Geofluids (2016) 16, 565–584 doi: 10.1111/gfl.

12176

Geochemical fingerprinting of hydraulic fracturing fluids

from Qusaiba Hot Shale and formation water from
Paleozoic petroleum systems, Saudi Arabia
P. BIRKLE
Geology Technology Team, EXPEC Advanced Research Center (EXPEC ARC), Saudi Aramco, Dhahran, Saudi Arabia

ABSTRACT
Provenance studies of produced water are essential to trace flow dynamics and reservoir compartmentalization in
petroleum systems and to quantify fluid recovery rates from unconventional fracturing. Produced water from a
hydraulically fractured well in the Qusaiba Hot Shale in the Northern Exploration Area, Saudi Arabia, was daily
monitored and analyzed for water chemistry, and environmental (d2H, d13C, d18OH2O, d18OSO4, d34SSO4, d37Cl,
87
Sr/86Sr) and cosmogenic isotopes (3H, 14C, 36Cl), to differentiate from reference fluids of supply water, fractur-
ing fluids, and formation water from adjacent Paleozoic units. Initially, recovered water is composed of fracturing
fluids and subsequently replaced by a homogeneous cut of pristine formation water. Formation water is com-
posed of dominant meteoric water (approximately 84 vol%) and minor fossil evaporated seawater. The young
14
C-apparent age between 6000 and 6700 years BP and depleted d18O/d2H values for the meteoric component
confirm the infiltration of surface water into the Qusaiba Hot Shale interval or adjacent units during the Early
Holocene Pluvial Period under cooler and wetter climatic conditions than present, which suggest the presence of
a very recent, dynamic hydraulic flow system. 36Cl/Cl ratios between 102 9 10
15 and 31 9 10
15 are ambigu-
ous and can be attributed to atmospheric recharge close to the coast, mixing of 36Cl-enriched Quaternary mete-
oric recharge with 36Cl-depleted fossil seawater, and/or hypogene production by U-Th-enriched host rock.
Produced waters from Qusaiba Hot Shale are within the compositional range of Na-Cl-type formation water from
Paleozoic reservoir units in northern Saudi Arabia with salinities from 30 000 to 130 000 mg l
1. As a novel tech-
nological approach for exploration wells in Northern Saudi Arabia, multi-isotopic methods were successfully
implemented to quantify flowback volumes from hydraulic fracturing, and to fingerprint pristine formation water
or pore water in Paleozoic systems on their provenance, residence time, migration pathways, and secondary
alteration processes.

Key words: cosmogenic isotopes, environmental isotopes, flowback, hydraulic fracturing, Northern Saudi Arabia,
Paleozoic formation water, Qusaiba Hot Shale

Received 9 June 2015; accepted 24 March 2016

Corresponding author: Peter Birkle, Geology Technology Team, EXPEC Advanced Research Center (EXPEC ARC),
Saudi Aramco, 31311 Dhahran, Saudi Arabia.
Email: peter.birkle@aramco.com. Tel: +966 13 8732260. Fax: +966 13 8730572.

Geofluids (2016) 16, 565–584

the fracturing process. During the postfracturing stage, a

INTRODUCTION
Hydraulic fracturing of unconventional shale resources to
stimulate wells and recover natural gas typically implies the
injection of water with sand and chemicals at high pres-
sures into the wellbore to create small (<1.0 mm) frac-
tures. As a standard technique, supply water from nearby
surface or close-to-surface resources is mixed with a variety
of additives, such as diluted acid, gelling agent to form the
primary fracturing fluid (‘slickwater’), and KCl to optimize
variety of chemically distinct water types are produced from
fracturing wells, causing a technical challenge to character-
ize the type and origin of produced water. In this study,
the expression ‘flowback water’ refers to any fraction of
recovered fracturing fluid, mainly from the first few days of
the postfracturing period. ‘Produced water’ defines any
type of recovered water, co-produced with gas, ranging
from flowback water to formation water. In the petroleum
industry, the terms ‘formation water’ and ‘pore water’

© 2016 John Wiley & Sons Ltd

566 P. BIRKLE
stand as synonymous for interstitial water naturally occur-
ring within the pore space of a rock unit, although the lat-
ter term is more commonly used to describe entrapped
water in low-permeable clay units. In general, the correla-
tion between brine chemistry and bulk rock geochemistry,
as well as the source of total dissolved solids, is not well
understood.
Standard geochemical fingerprinting techniques for pro-
duced water in the oil industry were historically based
upon the correlation and visualization of major ion con-
centrations and ratios, such as the Stiff plot (Stiff 1951) or
Piper diagram (Piper 1944). Since the late 1990s, novel
applications of multi-isotopic techniques were developed to
fingerprint formation water in hydrocarbon exploration
and production operations, such as for the stray-fluid
migration associated with unconventional hydrocarbon
production in the Midale area, Saskatchewan, Canada
(Rostron & Holmden 2000), fluid migration on a basinal-
scale in the Northern Appalachian (Osborn et al. 2012),
brine contamination in the Popular oil field, Montana
(Peterman et al. 2010), and production-related mobiliza-
tion of multi-aquifer systems in conventional carbonate
reservoirs, Gulf of Mexico (Birkle et al. 2002, 2009). A
representative recompilation of formation water-related
studies and applied technologies in petroleum reservoirs is
given in Kharaka & Hanor (2014).
In general, most geochemical studies on flowback waters
from unconventional production in shale gas are limited to
hydrochemical analysis of major and few minor elements
(i.e. Fe, Ba, Sr) to fingerprint the origin of produced water.
Although over 100 flowback samples from the southwest-
ern and northeastern regions of the Marcellus Shale play in
USA were analyzed on their basic water chemistry (Blauch
et al. 2009), multiple options still prevail on the provenance
of flowback fluid from Marcellus Shale, such as the migra-
tion of deep basinal brine from Devonian sandstone units
into the shale package (‘allochthonous model’) or by pri-
mary salt dissolution from the shale (‘autochthonous
model’). Laboratory experiments with drilling cuttings and
cores suggest the latter hypothesis (Blauch 2011). More
likely, data for chlorine, bromine, sodium, and MCl2 show
that most brines in Western Pennsylvania are composed of a
mixture of two end members: Brines originated as the resid-
ual pore fluid in halite evaporites from the Silurian Salina
Group and were mobilized—in a second stage—out of the
salt during compaction by overlying beds and during Late
Paleozoic deformation. The mixing of surface water with
the residual brines during Tertiary or Quaternary, plus the
secondary alteration of the fluid by dolomitization and
reactions with clay minerals (such as smectite to illite con-
version) explains the final, current composition of forma-
tion water (Dresel & Rose 2010; Engle & Rowan 2014).
Potential source brines, that is, Silurian brines, are com-
monly found in rock units underneath the Marcellus Shale
(Warner et al. 2012; Haluszczak et al. 2013). Stable iso-
tope fingerprinting of produced water can provide quantita-
tive information on recovery rates of fracturing fluids and
mixing proportions with aquifer water. By correlating d18O
and d2H isotope ratios of producing wells, binary mixing
models showed a contribution of 6% to 40% of the overly-
ing Lodgepole formation water to the produced fluids from
an unconventional gas well in the Bakken Formation (Sas-
katchewan, Canada) (Rostron & Arkadakskiy 2014).
Knowledge of the source and the amount of unwanted flu-
ids can be applied to the design of the hydraulic fracture
treatment to reduce water cut from overlying aquifers in
future wells.
This study presents a specific case study on hydraulic
fracturing of the Silurian Qusaiba Hot Shale in the North-
ern Exploration Area in Saudi Arabia, where sampling of
produced water during the postfracturing period of a
hydraulically fractured well (Well A) was performed on a
daily basis for their respective geochemical analysis on
major ions, selected trace elements (B, Ba, Br, Fe, Li, Sr),
environmental (d2H, d13C, d18OH2O, d18OSO4, d34SSO4,
d37Cl, 87Sr/86Sr), and cosmogenic isotopes (3H, 14C,
36
Cl) on selected samples. A mass balance of flowback
recovery rates and potential mechanism for flow migration
with implications on fracture geometry in Well A are pre-
sented in Birkle (2016). Within this article, water geo-
chemistry of produced water from Qusaiba Hot Shale in
Well A is compared with reference samples of fracturing-
related fluids (fracturing fluid, completion brine, mud fil-
trate, and supply water from Jilh Formation) and with
groundwater prototypes from Paleozoic formations (Jubah,
Qusaiba, Sarah, Quwarah, Raan, Kahfah) in Northern
Saudi Arabia (Well C to Well G), Arabian Gulf (Well H)
and Southern Ghawar Production Area (Well I). Figures 1
and 2 show the well location and stratigraphic affiliation of
sampled produced water, respectively, in the Northern
Exploration Area, Arabian Gulf region and Southern Gha-
war Production Area.
The applied combination of multigeochemical techniques
is providing practical solutions with an immediate technical
and economic impact for the hydraulic fracturing industry.
The knowledge of precise volumes of flowback recovery is an
essential economic factor to predict and quantify the potential
reuse of recovered and treated fracturing fluid for subsequent
re-injection stages. Isotopic affinities or heterogeneities
between involved fluid types represent natural fingerprints for
the presence (or lack in the second case) of potential migra-
tion pathways from under- or overlying groundwater systems
toward the fractured zone and can also be applied to trace
potential leaks through annulus cement, production casing,
or underground well failure. The provenance of composi-
tional heterogeneities in produced fluids, that is, by salt disso-
lution, evaporation of seawater, or by secondary diagenetic
processes is still in debate for most petroleum systems.
© 2016 John Wiley & Sons Ltd, Geofluids, 16, 565–584
 Geochemistry of fracturing fluids and Paleozoic formation water, Saudi Arabia 567

Fig. 1. Location of sampled wells from the Northern Arabia Exploration Area (Wells A–G), Arabian Gulf (Well H) and Southern Ghawar Production Area
(Well I) and major oil (green color) and gas (red color) production fields in Saudi Arabia (Field location map is provided from Unconventional Resource Explo-
ration Development Department and CartoGraphy, Saudi Aramco).

