B were significantly lower than mean ORP values for sampling sites
with >30% area within a 1 km radius covered by surface mining
when compared alternatively by ANOVA (Fig. 6).
8

The measured DO concentrations ranged from 0.13 mg/L to

10.11 mg/L (Suppl. Table S2). While most sampling sites demon-
[CH4] (mg/L)

strated very low DO concentrations (<1 mg/L), a subset of samples

6

did exhibit elevated DO concentrations (2e10 mg/L). The more

oxidized samples were also more correlated with Type 2 ground-
water, and had relatively low CH4 concentrations (<1 mg/L) and
high SO2

4 concentrations (>10 mg/L). The CH4 and DO concentra-
4

tions were inversely correlated using Spearman’s rank-order cor-

relation (r ¼
0.53; Fig. 5C).
2

5. Discussion

5.1. Origin of CH4

0

0 2000 4000 6000 8000 10000 According to the U.S. Department of the Interior, groundwater
Distance (m) wells that contain more than 10 mg/L of CH4 should undergo
continuous monitoring and wells with >28 mg/L require immedi-
10

ate remediation (Eltschlager et al., 2001). Several states have

C
defined even lower thresholds (~7 mg/L) from which household
utilization of CH4-rich groundwater is not recommended (Vengosh
et al., 2014). Generally, in groundwater directly impacted by stray
8

gas migration in the northern Appalachian Basin the CH4 concen-

trations regularly exceed these thresholds, reaching as high as
[CH4] (mg/L)

70 mg/L (Osborn et al., 2011; Jackson et al., 2013; Siegel et al., 2015).
6

In our study, however, the CH4 concentrations of groundwater were

considerably lower <0.5e10 mg/L (Fig. 2, Suppl. Table S4) sug-
gesting that in spite of a relatively high density of gas wells (Fig. 1),
4

the contamination of groundwater by stray gas migration is insig-

nificant compared to the northern Appalachian basin.
Although some previous studies have argued that the concen-
2

tration of CH4 in groundwater increases with proximity to hy-

draulically fractured natural gas wells (Jackson et al., 2013; Osborn
et al., 2011; Vengosh et al., 2014), there is an increasing number of
studies showing no such correlation (Warner et al., 2013b;
0

0 2000 4000 6000 8000 10000

Distance (m) Fig. 2. CH4 concentrations as a function of proximity to ALL (A), DEVIATED (B) and
ACTIVE (C) hydraulically fractured natural gas wells in eastern Kentucky. The following
correlations were determined using Spearman’s rank-order correlation: r ¼
0.06,
r ¼ 0.26, and r ¼
0.07 respectively.
78 St.T.M. LeDoux et al. / Applied Geochemistry 71 (2016) 73e85