(green and dark-red filled intervals, respectively, in Fig. 2)

PALEOZOIC STRATIGRAPHY AND
PETROLEUM SYSTEMS OF SAUDI ARABIA
The stratigraphic section of Central Arabia and the Greater
Ghawar Uplift province is commonly divided into a clastic
‘pre-Khuff’ and a carbonate-dominated ‘Khuff and
younger’ section (Wender et al. 1998; Fig. 2). The pre-
Khuff Paleozoic succession of Saudi Arabia is dominantly
siliciclastic and represents the product of depositional
cycles that were influenced, to variable degrees, by the evo-
lution of the Prototethys and Paleotethys oceans (Cantrell
et al. 2014). Four erosional events have been recognized
in the Paleozoic section of the Greater Ghawar area (Wen-
der et al. 1998), with the Hercynian Orogeny as a major
erosional event through the Carboniferous uplift of the
Arabian Plate (Cantrell et al. 2014). The Silurian basal
‘Qusaiba Hot Shale’ is the principal source rock for reser-
voirs extending from the Ordovician to Early Triassic
(black flag in Fig. 2) (Abu-Ali et al. 1999; Abu-Ali and
Littke 2005, Cantrell et al. 2014). Paleozoic oil and gas
are mainly produced from sandstones of the Permian
Unayzah and Devonian Jauf Formation, and from basal
transgressive marine sandstones and cyclic, dolomitic shelf
carbonates of the Late Permian Khuff Formation, with
minor oil reservoir rocks in Lower Paleozoic units. During
Late Permian time, a major transgression event initiated
the deposition of an extensive carbonate sequence through
Mesozoic and Cenozoic (not shown in Fig. 2), including
the deposition and formation of world’s largest petroleum
system, the Upper Kimmeridgian to Lower Tithonian Arab
Formation in the Ghawar field (Fig. 1).
HYDRAULIC FRACTURING IN SAUDI ARABIA
As part of an active exploration program for unconven-
tional gas resources in three areas of Saudi Arabia (North-
ern Arabia, South Ghawar, and the Rub’ al-Khali), the first
Silurian shale gas well SHALE-1 was drilled in 2007 in the
low sand dunes to the north of Rub’ al-Khali desert

© 2016 John Wiley & Sons Ltd, Geofluids, 16, 565–584

568 P. BIRKLE

Fig. 2. Generalized Cambrian-Triassic stratigraphic column and depositional profile for Saudi Arabia showing major reservoir and source intervals (modified
from Abu-Ali and Littke 2005, Haq and Al-Qahtani 2005). The stratigraphic location of discussed groundwater samples is marked with blue asterisks.

(Alexeyenko et al. 2013). Between November 24, 2012,
and December 21, 2012, a multistage, horizontal hydraulic
fracturing project with a total of 12 stages was performed
at a drilling site (‘Well A’) in the Northern Arabia Explo-
ration Area of Saudi Arabia within an unconventional play
(Fig. 1). A combination of supply water, breaker, crosslin-
ker, polymer, acids, and fluids from injection and pump
down was injected, together with proppants, into the
Qusaiba Hot Shale interval as the identified target for frac-
ture stimulation. Supply water was provided from a low-
saline aquifer in the overlying Triassic Jilh formation as
basic slickwater ingredient. Additionally, 5% KCl brine was
used during the postfracturing cleanout of proppant (frac
plugs) using coiled tubing from December 23, 2012, to
December 30, 2012.
After the pressure shutdown, a total of 41 produced
water samples were collected from Well A (Fig. 1) on a
daily basis within the postfracturing period from December
30, 2012, to February 10, 2013. As reference data for sup-
ply water composition, two samples of low-saline water
from Jilh Formation were taken from an adjacent ground-
water well (Well B in Fig. 1) on February 3, 2013, to

© 2016 John Wiley & Sons Ltd, Geofluids, 16, 565–584

 Geochemistry of fracturing fluids and Paleozoic formation water, Saudi Arabia
February 4, 2013. Supply water from Jilh was mixed with
applied chemical reactants (breaker, crosslinker, and poly-
mer) to reproduce the primary chemical composition of
injected fracturing fluid (‘slickwater’).
DYNAMICS AND RESIDENCE TIMES OF
FRESHWATER AQUIFERS AND DEEP
GROUNDWATER SYSTEMS IN SAUDI ARABIA
In Saudi Arabia, principal freshwater aquifers are found in
arenaceous and/or carbonate formations, including the
major formations of Saq, Tabuk, and Wajid of Paleozoic
age, Minjur Dhurma, Biyadh-Wasia of Mesozoic age and
Umm er Radhuma and Dammam of the Tertiary age
(FAO 1998; Chowdhury & Al-Zahrani 2015). In the
northern part of Saudi Arabia, the extensive Paleozoic Saq
and Tabuk sandstones in the Tabuk Basin and Neogene
sands in the Wadi as Sirhan Basin form the principal aqui-
fers (Edgell 1997). In particular, the Saq aquifer consti-
tutes the most productive and most developed
groundwater reservoir in the northwest with an average
and maximum depth of 830 and 1223 m, respectively
(Edgell 1997; Al-Ahmadi 2009). Relatively short residence
times, elevated discharge rates from 804 to
1728 m3 day
1, and an average transmissivity and storativ-
ity of 1572 m2 day
1 and 2.86 9 10
4, respectively, sug-
gest the presence of a dynamic, porous Saq groundwater
system at depth from 632 to 1223 m (Al-Ahmadi 2009).
Above, the Middle to Late Ordovician Qasim Formation
represents an interlayered sequence of clastic aquifers (Kah-
fah, Quwarah) and sealing aquitards (Hanadir, Ra’an) (Al-
Aswad & Al-Bassam 1997) (Fig. 2). The Silurian Qusaiba
Shale is considered a sealing horizon above the Late
Ordovician Sarah sandstones. Post-Qusaiba aquifers, such
as the Qasr aquifer of the Jauf Formation, are described in
Al-Aswad & Al-Bassam (1997), Al-Bassam et al. (2000),
Al-Mahmoud (2015), and elsewhere. The Triassic Jilh
aquifer system, recently used as a water source for slickwa-
ter hydraulic fracturing projects in the Northern Explo-
ration Area, is one of the secondary, minor groundwater
systems of Saudi Arabia consisting sandstone and shale
(Loni et al. 2014) with increasing limestone content and
carbonate facies toward the northeast (Carrigan 1994).
Saudi Aramco is recently evaluating alternative water
sources (i.e. treated wastewater, seawater) for hydraulic
fracturing with the intension to preserve freshwater
resources for the Kingdom.
The present-day hyperarid climate of Saudi Arabia allows
minimal recharge, so aquifers contain ‘fossil’ groundwater
10 000–36 000 years old (Edgell 1997). The groundwater
in the deep sandstone aquifers, such as the Saq, Tabuk,
and Wajid of Paleozoic age, is classified as nonrenewable
water (i.e. nonrechargeable), which was formed approxi-
mately 10 000–32 000 years ago (MAW 1984; Edgell
© 2016 John Wiley & Sons Ltd, Geofluids, 16, 565–584
569
1997). Carrigan (1994) reported a residence time of
4600  2000 years BP for low-saline groundwater (TDS
value of 1200 mg l
1) from the underlying Cambrian Siq
formation in northern Saudi Arabia. It is possible that deep
Siq groundwater originated by the downward flow of water
from shallow aquifers in the region, along a major fault
zone.
ANALYTICAL METHODS
Hydrochemical analysis of major ions and selected trace
elements (B, Ba, Li, Sr) from selected produced water,
supply water, and fracturing fluid samples were performed
by GC, ICP-MS, and ICP-OES at the Chemistry Analysis
Unit (R & DC) of Saudi Aramco. For 87Sr/86Sr analysis,
strontium was extracted from solution on ion exchange
columns and re-eluted for precipitation on tungsten fila-
ments for analysis by thermal ionization mass spectrometry
(TIMS) on a Thermo-Finnigan Triton at the Isotope Geo-
chemistry & Geochronology Research Centre at Carleton
University, Ottawa, Canada. For 37Cl analysis, chloride was
precipitated from filtered sample water as AgCl and then
converted using methyl iodide to methyl chloride (CH3Cl)
gas for analysis by CF-IRMS. Analyses are reported as per-
mil difference from Standard Mean Ocean Chloride
(SMOC) with an analytical precision of approximately
 0.1&, as determined with standards for each analysis.
Analyses were carried out in the Isotope Tracer Technolo-
gies Laboratory, Waterloo, Canada. Samples for the analy-
sis of 34S and 18O in sulfate were filtered through 0.45 lm
pore diameter and brought to pH 5 with nitric acid fol-
lowed by the addition of BaCl2 to precipitate solid BaSO4.
The BaSO4 was filtered from the solution and washed with
deionized water and dried at 50°C. An approximately
1 mg subsample was weighed into a tin capsule with WO3
for d34S analysis by combustion to SO2 with an elemental
analyzer (EA, VarioEL) and isotope analysis by continuous
flow isotope ratio mass spectrometry (CF-IRMS) with a
Thermo-Finnigan Delta Plus mass spectrometer in the Iso-
tope Tracer Technologies Laboratory. Results are
expressed as the permil difference from the Canyon Diablo
Troilite (CDT). Analytical precision of 18OSO4 was mea-
sured on a second subsample of the dried BaSO4 precipi-
tate by high-temperature pyrolysis in a glassy carbon
combustion oven (Thermo-Finnigan TCDC) to produce
CO for isotope analysis by CF-IRMS. Results are normal-
ized to the permil difference from Vienna Standard Mean
Ocean Water (VSMOW) with an analytical precision of
 0.5&.
After water samples passed through 0.45-lm filters,
d18O and d2H ratios were measured using a Thermo--
Fisher Delta Plus XP mass spectrometer coupling with a
Thermo-Fisher Gasbench at the Isotope Lab of the Geo-
chemistry Unit in EXPEC ARC (Saudi Aramco, Dhahran,
570 P. BIRKLE
Saudi Arabia). d18O and d2H were determined on CO2
and H2 gas, respectively, equilibrated with the water sam-
ples for 24 h at 25°C in the presence of a Pt catalyst.
Three in-house standards were calibrated with international
standards VSMOW and SLAP and analyzed together with
water samples to calibrate isotope ratios of samples and to
check the overall reproducibility and accuracy. The stan-
dard deviations of d2H and d18O based on the repeated
analyses of standards are better than 0.95& and 0.10&,
respectively.
Tritium (T½ = 12.32 years) was analyzed by electrolytic
enrichment of filtered and deionized sample aliquots to
increase the tritium concentration by a factor of 10. Fol-
lowing enrichment, samples were analyzed in a Perkin
Elmer Quantulus ultra low background liquid scintillation
counter (LSC) with a background detection of <1 Bq.
Results are expressed in tritium units, TU, where 1 TU is
equal to 0.118 Bq l
1 or a tritium to hydrogen ratio, 3H/
H = 10
18. Analytical precisions for enriched samples are
reported with each analysis and are approximately  0.8
TU. Stable 13C in dissolved inorganic carbon (DIC) is ana-
lyzed by acidification and extraction as CO2 with a He
purge configured in-line with a Delta Plus continuous flow
mass spectrometer in the Isotope Tracer Technologies
Laboratory. Radiocarbon is measured in DIC by acidifica-
tion of 200 ml filtered sample water under vacuum and
cryogenic trapping of evolved CO2. CO2 was converted to
graphite by reaction with H2 in the presence of zero-valent
iron beads (approximately 200 lm dia) at 700°C. The gra-
phite is pressed into a 1-mm-diameter target and mounted
in a Cs+ ion sputter source of a 3 MV tandem accelerator
mass spectrometer (AMS) at the Lalonde AMS facility at
the University of Ottawa. Radiocarbon to carbon-12 iso-
tope ratios are calibrated with NIST oxalic acid standard
and normalized to d13C =
25&. Results are reported as
a fraction of Modern Carbon. Analytical uncertainty is
measured individually and reported for each sample. For
36
Cl analysis, chloride was precipitated from filtered sample
water as AgCl, then cleaned with deionized water and
dried. Approximately 1 mg of solid AgCl was pressed into
a target and analyzed using a 6 MV tandem accelerator
mass spectrometer (AMS) at PRIME Lab, Purdue. Isotope
ratios are normalized to true ratios with internal standards.
RESULTS
Water Geochemistry in Paleozoic Reservoirs from Saudi
Arabia
Hydrochemical characteristics of produced water in explo-
ration wells from northern Saudi Arabia are compared with
reference samples from drilling and hydraulic fracturing-
related fluids to differentiate potentially anthropogenic
affected flowback samples from representative formation
water. Classified water types are listed as cations followed
by the anions in the order of decreasing concentrations.
The concentration, in milligrams per liter, of any given ion
contributes ≥5% to the concentration of TDS in the fluid
sample (Kharaka & Thordsen 1992). Hydrochemical com-
position, water types, and well location of representative
formation water samples from Paleozoic formations in the
Northern Exploration Area (Wells C to G) and Arabian
Gulf Production Area (Well H) of Saudi Arabia, as well as
reference samples from fracturing fluids, completion brine,
mud filtrates, and mixed produced water samples with
minor and major flowback of anthropogenic fluids are
shown in Table 1 and Fig. 1, respectively. The strati-
graphic context of the Paleozoic groundwater samples is
shown in Fig. 2. In general, little information is available
about the chemical composition of produced water from
the Early Silurian Qusaiba Hot Shale in Northern Saudi
Arabia. Except one sample set from Qusaiba Hot Shale
and Upper Qusaiba in Well E (Location in Fig. 1 and vio-
let circles in Fig. 3), water chemistry from Paleozoic for-
mations in the Northern Arabia Exploration Area is limited
to underlying strata from Early Silurian Sarah Formation
(sample set from Wells C, E, and F in Fig. 3) and Late
Ordovician formation members from Quwarah, Raan, and
Kahfah (Wells C and D), and from the overlying Middle
Devonian—Early Carboniferous Jubah Formation (Wells G
and H). Chemical characteristics of reference samples are
available for fracturing fluid from Well C (filled star in
Fig. 3), and different types of completion brines and mud
filtrates from Wells C and D (blank star and filled-crossed
star in Fig. 3, respectively). In Fig. 3, Na has been chosen
as conservative element to correlate against K (Fig. 3A)
and Ca (Fig. 3B), as the latter ones resulted to be relatively
abundant in anthropogenic fluids used during hydraulic
fracturing (‘Fracturing fluids’ in Table 1), and drilling
(‘Completion brines’ and ‘Mud filtrates’ in Table 1). In
general, the heterogeneous composition of drilling fluids
with salinity variations from 18 080 mg l
1 (K-Cl type) to
305 400 mg l
1 (Ca-Cl type) for completion brines and
55 890 mg l
1 (Na-Cl type) to 139 300 mg l
1 (Na-Ca-
Cl type) for mud filtrates complicates the volumetric quan-
tification of mixing members for produced water.
Representative formation water samples are dominated
by Na-Cl water type with a relatively low abundance of Ca
and K (‘Primary formation water (NaCl type)’ in Fig. 3)
which is available for Sarah (Well F, filled square in Fig. 3),
partially for Quwarah (Well C, yellow diamonds), and
combined Quwarah (QWRH)—Raan (RAAN)—Kahfah
(KHFH) formations (Well D, open diamonds). More than
70% of the recovered water samples show mixing trends
between anthropogenic fluids and formation water, as evi-
denced by Na-K-Cl, K-Na-Cl, K-Cl, Ca-Na-Cl, and Ca-Cl
water types with elevated K/Na, K/Cl and Ca/Na ratios.
The trend ① in Fig. 3A illustrates the mixing of NaCl-type
© 2016 John Wiley & Sons Ltd, Geofluids, 16, 565–584
 Table 1 Water hydrochemistry of representative formation water samples from Paleozoic formations in the Northern Arabia Exploration Area (Wells C to G) and Arabian Gulf Production Area (Well H) of Saudi
Arabia produced water samples with multiple components and reference samples from fracturing fluids, completion brine, and mud filtrates. Location of sampled wells is shown in Fig. 1.

Well Date Formation Member/Unit Period Water type TDS Density pH Na K Mg Ca Sr Ba Cl SO4 HCO3 CO3

Representative formation water samples

F Jun-11-10 Sarah Sarah L. Ord. - E. Silurian Na-Cl 45 140 1.0342 7.5 16 590 62 2.0 139 n.a. n.a. 26 360 447 1550 0.00
C Oct-26-09 Qasim QWRH L. Ordovician Na-Cl 128 750 1.0866 8.9 49 950 283 <1.00 <1.00 n.a. n.a. 71 550 1360 4580 1320
C Oct-26-09 Qasim QWRH L. Ordovician Na-Cl 129 300 1.0911 8.7 52 650 303 <1.00 <1.00 n.a. n.a. 69 020 1420 5120 1080
D Jan-29-11 @ 07:00 Qasim QWRH- M. - L. Ordovician Na-Cl 57 090 1.0485 6.3 23 150 239 48.0 703 13.0 <1 31 150 1060 980 0.00
Raan-KHFH
D Jan-31-11 @ 09:00 Qasim QWRH- M. - L. Ordovician Na-Cl 33 160 1.0281 7.2 14 180 192 9.0 252 18.0 <1 17 360 493 861 0.00
Raan-KHFH
D Jan-31-11 @ 21:00 Qasim QWRH- M. - L. Ordovician Na-Cl 51 080 1.0418 7.1 21 350 303 8.0 272 33.0 <1 27 860 673 914 0.00
Raan-KHFH
D Feb-01-11 @ 09:00 Qasim QWRH- M. - L. Ordovician Na-Cl 38 560 1.0319 7.2 15 910 210 13 291 23.0 <1 21 330 559 460 0.00
Raan-KHFH
Produced water (minor flowback of fracturing fluids or drilling fluid)
H* May-9-08 Jubah Jubah M. - L. Devonian Na-Cl-SO4-HCO3 74 740 1.0549 6.9 28 290 1230 36 491 n.a. n.a. 30 520 8530 5640 0.00
E Feb-06-12 @ 06:30 Qalibah QHS E. Silurian Na-K-Cl 30 810 1.0256 6.2 9930 3110 135 1060 82 65 18 830 14.0 846 0.00
E Mar-06-12 @ 05:00 Qalibah QHS E. Silurian Na-K-Cl 41 670 1.0322 7.2 15 050 2390 129 631 73.0 13.0 25 060 16.0 791 0.00
E Jul-4-12 Qalibah QHS E. Silurian Na-K-Cl 43 780 1.0348 6.7 13 710 4070 173 1300 85.0 46.0 28 430 34.0 129 0.00

© 2016 John Wiley & Sons Ltd, Geofluids, 16, 565–584

E Jul-4-12 Qalibah U. QHS E. Silurian Na-K-Cl 42 780 1.036 6.6 13 910 4010 189 1460 95.0 52.0 27 080 23.0 113 0.00
E Jun-18-12 Qalibah U. Qusaiba E. Silurian Na-K-Cl 27 380 1.0222 6.5 8200 2750 147 1030 86.0 42.0 17 980 <10.0 17.0 0.00
E Jun-18-12 Qalibah U. Qusaiba E. Silurian Na-K-Cl 45 800 1.0361 5.4 15 240 2460 182 1560 132 134 28 790 <10.0 12.0 0.00
E May-25-12 @ 16:00 Sarah Sarah L. Ord. - E. Silurian Na-Cl 41 140 1.0308 5.7 12 620 1830 196 2080 185 189 25 890 4.0 348 0.00
Produced water (major flowback of fracturing fluids or drilling fluids)
G Jul-10-09 Jubah Jubah M. - L. Devonian Na-K-Cl-HCO3 3210 1.0026 7.7 898 244 18 64 n.a. n.a. 1540 151 295 0.00
E* Jul-4-12 Qalibah U. QHS E. Silurian Na-Ca- 560 0.9996 7.0 69.3 19.4 4.16 42.2 0.257 1.41 35.2 102 307 0.00
HCO3-SO4-Cl
C* Jan-10-10 @ 13:30 Sarah Sarah L. Ord. - E. Silurian Ca-Na-Cl 213 300 1.161 5.1 17 770 611 75.0 66280 n.a. n.a. 128 100 381 726 0.00
C* Jan-10-10 @ 14:45 Sarah Sarah L. Ord. - E. Silurian Ca-Na-Cl 219 300 1.1702 5.1 15 270 635 82.0 72150 n.a. n.a. 130 900 339 622 0.00
C Jan-14-10 @ 00:00 Qasim L. QWRH L. Ordovician Na-K-Cl 32 040 1.0275 7.6 10 080 7480 47.0 239 n.a. n.a. 20 750 48.0 872 0.00
C Jan-21-10 @ 20:00 Qasim QWRH L. Ordovician K-Cl 22 560 1.0264 8.3 837 20770 97.0 52.0 n.a. n.a. 20 950 163 456 0.00
C Jan-22-10 @ 16:30 Qasim QWRH L. Ordovician K-Cl 8230 1.0101 7.9 346 8500 18.0 27.0 n.a. n.a. 7580 58.0 199 0.00
C Jan-28-10 @ 09:00 Qasim QWRH L. Ordovician Na-K-Cl 39 800 1.0368 7.0 11 310 10940 37.0 584 n.a. n.a. 26 470 188 1220 0.00
C Jan-31-10 @ 05:00 Qasim QWRH L. Ordovician Na-K-Cl 45 570 1.0376 8.2 13 230 6930 77.0 845 n.a. n.a. 30 180 <100 1140 0.00
C Feb-02-10 @ 07:00 Qasim QWRH L. Ordovician Na-K-Cl 53 290 1.0399 8.2 16940 5570 75.0 1020 n.a. n.a. 34 200 <100 950 0.00
C Jan-05-10 @ 21:00 Qasim Raan L. Ordovician K-Na-Cl 28 980 1.0314 7.1 5160 18 140 65.0 227 n.a. n.a. 22 580 125 824 0.00
C Jan-06-10 @ 03:00 Qasim Raan L. Ordovician K-Na-Cl 30 940 1.0307 7.6 6730 15 960 63.0 248 n.a. n.a. 22 990 100 811 0.00
C Dec-27-09 @ 09:35 Qasim L. KHFH M. Ordovician Na-K-Cl-SO4 34 400 1.0269 7.1 9960 6630 39.0 207 n.a. n.a. 20 910 2400 891 0.00
C Dec-27-09 @ 15:40 Qasim L. KHFH M. Ordovician Na-K-Cl 30 330 1.027 7.2 9570 6790 41.0 206 n.a. n.a. 19 510 <100 903 0.00
Fracturing fluids
C Jan-26-10 – – K-Cl 25 230 1.0331 7.8 770 24 620 125 57.0 n.a. n.a. 23 580 123 578 0.00
C Jan-26-10 – – K-Cl 22 090 1.0329 11.8 803 21 860 53.0 15.0 n.a. n.a. 19 930 127 0.00 1100
Completion brine
D Jan-30-11 – – Na-Cl 228 800 1.1571 9.9 90 030 161 37.0 66.0 <1 <1 134 900 2240 868 197
C* Oct-5-09 – – Ca-Cl 305 400 1.2174 5.9 4940 914 40.0 114100 n.a. n.a. 184 700 31.0 n.a. n.a.
C Dec-29-09 – – K-Cl 22 720 1.0284 7.7 858 19 100 116 298 n.a. n.a. 20 750 223 468 0.00
C Jan-23-10 – – K-Cl 18 080 1.0209 7.4 733 17 540 101 53.0 n.a. n.a. 16 570 132 486 0.00
Mud filtrates
D Jan-30-11 – – Na-Cl 55 890 1.0448 8.7 22 140 120 22.0 118 <1 <1 32 430 854 315 6.0
C Oct-5-09 – – Na-Ca-Cl 139 300 1.1134 8.0 34 260 314 21.0 26 170 n.a. n.a. 76 580 2250 n.a. n.a.
Geochemistry of fracturing fluids and Paleozoic formation water, Saudi Arabia