Molofsky et al., 2013; Siegel et al., 2015). Accordingly, in our study

area the concentrations of CH4 were not correlated with proximity
to hydraulically fractured natural gas wells of any production
category (Fig. 2A). There are, however, contextual limitations pre-
venting this study from better characterizing the occurrence of CH4
in shallow groundwater in relation to gas well proximity. The
studied area has been greatly affected by natural gas development,
thus, it was difficult to find households far away from any hydraulic
fracturing activity (Fig. 1). This means that for the broadest gas well
category e ALL (1980e2014) e it was impossible to establish any
kind of reliable subset of control data (e.g., more representative of
pristine conditions) against which to compare potentially impacted
sites. The other two categories of hydraulically fractured natural
wells (i.e., ACTIVE 2011e2014 and DEVIATED 2006e2012) were
more sparsely distributed across the study area (Fig. 1). Conse-
quently, the proximity analyses for the occurrence of CH4 in relation
to these newer forms of hydraulic fracturing were possible and
indicated that more recent ACTIVE and DEVIATED hydraulically
fractured natural gas wells has no significant effect on groundwater
CH4 concentrations in eastern Kentucky (Fig. 2B,C).
Previous research has shown that in some cases, valley forma-
tion associated with a greater density of fractures and lineaments
may serve as enhanced pathways for gas migration and lead to
elevated CH4 concentrations at topographic lows (Molofsky et al.,
2013). Furthermore, major faults and stress fractures may be
conduit structures through which deep fluids, particularly dis-
solved gases, will propagate (Lopez and Smith, 1995). In our study
area, however, the CH4 concentrations in groundwater did not
show any relationship with topography or elevation (Fig. 7). Addi-
tionally, the CH4 concentrations were not correlated with proximity
to the Pine Mountain thrust fault (Fig. 8), a major tectonic feature
along the northern base of the Pine Mountain Ridge (Suppl. Fig. S1).
This implies that CH4 in the studied groundwater was rather of
shallow origin.
The source of CH4 can potentially be determined by looking at its
isotope composition. Previous studies have shown that d13C and
d2H of CH4 are useful in distinguishing between deep thermogenic
and shallow microbial CH4 (Osborn et al., 2011; Jackson et al., 2013;
Vengosh et al., 2014; Humez et al., 2016). CH4 from deep, thermo-
genic shale gas reservoirs is generally enriched in the heavier 13C
and 2H isotopes (d13C >
45‰, d2H >
225‰), while CH4 of
biogenic origin is conversely depleted in the heavier isotopes
(d13C <
55‰, d2H <
150‰) (Schoell, 1980). Additionally, CH4
from less mature shallower thermogenic origin is depleted in the
heavy 2H isotope but not as depleted in 13C as biogenic CH4
(Fig. 3A). Generally, in the studied groundwater of eastern Ken-
tucky, the d13C and d2H values of CH4 were primarily characteristic
of a less mature thermogenic and mixed thermogenic/biogenic
origin (Fig. 3A). The less mature thermogenic source of CH4 is likely
the extensive coalbeds that are present in this area, and the isotopic
composition matches coalbed CH4 from the Pennsylvanian coal
fields in western Kentucky (Stra˛ po c et al., 2007) (red field on
Fig. 3A). The mixed thermogenic/biogenic source may include
bacteria that produce CH4 in shallow, anaerobic environments and
a thermogenic source which could be either the coal deposits and/

Fig. 3. (A) d2HeCH4 as a function of d13CeCH4. The greyscale shading refers to CH4
concentration indicated on the right-side bar. Source classification was adopted from
Jackson et al. (2013). Red field indicates the isotopic composition of CH4 for Pennsyl-
vanian coalbeds (after Stra˛ poc et al., 2007; Pashin, 2007) and blue field for Devonian
shale in northern Appalachia (after Jackson et al., 2013; Rice and Ladwig, 1983;
Whiticar, 1999; Schoell, 1980). (B) Histogram of d13CeCH4 values compared to CH4
concentrations. (C) Histogram of d2HeCH4 compared to CH4 concentrations. (For
interpretation of the references to color in this figure legend, the reader is referred to
the web version of this article.)
 St.T.M. LeDoux et al. / Applied Geochemistry 71 (2016) 73e85
Fig. 4. (A) d34S of groundwater SO4 compared to d34S of bedrock (F1,54 ¼ 17.96, P < 0.0001 using ANOVA). Open circles indicate the measured outliers, the box 25e75% of variance,
and solid (thick) line 50% of variance. (B) d18O as a function of d34S in the studied groundwater (R2 ¼ 0.47, P < 0.0001, regression dotted line in blue).
or the deeper Chattanooga Shale.
In organic-rich sediments such as coal and shale, biogenic CH4 is
often formed via microbial CO2 reduction (e.g., Osborn and
McIntosh, 2010; Schlegel et al., 2011; McIntosh et al., 2014;
Humez et al., 2016). During this process, all of the hydrogen is
derived from coexisting water and accompanied by hydrogen
isotope fractionations of
160‰ between CH4 and water (Schoell,
1980). While d2H of CH4 in some of our groundwater samples
(
210 to
190‰) might be indicative of microbial CO2 reduction,
the overall variation of d2H (
280 to
80‰) suggest multiple
sources of CH4 in the studied area (Suppl. Fig. S.6).
The few samples which indicate a more mature thermogenic
source, similar to the Marcellus shale of the northern Appalachian
basin with higher d13C and d2H values (blue field on Fig. 3A), all
contain low concentrations of CH4 (Suppl. Tables S4, S5). This might
suggest some point-source contamination by stray gas in the
studied wells. Nevertheless, the d13C of CH4 did not increase
significantly with closer proximity to any of the gas well categories
ALL, DEVIATED and ACTIVE (Suppl. Fig. S.7), implying minor/trace
amounts of CH4 from the Chattanooga shale. Although isotopic
compositions are useful in characterizing CH4 origin, there are
additional processes which can alter its isotopic ratio. Microbial
oxidation, for example, can increase the isotopic ratios of CH4 to
create a falsely thermogenic isotopic signature (Van Stempvoort
et al., 2005; Humez et al., 2016) and could alternatively explain
the observed high d13C and d2H of CH4 (
35 to
20‰ and
170 to

75‰, respectively) in a few groundwater samples (Fig. 3,
Suppl. Fig. S.7).
5.2. CH4 occurrence in relation to chemical and isotopic
composition of groundwater
5.2.1. Water origin and mixing processes
The isotopic composition of water is a valuable tracer for eval-
uating water sources and mixing processes in aquifers. Usually, the
d2H and d18O values of shallow groundwater represent the average
isotopic composition of local precipitation (e.g., Sharp, 2007). The
d2H and d18O values of groundwater sampled in eastern Kentucky
were normally distributed and varied in a relatively narrow range
(
47‰ to
37‰ and
8‰ to
6‰, respectively; Suppl. Fig. S.5).
These values were consistent with previously reported H and O
isotope compositions for the Kentucky meteoric water line (Kendall
and Coplen, 2001). This indicates that groundwater sampled in this
79
study was primarily sourced from local meteoric precipitation (e.g.,
rain and snowmelt). The d2H and d18O values of Type 1 and 2
groundwater containing high (1e10 mg/L) and low (<1 mg/L)
concentrations of CH4, respectively, were indistinguishable, sug-
gesting that they both originated from local precipitation
(Suppl. Fig. S.5). However, the considerable differences observed
between the chemical compositions of Type 1 (NaeHCO3eCl-rich)
and Type 2 (CaeHCO3eSO4-rich) groundwater suggest that addi-
tional processes are responsible for further changing groundwater
chemistry. Aside from anthropogenic factors, many natural pro-
cesses control the chemical composition of groundwater, such as
dissolution of bedrock minerals along the flow path, mixing pro-
cesses, and overall residence time of groundwater within an
aquifer. In Appalachia, groundwater chemistry is generally domi-
nated by high concentrations of HCO
3 originating from dissolution
of calcite (CaCO3) and dolomite (CaMg(CO3)2) present in Paleozoic
carbonate formations (Sheets and Kozar, 2000). This is consistent
with the observed elevated concentrations of HCO
3 in both water
types found in eastern Kentucky.
Previous studies have suggested that NaeCl-rich groundwater
with elevated concentrations of CH4 (i.e., Type 1 water) might occur
as a result of diffuse mixing with basinal brine water residing at
greater depths (Osborn and McIntosh, 2010; Warner et al., 2012;
Wunsch, 1993). Given the elevated Naþ and Cl
concentrations of
Type 1 groundwater (up to 268 mg/L and 310 mg/L, respectively),
this process could provide an explanation for the presence of CH4
(1e10 mg/L) in the studied groundwater. Usually, deep basinal
brines have distinctively higher d2H and d18O isotope values
compared to meteoric precipitation because they either i) origi-
nated from paleoseawater trapped in sedimentary formations
(Davisson et al., 1994), or ii) have undergone prolonged isotope
exchange with the surrounding bedrock (Clayton et al., 1966). In
Appalachia, the d2H and d18O values of basinal brines range from

46 to
30‰ and from
6 to 0‰, respectively (Warner et al., 2012;
Suppl. Fig. S.5). Additionally, basinal brines are extremely saline,
with total dissolved solids (TDS) > 50 g/L, Cl

concentrations > 60,000 mg/L, and Naþ
concentrations > 20,000 mg/L (Gat, 1996; Osborn et al., 2011).
Warner et al. (2012) suggested that shallow groundwater having
undergone limited mixing with basinal brines (<20% brine water in
solution) should exhibit increases in Naþ and Cl
concentrations
(>100 mg/L), but would still remain indistinguishable from mete-
oric water using d2H and d18O values. Alternatively, Gat (1996)
80 St.T.M. LeDoux et al. / Applied Geochemistry 71 (2016) 73e85

suggested that shallow, meteoric groundwater interacting with

200
10

A deeper basinal brines should exhibit increases in d18O values as a

function of TDS (Fig. 9).
In eastern Kentucky, the d18O values of groundwater did not
show a strong relationship to Naþ or Cl
(R2 ¼ 0.045, P > 0.05 and
8

150
R2 ¼ 0.12, P < 0.01, respectively) (Fig. 9A, B). The weak relationship
of d18O to Cl
and the presence of elevated Br concentrations in two
[CH4] (mg/L)