QWRH, Quwarah Formation; KHFH, Kahfah Formation; QHS, Qusaiba Hot Shale; n.a., not analyzed.Units: Density [g cm
3]; Elements [mg l
1].*Samples of semi-quantitative character by deviation >10% in ion
balance.
571
572 P. BIRKLE
Fig. 3. Logarithmic scale diagram of Na versus K (A) and Na versus Ca (B)
concentrations of produced water from Jubah, Qusaiba, Sarah, Quwarah
(QWRH), Raan (RAAN), and Kahfah (KHFH) reservoirs in the Northern
Exploration Area (Wells C to G) and the Arabian Gulf (Well H). Well loca-
tion is shown in Fig. 1. Pristine formation water is mainly composed of Na-
Cl type, but mixing with drilling and fracturing fluids of K-Cl (Trend ①)
and Ca-Cl (Trend ②) type causes the flowback of commingled produced
water (‘Produced water (Contaminated)’). Produced water samples with
low salinity seem to be mixed with supply water (Trend ③). Blue lines
show mixing trends of original formation water with drilling and hydraulic
fracturing-related fluids (Fracturing fluid, CaCl2 brine, KCl mud filtrate).
formation water with increasing portions of K-Cl-domi-
nated fracturing fluid or completion brine (‘KCl-type flu-
ids’ in Fig. 3A). Produced water from Sarah Formation
(Well E, red-framed square in Fig. 3A) and Jubah Forma-
tion (Well H, filled diamond) are slightly affected by dril-
ling fluids. In contrast, most samples from Raan (Well C,
brown-filled diamond in Fig. 3A), Kahfah (Well C, empty
diamond), and Quwarah (Well C, yellow-filled diamond)
are strongly mixed with low-saline, K-enriched drilling flu-
ids, as evidenced by K-Na-Cl to Na-K-Cl-SO4 dominance.
Two produced water samples from the Quwarah Forma-
tion (from January 21, 2010, and January 22, 2010) show
a complete flowback of completion brine (sample from
January 23, 2010), as evidenced by very similar Na (346–
837 mg l
1 vs. 733 mg l
1), Ca (27–52 mg l
1 vs.
53 mg l
1), K (8500–20 770 mg l
1 vs. 17 540 mg l
1),
and Cl (7580–20 950 mg l
1 vs. 16 570 mg l
1) compo-
sition for produced water and completion brine, respec-
tively. Depletion in Na, Ca, and K concentrations,
combined with enrichment in HCO3 and SO4, suggests
the commingled flowback of formation water with supply
water for Well G (Jubah Fm, half-filled diamond in
Fig. 3A) and for one specific samples from Well E (U.
Qusaiba Hot Shale, filled circle in Fig. 3) of Na-K-Cl-
HCO3 and Na-Ca-HCO3-SO4-Cl composition, respec-
tively (Trend ③ in Fig. 3A). A third sample group (‘CaCl-
type fluids’ in Fig. 3B) is affected by mixing with comple-
tion brine and mud filtrate of Ca-Cl type (Trend ② in
Fig. 3B). Chemical fingerprints of Ca-Cl-type produced
water from Well C (Sarah Fm, right-side filled square in
Fig. 3B), sampled on January 10, 2010, are almost identi-
cal to one completion brine (Ca-Cl type) and one mud fil-
trate samples (Na-Ca-Cl type), sampled from the same well
on October 5, 2009, and January 23, 2010, respectively
(Table 1), confirming the flowback of Ca-Cl-dominated
drilling fluids from Well C during that period.
Produced water from the Qusaiba Hot Shale (Well E,
filled circles in Fig. 3) is slightly affected by the partial
flowback of KCl, as evidenced by dominant Na-K-Cl-type
recovery. Produced water from the Jubah Formation in
off-shore Well H (filled diamond in Fig. 3) with a TDS
concentration of 74 740 mg l
1 shows the characteristic
Na-Cl composition of formation water, although elevated
SO4 and HCO3 concentrations suggest a minor impact by
atmospheric oxidation.
Well C represents a special case, as water samples were
obtained from different Paleozoic units and also end member
samples of completion brines (three samples between Octo-
ber 5, 2009, and January 23, 2010) and CaCl2 mud filtrates
(from October 5, 2009) from the drilling phase, and fractur-
ing fluids (from January 26, 2010) from the subsequent
hydraulic fracturing of the well. Representative Na-Cl-type
formation water with a TDS of about 129 000 mg l
1 was
recovered from Quwarah Formation on October 26, 2009,
while water samples from Quwarah, Raan, and Lower Kahfah
Formations from December 2009 to February 2010 were
affected by the return flow of injected KCl, as reflected by ele-
vated K concentrations between 5570 and 20 770 mg l
1.
This is in agreement with reference samples of completion
brine (from December 29, 2009, and January 23, 2010) with
© 2016 John Wiley & Sons Ltd, Geofluids, 16, 565–584
 Geochemistry of fracturing fluids and Paleozoic formation water, Saudi Arabia
potassium concentrations of 19 100 and 17 540 mg l
1,
respectively (Table 1). For the same Well C, Ca-Na-Cl-type
produced water from Sarah Formation (right-side filled
square in Fig. 3) with extreme Ca concentrations of 66 280–
72 150 mg l
1 (10 January 2009) is affected by the backflow
of CaCl2 completion brine, analyzed on October 5, 2009,
with a calcium concentration of 114 100 mg l
1 (empty-
crossed star in upper right corner of Fig. 3B). It is remarkable
that none of the Paleozoic formation water samples has an
extreme hypersaline composition, as salinity for formation
water from Middle Ordovician to Late Devonian reservoir
units ranges from close-to-seawater composition
(33 160 mg l
1) to an approximate fourfolded salinity
enrichment beyond seawater (129 300 mg l
1).
Geochemical Fingerprinting of Produced Water from
Qusaiba Hot Shale
Hydrochemical trends
Subsequently to the hydraulic fracturing stages of Qusaiba
Hot Shale in Well A, daily sampling of produced water
from December 30, 2012, to February 10, 2013, allowed
the temporal reconstruction of hydrochemical trends and
fluid types in the postfracturing period. The Piper Dia-
gram (Piper 1944) in Fig. 4 shows the temporary trend for
the relative abundance and variations of major cations (Na,
Fig. 4. Piper classification diagram with the
evolving chemical trend of produced water
from the Hot Qusaiba Shale fracturing project
during the time period from December 30,
2012, to February 10, 2013, as well as the
reference composition of KCl brine, supply
water, and fracturing fluid. The red line
shows the increasing production of formation
water during the postfracturing period.
© 2016 John Wiley & Sons Ltd, Geofluids, 16, 565–584
573
Ca, K) and anions (Cl, SO4, HCO3) for the involved water
types. The concentrations of major elements and TDS are
shown in Table 2. Between December 30, 2012, and Jan-
uary 6, 2013, total dissolved solids of produced water
increase from 11 770 to 29 960 mg l
1 with a trend from
a K-Cl water type via K-Na-Cl (on 01 January 2013)
toward a Na-Cl type (Fig. 4). Between January 07, 2013,
and February 10, 2013, produced water maintains a homo-
geneous chemical composition with a relatively small varia-
tion in TDS between 37 510 mg l
1 (January 10, 2013)
and 51 570 mg l
1 (February 9, 2013). Two outlier sam-
ples collected on January 5, 2013, and January 29, 2013,
are characterized by a K-Cl water type with extreme K con-
centrations ranging from 18 890 to 11 800 mg l
1.
The produced water from Well A is compared to
groundwater from the overlying Triassic Jilh aquifer, col-
lected from Well B (Fig. 1) located approximately 500 m
NW of the fracturing project and used as supply water for
the hydraulic fracturing of Well A. The low-saline ground-
water has a TDS concentration of about 1700 mg l
1 with
a Na-Ca-Cl-SO4-HCO3 to Na-Ca-Cl-HCO3-SO4 water
type. ‘Slickwater’ (‘Fracturing fluids’ in Fig. 4), used for
the hydraulic fracturing of Well A, is a mixture of Jilh sup-
ply water with chemical constituents of breaker, crosslin-
ker, and polymer, resulting in TDS of about 3500 mg l
1
and a Na-CO3-SO4-Cl to Na-B-Cl-SO4-CO3 water type
574 P. BIRKLE

Table 2 Analytical results from major elements and environmental isotopes for produced water from Well A (Qusaiba Hot Shale), supply water from
Well B (Jilh Formation), and prepared fluids for hydraulic fracturing.