[SO4] (mg/L)
samples (1.3e2.2 mg/L; Suppl. Table S.4) may be indicative of some
6

brine influence. Nevertheless, most of the analyzed groundwater

100
samples showed relatively low salinity (TDS < 0.7 g/L) and Br
concentrations (<0.5 mg/L) suggesting rather negligible mixing
with any brine (formation) groundwater. Alternatively, the Naþ and
4

Cl
present in the studied groundwater may have originated from

halite (NaCl) dissolution along the flow path. This process would

50
not affect the d18O of groundwater in our study area (Fig. 9C). Halite
2

is a common mineral that occurs in trace amounts in sedimentary

rocks of marine origin (e.g., Chi and Savard, 1997; Kesler et al., 1996)
which are common in the studied area. Because of high solubility of
halite in water, Naþ and Cl
concentrations generally increase over
0

0
time as groundwater interacts more extensively with bedrock. Type
-300 -200 -100 0 100 200 1 groundwater, with higher CH4 and lower O2 concentrations, may
ORP (mV) therefore represent groundwater that has had a greater water-rock
interaction, perhaps moving along deeper flow paths. If much of the
CH4 is indeed biogenic in origin as inferred from lower d13C values
10

B (Fig. 3A), these flow paths likely include anaerobic conditions

because microbial methanogenesis has been observed only in O2
deficient environments (e.g., Whiticar, 1999).
8

Another major difference between Type 1 and Type 2 ground-

water is the amount of SO2
4 present with a mean of 54 mg/L for
[CH4] (mg/L)

Type 2 as compared to a mean of 6 mg/L for Type 1. Generally, Type

6

2 groundwater was more oxygenated (>1e10 mg/L) and could

reflect a shallower flow path with more sulfide mineral oxidation.
In order to distinguish major SO4 sources in the studied ground-
4

water, we sampled a variety of bedrock types and used sulfur

sequential extraction techniques to separate elemental sulfur, acid-
soluble sulfate, and acid-volatile and chromium-reducible sulfur
2

characteristic of various sulfide bedrock minerals (Szynkiewicz

et al., 2009). Gypsum/anhydrite-rich formations do not appear to
be present in the study area. Therefore, the majority of ground-
0

water SO2
4 is likely to be sourced from the oxidation of sulfide

0 50 100 150 200 250 300 minerals, primarily pyrite (FeS2), which is a common mineral in
[SO4] (mg/L) coal and shale deposits and is present in the studied area.
Accordingly, the majority of extracted sulfate phases from bedrock
samples had very similar d34S values (
2.5 to þ4.7‰) to bedrock
sulfide phases (
1.9 to þ4.6‰), implying that sulfide-derived SO2

10

C 4
was the major source of SO2
4 (Fig. 4A). However, the groundwater
SO4 had a wide range in d34S and d18O values from
1 to þ59‰
and þ2 to þ19‰, respectively, and the two isotopic ratios were
8

positively correlated with each other (Fig. 4B). As the formation of

SO2

4 by sulfide oxidation does not involve significant S isotope
[CH4] (mg/L)
6

fractionation (Krouse and Grineko, 1991; Clark and Fritz, 1997),

there must be additional processes altering the isotopic ratios of
dissolved SO2
4 , such as microbial sulfate reduction (see next sec-
4

tion 5.2.2 for more details).

Interestingly, the oxidation reduction potential (ORP) appeared
to be a useful geochemical predictor of CH4 and SO2
4 concentra-
2

tions in the studied area (Fig. 5A). Type 2 groundwater was more
0

Fig. 5. (A) CH4 (in pink) and SO4 (in blue) concentrations as a function of ORP; both
analyzed using linear regression (for CH4 vs. ORP: R2 ¼ 0.40, P < 0.0001; for SO4 vs.
0 2 4 6 8 10 ORP: R2 ¼ 0.21, P < 0.001). (B) CH4 concentrations as a function of SO4 concentrations,
DO (mg/L) Spearman’s rank-order correlation (r ¼
0.75). (C) CH4 concentrations as a function of
DO, Spearman’s rank-order correlation (r ¼
0.53). On B and C, Type 1 groundwater is
in red and Type 2 in green. (For interpretation of the references to color in this figure
legend, the reader is referred to the web version of this article.)
 St.T.M. LeDoux et al. / Applied Geochemistry 71 (2016) 73e85 81

10
200
100

8
[CH4] (mg/L)
ORP (mV)
0

6
-100

4
-200

2
-300

< 30 % > 30 %
Percent Mining w/in 1km
Fig. 6. ORP as a function of proximity to surface mining with <30% area within a 1 km
radius covered by surface mining versus sampling sites with >30% area within a 1 km
radius covered by surface mining. Statistical analyses done using ANOVA (F1,57 ¼ 9.69,
P ¼ 0.0029). Open circles indicate the measured outliers, the box 25e75% of variance,
and solid (thick) line 50% of variance.
oxidizing (ORP >
120 mV) and had less dissolved solids and low
CH4 content (<1 mg/L). In contrast, Type 1 groundwater was more
reducing (ORP <
120 mV) with higher dissolved solids and higher
CH4 contents (1e10 mg/L). This is consistent with our conclusion
that Type 1 groundwater had a longer residence time in a reducing
environment, while Type 2 groundwater had interacted for a
shorter time under oxygenated conditions with less CH4 entrain-
ment, less biogenic CH4 production, and/or removal of CH4 via
oxidation.
0
0 5000 10000 15000 20000
Distance (m)
Fig. 8. CH4 concentration as a function of proximity to the Pine Mountain thrust fault
(PMTF). Because data for a distance to the PMTF could not be transformed to meet the
assumption of normality required by linear regression, this relationship was analyzed
using a Spearman’s rank-order correlation (r ¼
0.20). Type 1 groundwater samples
are in red, and Type 2 are in green. (For interpretation of the references to color in this
figure legend, the reader is referred to the web version of this article.)
5.2.2. Microbial processes
Various microbial processes may oxidize CH4 in groundwater by
using it as an electron donor (e.g., Whiticar, 1999). Microbial CH4
oxidation would lead to increases of HCO3 in groundwater, result-
ing in a negative correlation between CH4 and HCO3 (Van
Stempvoort et al., 2005), which was not the case for the studied
groundwater (Suppl. Fig. S.8). Nevertheless, this relationship could
have been masked as HCO3 concentration is more likely to be
controlled by the widespread dissolution of carbonate bedrock,
rather than oxidation of much smaller, localized amounts of CH4

Fig. 7. Concentration of CH4 as a function of elevation. PMTF e Pine Mountain Thrust Fault. (For interpretation of the references to color in this figure legend, the reader is referred
to the web version of this article.)
82 St.T.M. LeDoux et al. / Applied Geochemistry 71 (2016) 73e85

Fig. 9. (AeB) d18O of groundwater as a function of Naþ and Cl
concentrations. Analyzed using linear regression (R2 ¼ 0.045, P ¼ 0.107 and R2 ¼ 0.12, P ¼ 0.0045, respectively;
regression lines in blue). Type 1 groundwater samples are in red, and Type 2 groundwater samples are in green. (C) d18O of groundwater as a function of total dissolved solids (TDS).
The grey fields of various brines and mixing trends were adopted from Gat (1996). The blue field shows the reported range of d18O and TDS values for the Appalachian Basin brines
in the northeastern United States by Warner et al. (2012). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

found during the course of this study. Therefore, we cannot rule out
the possibility of microbial oxidation of CH4 but have no direct
evidence for it.
There is evidence for the microbial reduction of SO2
4 , which has
been previously coupled to CH4 oxidation (e.g., Whiticar, 1999; Van
Stempvoort et al., 2005). Microbial sulfate reduction is a common
anaerobic process responsible for the removal of SO2
4 from
groundwater (Head et al., 2003), and causes an enrichment of d34S
and d18O values in the remaining SO2
4 (Canfield, 2001; Detmers
€ttcher et al., 2001). This occurs because microbes
et al., 2001; Bo
preferentially metabolize isotopically lighter 32S and 16O isotopes
(Detmers et al., 2001; Bo €ttcher et al., 2001). Microbial sulfate
reduction has been previously detected in shallow groundwater of
Kentucky’s coal fields (Wunsch, 1993). Given that bedrock S sources
sampled in the studied area showed relatively low d34S values
compared to groundwater SO2
4 (Fig. 4A) and that there was a
significant positive relationship between d34S and d18O in ground-
water (Fig. 4B), microbial sulfate reduction is likely taking place in
the studied groundwater system. Microbial sulfate reduction may
be the explanation for the great number of groundwater samples
containing very low or no SO2
4 (<5 mg/L and <0.05 mg/L, respec-
tively). This may also account for the nearly exclusionary relation-
ship between SO2
4 and CH4 (Fig. 5B) because microbial CH4
generation is often inhibited at elevated SO2