Date TDS Na K Ca Br Cl SO4 HCO3 d2H d 2H

Well Formation [dd-m-yr] [mg l
1] [mg l
1] [mg l
1] [mg l
1] [mg l
1] [mg l
1] [mg l
1] [mg l
1] [&] 1r

Flowback from hydraulic fracturing

A QHS Dec-30-12 11 770 349 5050 128 45.7 5320 468 315
67.29 0.62
A QHS Dec-31-12 14 270 364 6290 139 63.4 6550 492 276
65.75 0.84
A QHS Jan-1-13 13 270 1990 3760 203 65 6150 430 550
61.24 1.26
A QHS Jan-2-13 18 860 5260 1740 391 131 10 190 213 789
59.43 0.43
A QHS Jan-3-13 18 580 5110 1680 363 130 10 060 213 885
A QHS Jan-5-13 38 890 550 18 890 127 360 18 110 392 352
68.68 0.95
A QHS Jan-6-13 29 960 9760 557 956 279 17 640 <100 502
50.66 0.40
A QHS Jan-7-13 41 860 13 580 525 1350 354 25 060 <100 583
42.62 1.04
A QHS Jan-10-13 37 510 12 330 540 1230 160 22 380 <100 550
45.71 0.86
A QHS Jan-11-13 42 210 13 940 590 1390 410 24 990 <100 468
A QHS Jan-12-13 42 660 14 110 560 1300 409 25 390 <100 497
41.56 0.79
A QHS Jan-13-13 42 670 14 960 690 1390 358 24 200 <100 673
A QHS Jan-16-13 46 110 18 280 480 1500 376 24 390 <100 656
42.27 2.01
A QHS Jan-18-13 39 150 15 730 436 1450 394 20 070 <100 657
41.01 0.10
A QHS Jan-20-13 46 980 17 600 429 1510 421 25 900 <100 691
40.66 0.51
A QHS Jan-22-13 44 530 16 510 425 1480 381 24 750 <100 572
39.94 2.11
A QHS Jan-24-13 44 900 16 000 412 1480 423 25 480 <100 684
41.05 0.43
A QHS Jan-29-13 24 240 519 11 800 191 143 10 710 318 420
68.79 0.88
A QHS Feb-6-13 49 400 17 380 377 1610 544 28 530 <100 473
39.72 1.12
A QHS Feb-7-13 50 700 18 520 391 1660 554 28 640 <100 440
A QHS Feb-8-13 50 070 18 400 377 1640 534 28 230 <100 414
A QHS Feb-9-13 51 570 19 210 382 1650 536 28 870 <100 439
Supply water for hydraulic fracturing†
B Jilh Feb-4-13 1850 296 53 173 <10 459 466 316
69.93 0.95
B Jilh Feb-3-13 1660 318 51 120 <10 466 313 321
70.25 2.70
†
Prepared fracturing fluid
B* Jilh Feb-14-3 3120 1360 57 35 <10 466 603 0
69.22 0.46
B‡ Jilh Feb-4-13 3490 1430 64 82 <10 470 604 0
71.12 0.88

l.c. no peak or low concentration. mm at ^ = million atoms. *Supply water from Well B + Breaker + Crosslinker. †Used for hydraulic fracturing of QHS
in Well A. ‡Supply water + Breaker + Crosslinker + GuarPolymer.

with elevated concentrations of B (143 mg l
1) and with
an alkaline pH value of 11.5. It can be concluded, that
flowback water from the first 7 days of postfracturing
(December 31, 2012, to January 06, 2013) is mainly com-
posed of fracturing fluid (supply water and KCl brine), and
became subsequently replaced by dominant pore water or
formation water in recovered samples from January 07,
2013, to February 10, 2013. Further discussions on hydro-
chemical trends of produced water from the presented frac-
turing project are shown in Birkle (2016).
The ratio of Br versus Cl is an ideal parameter for identi-
fying the origin of solutes, mixing and dilution of brines,
and various water–rock interaction processes without dia-
genetic alterations (Fig. 5). Low Cl/Br molar ratios of
115–155 for QSH formation water and 105 for Jilh forma-
tion water are remote from a global seawater composition
(Cl/Br ratio of 655  4) and are located outside of the
trajectory for evaporated seawater (SET). A salinity of
about 1700 mg l
1 suggests a meteoric origin for ground-
water from Jilh Formation, whereas the Br/Cl ratio and
average salinities of 46 000–50 000 mg l
1 for pore water
from Qusaiba Hot Shale can be reconstructed by mixing
about 84% of a dominantly meteoric water component
(assuming TDS of 1000 mg l
1), with a minor contribu-
tion of 16% of evaporated seawater. For the latter end
member, an initial salinity of 359 000 mg l
1 was assumed
for saturated conditions.
Environmental isotopes
Several environmental isotopes (2H, 13C, 18O, 37Cl,
87
Sr/86Sr) were analyzed to trace the origin of produced
water, recovered from the Qusaiba Hot Shale interval
during the post-fracturing period in Well A. Coherent
87
Sr/86Sr ratios of 0.70838 for the flowback water sam-
ple from December 30, 2012 (white circle in Fig. 6),
and 0.70859 for groundwater from the Jilh Formation
(green triangle in Fig. 6) confirm the dominance of Jilh
supply water on the ultimate day of postfracturing clean-
out, calculated to be 80% of the total return flow vol-
ume (Birkle 2016). In contrast, 87Sr/86Sr ratios of
0.71576 and 0.71651 from produced water on January
3, 2013, and February 8, 2013 (blue and violet circles
in Fig. 6), respectively, support the increasing dominance
of formation water cut after several day of postfracturing
backflow. On January 3, 2013, formation water con-
tributes with 28% to the total produced water volume,

© 2016 John Wiley & Sons Ltd, Geofluids, 16, 565–584

 Geochemistry of fracturing fluids and Paleozoic formation water, Saudi Arabia 575

d18OH2O 87
Sr/86Sr 3
H 14
CDIC
d18OSO4 d34SSO4 d37Cl d37Cl d13CDIC 36
Cl/Cl 36
Cl l
1
[&] 1r [&] [&] [&] 1r [2r] [T.U.] 1r [&] [pmC] 1r 9 [10-15] [mm at]^

8.55 0.05
0.49 0.07 0.70838 2E-05

8.31 0.02

8 0.07

7.99 0.02

0.62 0.13 0.71576 2E-05

8.94 0.07

7.18 0.02

6.13 0.01

6.53 0.10
l.c. l.c. <0.8 0.6
11.4 73.77 0.23

6.1 0.02
0.31 0.04 102 43 981
<0.8 0.6

6.03 0.03

5.98 0.02

5.89 0.01

5.87 0.11

5.89 0.01

9.19 0.01

5.77 0.01 l.c. l.c.

2.91 40.94 0.17

0.36 0.11 0.71651 3E-05 31 14 860
<0.8 0.6

9.46 0.02

9.52 0.03 11.8 16.52
0.22 0.03 0.70842 2E-05 <0.8 0.6
13.76 1.53 0.04 690 5460

8.66 0.02

9.19 0.02 10.75 6.98

with a trend toward a 100% invasion of formation water
on February 8, 2013, as derived by end member calcula-
tions.
Homogenous d37Cl ratios of
0.22& and
0.36& for
representative formation water samples from Jilh and QSH
(sample from 8 February 2013), respectively, indicate a
common salt source for both groundwater systems
(Fig. 7). Both values are close to present seawater (and
also to Jurassic seawater) composition of 0.0&. Depleted
d37Cl ratios of
0.49& and
0.62& for produced water
from December 30, 2012, and January 3, 2013, respec-
tively, suggest the partially flowback of injected KCl brine
with potentially depleted d37Cl concentrations. Approxi-
mately 4890 bbls of 5% KCl brine were used during the
postfrac cleanout of proppant (frac plugs) by coiled tubing
from December 23, 2012, to December 30, 2012 (Birkle
2016). Potassium concentrations and d37Cl ratios are
found to be inversely related. A minor contribution of 7
vol% to 20 vol% of KCl brine for January 3, 2013, and
December 30, 2012, samples, respectively, is responsible
for the negative shift of about 0.26& of d37Cl values. The
combination of both, 37Cl and 87Sr/86Sr methods, can be
used to distinguish between water from Qusaiba Hot Shale
and Jilh supply water, as well as to trace mixing contribu-
tions of drilling and fracturing fluids.
Figure 8 illustrates d2H and d18O ratios of produced
water from Qusaiba Hot Shale in comparison with supply
water (Jilh Formation), Global Meteoric Water Line
(GMWL; Craig 1961), and Eastern Mediterranean Mete-
oric Water Line (EMWL; Gat & Carmi 1970). The d18O
and d2H values of produced water from December 30,
2012, to December 31, 2012, are isotopically almost iden-
tical to supply water from the Jilh Formation. The contin-
uing positive trend of d18O and d2H values reflects the
increasing invasion of in situ fluids through the replace-
ment of fracturing fluid by formation water, reaching a
homogeneous isotopic plateau composition of formation
water (since January 7, 2013), potentially derived from
Qusaiba Hot Shale. The blue arrow in Fig. 8 demonstrates
the mixing trend from slickwater-dominated flowback sam-
ples (fracturing fluid) toward increased contributions of
primary formation water. The presence of a complex frac-
ture system is suggested by the irregular flowback of frac-
turing fluids, as evidenced by a peak volume of recovered
KCl brine on January 5, 2013, and January 29, 2013 (Bir-
kle 2016). An interpretation on the provenance of