4 concentrations (e.g.,
Lovely and Klug, 1982; Osborn and McIntosh, 2010).
Although the process of microbial sulfate reduction produces
hydrogen sulfide (H2S), its concentrations were relatively low
(<1 mg/L) in most groundwater sampled for this study. This sug-
gests that microbially produced H2S may be undergoing further
alteration in situ, such as in the formation of secondary pyrite, a
common process in anaerobic sediments actively undergoing mi-
crobial sulfate reduction (e.g., Szynkiewicz et al., 2009).
5.3. CH4 occurrence in relation to surface mining
Surface mining has been previously demonstrated to expose
bedrock minerals to chemical weathering by meteoric precipitation
and to oxidize shallow groundwater (Evangelou et al., 1998;
Eychaner, 1998; Clarke, 1995). In eastern Kentucky, the proximity
to surface mining did have a significant effect on the groundwater
 St.T.M. LeDoux et al. / Applied Geochemistry 71 (2016) 73e85 83

Deviated fracked well

(post 2006)

Abondoned non-fracked Non-deviated fracked

well (pre 1980) well (post 1980)

Middle Breathitt
CH4
Freshwater CH4
COALBEDS CH4
Lower Breathitt

Microbial Microbial
SO4 Methanogenesis
Lee reduction

CH4

Pennington
CH4
Chattanooga CH4 CH4

Fig. 10. Conceptual model showing major processes controlling chemical composition of the studied groundwater in Letcher County, Kentucky. Blue dotted line indicates
approximate position of groundwater table. Red dots and arrows show major sources and plausible migration pathways of CH4, respectively. (For interpretation of the references to
color in this figure legend, the reader is referred to the web version of this article.)

ORP values when modeled using an analysis of variance test
(ANOVA). The studied groundwater appeared to have a higher
likelihood of oxidation for sampling sites with more surface mining
(i.e., sites with >30% area within a 1 km radius mined; mean
ORP ¼
75 mV) when compared to the sites with less surface
mining (i.e., sites with <30% area within a 1 km radius mined; mean
ORP ¼
175 mV) (Fig. 6). We imply that higher potential for
groundwater oxidation closer to mining sites likely results from the
increased infiltration of oxygenated meteoric precipitation in the
bedrock. The latter is greatly enhanced by methods of explosive
excavation (i.e., dynamite blasting) implemented for surface min-
ing, which increases the secondary permeability of newly exposed
strata (Guebert and Gardner, 2001). Additionally, surface mining
increases the total surface area of bedrock exposed to infiltration of
meteoric precipitation within macropore structures of the moun-
tain slopes that have been reconsolidated after excavation (Guebert
and Gardner, 2001). Over time, these factors enhance recharge of
shallow oxygenated water and, thus, increase the likelihood of CH4
and pyrite oxidation in shallow groundwater.
local precipitation, suggesting shallow recharge by meteoric pre-
cipitation. Two major groundwater types were recognized based on
their CH4 content: Type 1 groundwater enriched in CH4, Naþ, Cl
,
and HCO3 and Type 2 groundwater with low CH4 and high Ca2þ,
Mg2þ, HCO
2

3 and SO4 concentrations. Type 1 groundwater has
likely had a longer time to interact with bedrock under more
reducing conditions. Therefore, the higher CH4 concentrations in
Type 1 groundwater could be due to a combination of factors: more
thermogenic CH4 entrainment, more bacterial CH4 production, and
less CH4 oxidation. Given the higher ORP values of Type 2
groundwater, CH4 was more prone to oxidation and removal. There
was strong isotopic evidence for SO2
4 reduction in the studied
groundwater, which has been previously coupled to CH4 oxidation.
Local surface mining activity may have enhanced the recharge of
oxygenated water to the system due to extensive fracturing and
increased hydraulic conductivity, the result of which would be
higher ORP values and lower CH4 concentrations in groundwater.
6.2. Synthesis and recommendations