© 2016 John Wiley & Sons Ltd, Geofluids, 16, 565–584

576 P. BIRKLE
Fig. 5. log Br vs. log Cl diagram with potential differentiation trends for
seawater through extreme evaporation (Seawater Evaporation trajec-
tory = SET), halite dissolution, or by mixing with other fluid types. The
chemical composition of Qusaiba Hot Shale formation water can be recon-
structed by mixing approximately 16% of evaporated seawater (approxi-
mately TDS = 350 000 mg l
1) with approximately 84% of meteoric water
(assumed TDS of 1700 mg l
1 from Jilh formation water).
formation water and potential mechanism for water–rock
interaction processes is given later in this study.
Geochemical Fingerprinting of Formation Water from
Qusaiba Hot Shale and Jilh Formation
Age dating with Carbon-14 (14C) and Tritium (3H)
Produced water samples, recovered after January 6, 2013,
from Well A, are considered to be representative for forma-
tion water or pore water from the hydraulically fractured
Fig. 7. Comparison of d37Cl and 87Sr/86Sr characteristics for produced
water from Qusaiba Hot Shale (QHS) and Jilh formation water.
Qusaiba interval, and therefore can be used to characterize
provenance and secondary alteration of Qusaiba formation
water. Radiocarbon dating is the leading tool in estimating
the age of paleo- and fossil groundwater up to a residence
time of about 60 000 years. The Conventional Radiocar-
bon Age BP (before present) is calculated using the radio-
carbon decay equation:
t ¼
8033 lnðAsn =Aon Þ
Where
8033 represents the mean lifetime of 14C (Stu-
iver & Pollach 1977). Aon is the activity in counts per min-
ute of the modern standard, Asn is the equivalent cpm for
the sample, and ‘ln’ represents the natural logarithm. Based
on the known half-life of carbon-14 of 5730  40 years, a
measured concentration of 40.94  0.17 pmC (percent
Fig. 6. Strontium concentrations and
87
Sr/86Sr ratios of produced water from
Qusaiba Hot Shale (Well A) from the
Northern Exploration Area, with reference
composition of supply water from the Triassic
Jilh aquifer (Well B). Also shown is the
strontium isotopic composition of global
seawater during the deposition of discussed
reservoir units (see legend for colored lines)
and Late Pleistocene-present seawater (Burke
et al. 1982), plus the upper limit of 87Sr/86Sr
values from interlayer strontium on smectite
clays (Chaudhuri & Clauer 1993).
© 2016 John Wiley & Sons Ltd, Geofluids, 16, 565–584
 Geochemistry of fracturing fluids and Paleozoic formation water, Saudi Arabia
modern Carbon) for a Well A water sample from Qusaiba
Hot Shale collected on February 7, 2013, can be converted
into a Conventional Radiocarbon Age (CRA) of
7174  41 years BP (years before present) (‘Model # 1’ in
Table 3). As the atmospheric concentration of 14C was fluc-
tuating in the past, a modification of Aon from present 100
pmC to averaged 110 pmC during Early Holocene (Clark
& Fritz 1997) resulted in a modified CRA age of
7940  33 years BP for the formation water sample from
Well A (‘Model # 2’ in Table 3). A further produced water
sample collected on January 11, 2013, resulted in even
higher 14C concentrations of 73.77  0.23 pmC, which
would result in a hypothetical residence time of
2444  25 years BP (Model #1) or 3209  25 years BP
(Model #2). The calculated age represents the combined
residence time of multiple fluid types within the groundwa-
ter system. As the volume portion of 16% for fossil brine
(see previous chapter ‘Hydrochemical trends’) is free of
14
C, the measured concentration of 40.94 pmC for the
produced water mixture must be derived from a meteoric
end member, which comprises 84 vol% of the total mix. A
resulting 14C concentration of 47.49  0.17 pmC implies
an average recharge and residence time in Early Holocene
between 5953  29 years BP (for Aon = 100 pmC) and
6747  29 years BP (for Aon = 110 pmC; Model #4 in
Table 3) for the meteoric end member. More enriched K
concentrations, but more depleted concentrations in Cl,
Mg, Sr, Ba, and Br (in comparison with February 7, 2013,
sample) could indicate a minor atmospheric input of CO2
for the January 11, 2013, water samples. d13C ratios
between
2.9& and
11.4& support an atmospheric
influence by young meteoric recharge.
In contrast, water from a supply well (‘Well B’) from the
overlying Jilh formation, which was used as the source for
Fig. 8. d18O and d2H ratios of produced
water from Qusaiba Hot Shale (QHS) in Well
A, in comparison with seawater, supply water
(Jilh Formation), Global Meteoric Water Line
(GMWL; Craig 1961), Eastern Mediterranean
Meteoric Water Line (EMWL; Gat & Carmi
1970), and Bahrain and Oman average
rainwater (Rizk & Alshahran 1999). *
Meteoric water mixed with evaporated
seawater.
© 2016 John Wiley & Sons Ltd, Geofluids, 16, 565–584
577
slickwater associated with the hydraulic fracturing project
at ‘Exploration Well A’, resulted in depleted 14C activities
of 1.53  0.04 pmC with a calculated CRA residence time
of 33 577  182 years BP. Considering a higher atmo-
spheric concentration of 14C during Late Pleistocene (125
pmC at 32 000 years BP; Barbetti 1980), as well as an
average correction factor q of 0.65–0.75 due to potential
dilution effects by ‘dead carbon’ in carbonate–karst systems
(Vogel 1970), the derived absolute residence time varies
between 24 759  127 (considering atmospheric varia-
tions & dead carbon effect) and 35 370  182 years BP
(considering exclusively Late Pleistocene atmospheric varia-
tions) for Jilh formation water (Model #3 in Table 3).
Independently of applied correction factors, surface water
infiltrated into the Qusaiba Hot Shale and Jilh reservoirs
during Early Holocene and Late Pleistocene time period,
respectively. The shorter residence time for Qusaiba Hot
Shale fluids in comparison with Jilh groundwater indicates
a more dynamic fluid migration and laterally directed
recharge for the Qusaiba Hot Shale system in comparison
with Jilh fluids. Although the Jilh Formation consists par-
tially of carbonates, the relatively depleted d13C ratio of

13.76& suggests surface recharge as major process with
minor fluid alteration by carbon dissolution. Tritium con-
centrations for Qusaiba Hot Shale produced water and Jilh
supply water resulted to be below the detection limit of
0.8 T.U. (Tritium Units) (Table 3), confirming a prebomb
residence time for groundwater, which must have been
recharged prior to 1952. Negligible tritium concentrations
also confirm the absence of anthropogenic or atmospheric
contamination of the recovered samples. The reported
short residence times for Qusaiba and Jilh groundwater
coincide with growing evidences for fluid and solute trans-
port in intracratonic basins on small timescales (thousands
 578 P. BIRKLE

(Aon = 110 pmC,

of years) driven by continental glaciation, especially during

Asn = 47.49 
Pleistocene (McIntosh et al. 2011).

0.17 pmC)
6747  29
Model #4
Origin of recharge with Chlorine-36 (36Cl)

n.a.

n.a.
The long half-life of 301 000 years of 36Cl makes chlo-
rine-36 an applicable tool for dating old groundwater up
to 2 million years. 36Cl is naturally produced by cosmic ray

(Aon = 125 pmC,

24,759  127
interaction within the atmosphere (cosmogene) and at near
surface (epigene), and to a lesser degree by neutron activa-
Model #3

q = 0.7)
tion of 35Cl in the subsurface (hypogene). Additionally,
n.a.

n.a.

the subsurface distribution of 36Cl can be altered by evapo-

ration, transpiration, biological uptake, dissolution of
halite, weathering release of 36Cl from minerals, seawater
(Aon = 110 pmC)

(Aon = 125 pmC)

(Aon = 125 pmC)

intrusions, aquitard infiltration, differential transport

35,370  182
C) and modeled residence time for produced water from Qusaiba Hot Shale (Well A) and Jilh Formation (Well B).

7940  33

3209  25

through fast and slow paths, and mixing with high-salinity

Model #2

aquifers (Phillips et al. 1986). Pre-anthropogenic seawater

is characterized by low 36Cl/Cl ratios of 0.3 9 10
15,
C Residence time [yr BP]

whereas meteoric 36Cl/Cl ratios in aquifer recharge vary

between <20 9 10
15 close to ocean and 100 9 10
15 –
(Aon = 100 pmC)

(Aon = 100 pmC)

(Aon = 100 pmC)

1000 9 10
15 in continental interior settings. The mea-

33,577  182

sured 36Cl/Cl secular equilibrium for hypogene produc-

7174  41

2444  25
Model #1

tion varies between 5 9 10
15 and 30 9 10
15 for most

rocks with an average ratio of 5 9 10
15 for most mud-
14

stones and sandstones (Fabryka-Martin et al. 1987).

Two representative formation water samples from
73.77  0.23

Qusaiba Hot Shale at Well A, collected on January 12,

1.53  0.17

2013, and February 8, 2013, show a relatively homoge-

 0.17
[pmC]

40.94

neous range of 36Cl/Cl ratios of 102 9 10
15 and

C
14

31 9 10
15, respectively, suggesting a dominantly mete-

oric origin of the fluids, as evidenced by Br/Cl ratios
(Fig. 5) and lower 36Cl/Cl ratios of 0.3 9 10
15 for sea-
Residence

[yr BP]

water. The sample collected on 12 January 2013 is by vol-

time

>60

>60
n.a.
H

ume enriched in 36Cl in comparison with the February 8,

3

2013, sample (43 981 million atoms of 36Cl l
1 vs.

14 860 million atoms of 36Cl l
1), but lower TDS concen-
[T.U.]

 0.6

 0.6
<0.8

<0.8

trations (42 660 mg l
1 vs. 50 070 mg l
1) exclude evap-

n.a.
H
3

otranspiration as major process to explain the observed

salinity of Qusaiba Hot Shale samples. Radioactive decay
01/13/3013*
01/11/2013*

02/07/2013†

and subsurface production of 36Cl, as generally character-

11-01-2013

03-02-2013

ized by decreasing and increasing 36Cl/Cl ratios and 36Cl

concentrations, respectively, and stable Cl
values, seems
Date

to represent nonrelevant formation processes for ground-

C sampling.

water in Qusaiba Hot Shale. On the other hand, enriched

14

Hot Shale

Hot Shale

U and Th concentrations of 14.7–46.2 ppm and 3.4–

Formation
Table 3 Radiometric concentrations (3H,

Qusaiba

Qusaiba

12.1 ppm, respectively, analyzed on QHS drilling cuttings

14
Jilh

from Well A (internal report) could generate an elevated

*Date for 3H sampling. †Date for

neutron flux with a potential subsurface production of

36
Cl. Additionally, the mixing of two end members
Sample type

(young, 36Cl
enriched meteoric water and old, 36Cl
de-

Formation

Formation

pleted seawater) can cause an apparent decrease in 36Cl/Cl

water

water

water
Supply

ratios that might otherwise be attributed to simple decay

(Fontes & Andrews 1994). Additional chlorine isotope
studies should be performed on a regional scale for QHS
Well

formation water to develop a two-dimensional numerical

A

© 2016 John Wiley & Sons Ltd, Geofluids, 16, 565–584

 Geochemistry of fracturing fluids and Paleozoic formation water, Saudi Arabia 579

hydrodynamic model with decreasing 36Cl/Cl ratios and

increasing residence times along the flowpath, as evidenced
for deep groundwater of the Nubian Aquifer of the Wes-
tern Desert in Egypt (Patterson et al. 2005).
In contrast, groundwater from the Jilh Formation (Well
B) is extremely enriched in 36Cl/Cl (690 9 10
15), which
is likely to represent the primary cosmogenic production of
36
Cl during the recharging period in Late Pleistocene.
Assuming a relatively homogeneous 36Cl/Cl trend for the
atmospheric input from present period to Late Pleistocene,
elevated 36Cl/Cl ratios of 690 9 10
15 for Jilh groundwa-
ter could also imply a proximate location to a continental
recharge setting remote from the ocean. This interpreta-
tion agrees with the geographic location of the study area
and also with present 36Cl/Cl ratios of shallow groundwa-
ter from USA, where an increase from 20 9 10
15 in
coastal areas (S-Florida, NW-Washington State) toward val-
ues exceeding 640 9 10
15 in the continental Midwest
was observed (Bentley et al. 1986). In comparison, 36Cl
isotopic data from three water samples from a gas producer
well in the Southern Ghawar Production Area (Well I in
Fig. 1), recovered from the Silurian Sarah Formation,
underlying Qusaiba Hot Shale, are illustrated in Fig. 9. A
linear trend between 36Cl/Cl ratios, total Cl (Fig. 9B),
and 36Cl l
1 concentrations (Fig. 9A) indicates the effect
of evapotranspiration as principal process to explain the
hypersaline water composition (TDS = 265–426 g l
1)
from Sarah Formation in the Southern Ghawar area. Sub-
aerial evaporation of seawater is also reported to be the
dominant mechanism to originate hypersaline, d18O-
enriched brine in the Upper Permian—Lower Triassic
Khuff Formation and Upper Carboniferous—Lower Per-
mian Unayzah Group (Birkle et al. 2013). The nonlinear
trend between 36Cl/Cl ratios and 14C concentrations con-
firms independent interpretations for the provenance
mechanisms of both radioactive isotopes:
Fig. 9. Correlation of 36Cl concentration vs. 36Cl/Cl ratio (Fig. 9A), Cl vs.
(1) In the case of Jilh formation water (water supply from 36
Cl concentration (Fig. 9B) of produced water from Qusaiba Hot Shale (Well
Well B), 14C age dating suggests a time period around A: filled circles) in comparison with groundwater from Jilh (Well B: filled trian-
25 000 years BP (Late Pleistocene) as a major recharge gle) and Sarah (Well I: open square) Formation, standard meteoric water, and
vent for the infiltration of meteoric water into the Jilh seawater composition. Shown are also evolutionary trends for radioactive
decay, subsurface production, and evapotranspiration as potential processes
reservoir. This is in agreement with the reported Late
to reconstruct the provenance and evolution of formation water.
Pleistocene Pluvial period from 35 000 to
19 000 years BP for Rub’ al-Khali in Southern Saudi
Arabia (McClure 1976) and Nizwa area in Oman of 6000 to 6700 years BP for the meteoric component
(Clark & Fontes 1990) with documented savannah of the February 8, 2013, sample is in agreement with
grassland and deciduous vegetation, respectively. Ele- the onset of an Early Holocene Pluvial period of
vated 36Cl/Cl ratios (690 9 10
15) suggest an inland enhanced humidity (from 12 500 to 6100 years BP),
continental location of the recharge area during Late as described for the Oman region (Clark & Fontes
Pleistocene with a minimum distance of several hun- 1990). Also, the time period from 12 000 to
dreds of kilometers from the coast. 6000 years BP is characterized by the flooding of the
(2) For formation water from Qusaiba Hot Shale, elevated Arabian Gulf basin by the Indian Ocean, causing rising
14
C concentrations (41–74 pmC) indicate recharge of sea levels and the establishment of marine conditions
the groundwater system by low-saline meteoric water with the Gulf (Stoffers & Ross 1979). Lower 36Cl/Cl
during Early Holocene. The calculated residence time ratios for formation water from Qusaiba Hot Shale