6. Summary Similar to previous studies by Warner et al., 2013b; Molofsky

6.1. Major conclusions
Fig. 10 summarizes the major processes taking place that are
related to CH4 in the studied region of eastern Kentucky, Central
Appalachia. Overall poor correlations between CH4 concentrations
and the distance to deviated or active hydraulic fracturing wells
suggest that this type of hydraulic fracturing is not the major cause
of CH4 being present in the studied groundwater. The d13C and d2H
of CH4 indicate a dominantly mixed immature thermogenic and
biogenic origin. The Pennsylvanian coal deposits (Suppl. Fig. S.2)
are a likely source of CH4 in the studied groundwater along with
biogenically produced CH4. Some, probably minor/trace, amount of
thermogenic CH4 may be coming from the deeper Chattanooga
Shale.
The d2H and d18O of the studied groundwater in eastern Ken-
tucky were in good agreement with the isotopic composition of
et al., 2013; Siegel et al., 2015, our results suggest that currently
active hydraulic fracturing did not increase the likelihood of stray
gas migration or the occurrence of CH4 in the groundwater of
eastern Kentucky. Most of the CH4 appears to be sourced by shallow
bedrock sources such as coalbeds and microbial processes. This
likely suggests good integrity of existing conventional and hy-
draulically fractured gas wells, and/or limited connection via frac-
tures/faults between deep gas reservoirs (e.g., Chattanooga shale)
and shallow groundwater.
Although not apparent in our study, some residents have re-
ported occasional accidents of domestic well combustion as a result
of excessive CH4 accumulation. Therefore, additional research is
needed to determine whether natural and/or anthropogenic
(mining, hydraulic fracturing) processes have had impacts on
groundwater. In order to better address localized phenomena,
future research would likely benefit from a more intensive sam-
pling within a smaller area as the Eastern Kentucky’s mountainous
84 St.T.M. LeDoux et al. / Applied Geochemistry 71 (2016) 73e85
terrain creates relatively small, isolated valleys that increase spatial
heterogeneity, making the chemical and isotopic results more
difficult to compare.
Previous studies have mainly focused on comparing geochem-
ical/isotope tracers with proximity to gas wells (Osborn et al., 2011;
Jackson et al., 2013; Vengosh et al., 2014), and less attention has
been given to linking CH4 occurrence to hydraulic or tectonic fea-
tures (Molofsky et al., 2013; Warner et al., 2013b) and thermal
maturity of shale/coal deposits of a given area (Osborn and
McIntosh, 2010). Tectonic faults and fractures are conduits for
migration of deep fluids and gases. Therefore, the areas more
tectonically active in the past might be more prone to groundwater
contamination by stray gas due to subsequent hydraulic fracturing
activities. A better understanding or modeling of groundwater flow
paths could help explain the differences between the two
groundwater types distinguished in our study and more focus on
understanding of subsurface flow would be beneficial for all future
work.
More investigation of microbial sulfate reduction as possibly
coupled to CH4 oxidation would be quite beneficial for under-
standing biogeochemical processes in relation to the effects of
drilling and fracturing in eastern Kentucky and even in sites unaf-
fected by hydrocarbon exploitation. Microbial processes are usually
controlled by availability of simple organic compounds which de-
creases in more thermally-mature organic deposits (e.g., Osborn
and McIntosh, 2010). Consequently, microbially-mediated CH4
production and oxidation via sulfate reduction and methanotrophy,
respectively, might vary regionally and, thus, affect CH4 fluxes into
shallow groundwater. Nevertheless, limited number of studies ad-
dresses the natural constraints of local bedrock geology on CH4
fluxes into groundwater (Stra˛ po c et al., 2007; Osborn and McIntosh,
2010; McIntosh et al., 2014). Additional work aimed at under-
standing these processes would help in better predicting where
CH4 concentrations will be above acceptable limits and the
response to anthropogenic activities.
Acknowledgements
This study was supported by the 2014 Ralph E. Powe Junior
Faculty Enhancement Award from Oak Ridge Associated Univer-
sities awarded to Anna Szynkiewicz. Additional financial support
was provided by the Department of Earth and Planetary Sciences
and Graduate Student Senate of the University of Tennessee. We
greatly thank Annette Engel and Audrey Patterson for help with
chemical analysis, and Justin Coleman, Andre Merino, Jessica
Welch, and Caleb Smith for field and lab assistance. Review com-
ments of three anonymous reviewers greatly improved the quality
and clarity of this manuscript.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.apgeochem.2016.05.007.
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