© 2016 John Wiley & Sons Ltd, Geofluids, 16, 565–584

580 P. BIRKLE
(31 9 10
15 – 102 9 10
15) in comparison with Jilh
(690 9 10
15) could suggest enhanced events of mar-
ine transgression during Early Holocene, lowering the
36
Cl/Cl ratio by a closer location of the recharge area
to the ocean by sea spray effects. Furthermore, the
mixing of 36Cl-depleted, evaporated seawater (16 vol%)
with a 36Cl-enriched Quaternary meteoric water com-
ponent (84 vol%) or, as a second option, the hypogene
production of 36Cl by U-Th-enriched mudstone from
the Qusaiba host rock could also reproduce the
detected 36Cl/Cl ratios of QHS formation water.
DISCUSSION
Paleoclimate and provenance of formation water
d18O and d2H formation water values from both, the Jilh
and from Qusaiba Hot Shale, are close to the present Glo-
bal Meteoric Water Line (GMWL), which suggests mete-
oric water as their primary component (Fig. 8). None of
the groundwater samples show geochemical patterns of
recent regional meteoric water, as shown by its relative dis-
tance from the Eastern Mediterranean Meteoric Water Line
(EMWL) and average recent Bahrain and Oman rainwater
composition (Rizk & Alshahran 1999), which indicates dif-
ferent climatic conditions during the infiltration of surface
water into the reservoir. Extremely depleted d18O
(
9.5&) and d2H (
70&) ratios for Jilh formation water
indicate the infiltration of low-saline, paleo-meteoric water
during cooler climatic conditions than present. Carbon-14
dating confirms a Late Pleistocene period (25 000–
35 000 years BP) for the recharge event. In contrast, an
intermediate salinity (TDS = 50 000 mg l
1), higher d18O
and d2H ratios (
5.8& and
40&, respectively), and a
more recent average 14C residence time (7000–8000 years
BP) for formation water from the Qusaiba Formation con-
firm the presence of two water types (minor fraction of
evaporated seawater and meteoric water), whereby the lat-
ter one recharged the Qusaiba Hot Shale and/or adjacent
units during warmer climatic conditions in Early Holocene
(compared to Late Pleistocene). It is of interest that dis-
tinct residence times for meteoric water from Jilh
(25 000–35 000 years BP) and Qusaiba (6000–6700 years
BP) coincide with two major wet periods in Southern Ara-
bia during Late Pleistocene and Early Holocene. Radiocar-
bon dating on travertine and fracture calcite from
Northern Oman (Clark & Fontes 1990) confirmed the
presence of wet conditions through a Late Pleistocene plu-
vial phase from 35 000 to 19 000 years BP. Climatic dete-
riorations caused a period of hyperaridity in Latest
Pleistocene from approximately 16 300 to 13 000 years
BP, characterized by the desiccation of previously extensive
lakes in Northern Oman (Clark & Fontes 1990) and by
the deposition of red eolian sand in the Rub’ al-Khali by
17 000 years BP (McClure 1976). An Early Holocene
renewal of pluvial climatic conditions is evidenced by spe-
leothem records from stalagmites (10 500–6300 years BP;
Fleitmann & Matter 2009) and travertine (12 500–
6500 years BP; Clark & Fontes 1990) in Northern Oman.
Aquifer studies by the Ministry of Agriculture and Water
indicate that the meteoric water recharge during the Pleis-
tocene–Holocene has differentially flushed the aquifers
(Edgell 1997). In the vicinity of the Ghawar field (Eastern
Saudi Arabia), the flushing with Pleistocene–Holocene
meteoric water has reached a maximum depth of 7000 ft
(2130 m; Stenger et al. 2003), or even 8000 ft (2440 m),
as evidenced by low-salinity water in the Jurassic Arab-D
and Late Carboniferous-Early Permian Unayzah aquifers
(Al-Mahmoud 2015). Below a depth of 10 000 ft
(3050 m), the homogeneous column of hypersaline brine
indicates the presence of connate water, supersaturated
with salts (Al-Mahmoud 2015). As an analogue case for
recent flow migration, the probable mixing of surface
water with residual brines during Tertiary or Quaternary
period was reported for Paleozoic formations from oil and
gas wells in Western Pennsylvania (Dresel & Rose 2010).
Low salinities, depleted stable isotope ratios and young
14
C apparent ages for Jilh and Qusaiba Hot Shale waters
imply the infiltration of paleo-meteoric water during the
Late Pleistocene Pluvial Period (from 35 000 to
19 000 years BP) and Early Holocene Pluvial Period
(12 500–6300 years BP), respectively, under cooler and
more humid climatic conditions as present. A trend toward
slightly warmer climatic conditions from Late Pleistocene
(Circle ‘1’ in Fig. 8) toward Early Holocene (Circle ‘2’ in
Fig. 8) is reflected by increasing d18O and d2H ratios
between both recharge events. Meteoric water from pre-
sent-day, hot-arid climatic conditions (Circle ‘3’ in Fig. 8)
is distinctively enriched in stable isotopes, as reflected by
current rainwater composition from Bahrain and Oman
(Rizk & Alshahran 1999).
Origin of sulfates
The principal sources of sulfate in formation waters are dis-
solved marine sulfate, sulfate derived from the dissolution
of evaporites, and sulfate formed by the oxidation of sul-
fides. Present-day marine SO4 has isotopic ratios of
d34SCDT and d18OSMOW of 20.0& and 9.45&, respectively
(Longinelli 1989). Sulfate-reducing bacteria (SRB) causes
the incorporation of light sulfide into pyrite, and an
enrichment of aqueous SO4 populations (in seawater) in
34
S (Dworkin & Land 1996). d18OSMOW in sulfates are
also affected, but only one-quarter of the amount that S
experience (Holser et al. 1979). For temperatures above
90°C, thermally mediated SO4 reduction (TSR) causes a
residual SO4 population enriched in heavy S, but with
probable less fractionation on O isotopes. Temperatures
© 2016 John Wiley & Sons Ltd, Geofluids, 16, 565–584
 Geochemistry of fracturing fluids and Paleozoic formation water, Saudi Arabia
above 110 and 140°C are required for the formation of
H2S by TSR of sulfate minerals for oil (Worden & Carri-
gan 2005) and gas (Worden et al. 1995) reservoirs, respec-
tively.
In the case of produced water from Qusaiba Hot Shale
(Well A), concentrations of SO2
4 were too low
(<100 mg l
1) to analyze them for sulfur isotopes, which
can be ascribed to its low primary abundance in infiltrating
meteoric water, and/or the destruction of SO4 by anaero-
bic bacteria or thermochemical sulfate reduction. Figure 10
shows the abundance of d34SCDT and d18OSMOW for SO2
4 (640 mg l
1 vs. 0.0 mg l
1), but depleted in Ca
in a groundwater sample from the Jilh Formation (Well B,
3 February 2013) in comparison with global reference
composition of atmospheric SO4, terrestrial evaporites, and
modern, Cenozoic and Tertiary marine SO4 (Longinelli
1989; Clark & Fritz 1997). Isotopic fractionation by TSR
can be excluded as groundwater temperatures are below
40°C. As shown by Krouse (1977), SRB appears to be vol-
umetrically insignificant at depth below 2200 m and all
H2S is thermochemical. More likely, SRB depleted dis-
solved sulfates of the Jilh groundwater to a remnant SO2
4
concentration of around 300 mg l
1 and produced rela-
tively enriched d34SCDT and d18OSMOW values of +16.5&
and +11.8&, respectively (blue arrow in Fig. 10). The low
salinity (TDS = 1850 mg l
1), the presence of 14CDIC
(1.53  0.035 pmC), and depleted d13C ratios
(
13.76&) of Jilh groundwater confirm the recent atmo-
spheric input of sulfates and carbonates by the late
Fig. 10. Correlation between d18OSO4 and d34SSO4 for supply water from
Jilh Formation (Well B, filled triangle) and fracturing fluids (used in Well A,
filled star) in comparison with atmospheric SO4, terrestrial evaporites, and
modern, Cenozoic and Tertiary marine SO4 (Longinelli 1989; Clark & Fritz
1997).
© 2016 John Wiley & Sons Ltd, Geofluids, 16, 565–584
581
Pleistocene recharge of meteoric water. The depleted
d34SCDT value of fracturing fluid (+6.98&, green-filled star
in Fig. 10), which was applied for the hydraulic fracturing
of Qusaiba Hot Shale in Well A, is probably caused by the
mixing of the supply water component, composed of Jilh
groundwater, with isotopically depleted terrestrial evapor-
ites or chemical agents (red arrows in Fig. 10). In compar-
ison with supply water, fracturing fluid is enriched in Na
(1430 mg l
1 vs. 318 mg l
1), B (143 mg l
1 vs.
<10 mg l
1), SO4 (603 mg l
1 vs. 313 mg l
1), and CO3
(82 mg l
1 vs. 120 mg l
1) and HCO3 (0.0 mg l
1 vs.
321 mg l
1).
Secondary water–rock interaction
Low Cl/Br molar ratios of 115–155 for produced water
from Qusaiba Hot Shale and 105 for Jilh formation water
confirm the evolution of water salinity independently from
halite dissolution (e.g. from adjacent salt domes), as the
latter process would cause enrichment in Cl in comparison
with Br (Fig. 5). Also, salt dissolution from salt residuals
within the Qusaiba Hot Shale during the fracturing process
can be excluded to explain the increasing salinity accumula-
tion in produced water, as the stable plateau composition
after 1 week of postfracturing fluids indicates little impact
of ion leaching by diffusion processes. The inflow and mix-
ing of formation water or connate water with fracturing
fluids generates a faster rise in return water salinity than
leaching of minerals by fracturing water. This interpreta-
tion is in agreement with time-series of produced water
from Marcellus Shale wells, where major and trace elemen-
tal concentrations, combined with oxygen and hydrogen
isotope ratios, confirmed the progressive mixing and
replacement of injected water by formation water (Rowan
et al. 2015). Earlier experiments with drilling cuttings and
cores suggested dissolution of autochthonous salts—be-
sides the mobilization of hypersaline connate fluids—as a
major ion source in the produced water of some wells
(Blauch et al. 2009; Blauch 2011).
With strontium concentrations of 80 and 110 mg l
1
and radiogenic strontium ratios of 0.71576 and 0.71651,
respectively, a mixed flowback water sample (3 January
2013) and a representative formation water sample (8
February 2013) from Qusaiba Hot Shale are enriched in
comparison with Late Pleistocene to present seawater
(Sr = 8 mg l
1, 87Sr/86Sr = 0.709199, Burke et al. 1982),
but also elevated in comparison with 87Sr/86Sr ratios of
0.7078 to 0.7080 for average seawater during the deposi-
tion of the Qusaiba Hot Shale in Early Silurian (435–
439 m.y., Llandoverian) or to maximum 87Sr/86 ratios of
0.709180 for global seawater in Earth history (McArthur
et al. 2001) (Fig. 6). As a Late Pleistocene origin was
determined for the infiltration event of surface water into
582 P. BIRKLE
the reservoir (see section ‘Age dating with Carbon-14
(14C) and Tritium (3H)’), the alteration of primary
87
Sr/86Sr seawater ratios must have been caused by sec-
ondary water-rock alteration processes. The present enrich-
ment of radiogenic strontium may be due to reaction with
micas and feldspars or from the interlayer position of smec-
tite clays. Leaching studies on smectite clay minerals have
demonstrated that interlayer Sr can have 87Sr/86Sr values
up to 0.7220 (Chaudhuri & Clauer 1993). Within the lim-
itations of the current data set, especially due to the lack of
radiogenic fingerprints for the Qusaiba Shale host rock,
87
Sr/86Sr values of produced water may be interpreted as
being interlayer strontium expelled into solution during
smectite diagenesis. The presence of unusual K-rich ter-
rains within the Qusaiba Shale unit may have caused the
enhanced leaching of strontium from biotite and K-feld-
spars under relatively low-temperature conditions (approxi-
mately 100°C) with 87Sr/86Sr ratios between 0.71576 and
0.71651. Similar geochemical reactions are reported for
the Marcellus Shale, where clay–water reactions contribute
radiogenic Sr to flowback and produced water (Chapman
et al. 2012; Warner et al. 2012). Intermediate 87Sr/86Sr
ratios of 0.71000 to 0.71212 for produced water from the
Marcellus Shale (Warner et al. 2012) are reconstructed by
the diffusion of Silurian brine from the underlying Salina
Formation (87Sr/86Sr = 0.7083; McArthur & Howarth
2004) and subsequent interaction with radiogenic Marcel-
lus Shale (87Sr/86Sr = 0.730; Balashov et al. 2015).
In contrast, 87Sr/86Sr values of 0.70842 for groundwa-
ter from the Late Triassic Jilh Formation are within the
range of Carnian seawater (0.70772–0.70848, McArthur
et al. 2001), but are slightly deviated from the primary sea-
water composition during Early Holocene (0.0709199).
Significant differences in 87Sr/86Sr between representative
formation water from Qusaiba Hot Shale
(0.71576  0.00002 to 0.71651  0.00003) and Jilh
Formation (0.70842  0.00002) suggest the lacking of
hydraulic connectivity between Qusaiba Hot Shale and the
Triassic Jilh aquifer in the Northern Arabian Exploration
Area, as both are isolated by a more than 3000 ft (910 m)
thick lithological column of impermeable mudstone from
the Qusaiba Member. Isotopic-chemical fingerprinting
reconfirms the provenance of produced water from the
Qusaiba Hot Shale or from the underlying Sarah sand-
stone, which were recovered during the postfracturing per-
iod in Well A (Birkle 2016).
CONCLUSIONS
Hydrochemical monitoring of produced water from
hydraulic fracturing can provide clues regarding source and
origin of ions picked up during the fracturing process, but
an interdisciplinary combination of multi-isotope tech-
niques can contribute quantitative solutions on the
provenance and type of recovered fluids, location of
recharge zones, residence times, migration flowpaths, and
secondary alteration processes. The relative enrichment of
flowback water in specific elements (i.e. K, B, HCO3, and
Ca), as well as depleted elemental concentrations (i.e. Ba,
Br, I, Li, Sr) and ratios (i.e. Mg/Ca, Cl/K) can generally
be attributed to a recovery of different types of anthro-
pogenic fluid types from drilling or hydraulic fracturing.
In the present case of hydraulic fracturing of Early Sil-
urian Qusaiba Hot Shale, changes in the salinity of pro-
duced water seem not be related to dissolution processes
between fracturing fluid and newly formed hydraulic frac-
tures, but due to the inflow and mixing with higher saline
formation or pore water, as evidenced by low Cl/Br ratios
and isotopic fingerprints. In particular, radiogenic stron-
tium (87Sr/86Sr) and d2H-d18O techniques resulted in
being a quantitative tool used to distinguish between pro-
duced water from Qusaiba Hot Shale and groundwater
from the Triassic Jilh Formation, the later one used as sup-
ply water for the hydraulic fracturing of the first one. The
inflow of formation water into the stimulated Qusaiba
horizon may originate by the natural occurrence of mobile
pore water within a naturally fractured, black shale hori-
zon. A further feasible option is the rise of groundwater
from adjacent units, such as from the underlying Sarah
sandstones, via migration pathways of newly formed, verti-
cally induced hydraulic fractures. The potential inflow from
shallow groundwater systems can be excluded due to the
lack of genetic affinities between compared fluids. Ongoing
research on isotopic fingerprinting of formation water from
different reservoir units adjacent to the Qusaiba Hot Shale
is aimed at distinguishing in situ water types from
allochthonous groundwater sources.
Additional leaching experiments with subsurface cores or
cuttings could rule in or out the possibility of dissolution
processes of indigenous autochthonous salt as a thermo-
chemical mechanism to explain the observed salinity in
produced water. The monitoring of d37Cl ratios from local
meteoric water sources and potential salt layers and domes
could provide additional hints to reconstruct the prove-
nance of dissolved salt in formation water.
ACKNOWLEDGEMENTS
The author is grateful to Saudi Aramco for granting per-
mission to publish the results of this study and to the
EXPEC Advanced Research Center, especially to Waleed
A. Mulhim, Samer S. Ashgar, and Maher I. Al Marhoon,
for continuous research support. The author acknowledges
the project assignment and logistical support from the
Unconventional Resource Exploration Development
Department, namely to Brian E. Gratto, Hafiz J. Sham-
mery, Ahmed M. Hakami, Brian D. Coffin, and Kirk M.
Bartko, to perform the current study. Thanks to Ian A.
© 2016 John Wiley & Sons Ltd, Geofluids, 16, 565–584
 Geochemistry of fracturing fluids and Paleozoic formation water, Saudi Arabia
Gillis, Kirk M. Bartko, Serguey V. Arkadakskiy, Paul G.
Nicholson, Peter D. Jenden, Shaun Hayton, and Stephen
G. Cheshire (all Saudi Aramco) for constructive comments.
Technical support is acknowledged to Saleh Al-Sharidi and
Mossaed Al-Fahad from the Chemistry Analysis Unit for
hydrochemical analysis, Peter D. Jenden, Feng Lu, and Jaf-
far M. Dubaisi from the Geochemistry Unit (both Saudi
Aramco) for stable isotope analysis, to Ian D. Clark from
the University of Ottawa with collaborating laboratories
for multi-isotopic analysis and constructive technical dis-
cussions, and to Mohamed Rashed and Daniel Kalinin
from Schlumberger for providing fracturing fluid. Graphi-
cal support on maps is acknowledged to the Visual Solu-
tions Unit (CartoGraphy, Aramco). We appreciate the
editorial handling of the manuscript by Richard Worden
and Guiseppe Etiope, and the constructive review com-
ments from two anonymous reviewers.
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gfl_16_3_Issue_Toc_GFL 22-07-2016 11:52 Page 1

Geofluids
Volume 16, Number 3, August 2016
ISSN 1468-8115

CONTENTS
367 Effective gas permeability of Tight Gas Sandstones as a function of capillary pressure – a non-steady-state approach
A. Amann-Hildenbrand, J.P. Dietrichs and B.M. Krooss
384 Evaluation of recoverable energy potential from enhanced geothermal systems: a sensitivity analysis in a poro-thermo-elastic
framework
N. Gholizadeh Doonechaly, R. Abdel Azim and S.S. Rahman
396 Evolution of the transport properties of fractures subject to thermally and mechanically activated mineral alteration and
redistribution
I. Faoro, D. Elsworth and T. Candela
408 Low-temperature dunite hydration: evaluating CH4 and H2 production from H2O and CO2
A. Neubeck, D.T. Nguyen and G. Etiope
421 Fluid mapping in deeply buried Ordovician paleokarst reservoirs in the Tarim Basin, western China
Y.Y. Zhang, Z.D. Sun, J.F. Han, H.Y. Wang and C.Y. Fan
434 Earthquake-related temperature changes in two neighboring hot springs at Xiangcheng, China
Y. Ma
440 The salt chimney effect: delay of thermal evolution of deep hydrocarbon source rocks due to high thermal conductivity of
evaporites
Q.G. Zhuo, F.W. Meng, M.J. Zhao, Y. Li, X.S. Lu and P. Ni
452 Modeling earthquake effects on groundwater levels: evidences from the 2012 Emilia earthquake (Italy)
M. Nespoli, M. Todesco, E. Serpelloni, M.E. Belardinelli, M. Bonafede, M. Marcaccio, A.P. Rinaldi, L. Anderlini and
A. Gualandi
464 Capillary seal capacity of faults under hydrodynamic conditions
J. Underschultz and J. Strand
476 Modeling of hydrogen production by serpentinization in ultramafic-hosted hydrothermal systems: application to the
Rainbow field
C. Mügler, P. Jean-Baptiste, F. Perez and J.L. Charlou
490 A fluid inclusion record of magmatic/hydrothermal pulses in acid Salar Ignorado gypsum, northern Chile
F.J. Karmanocky III and K.C. Benison
507 Controls on fluid movement in crustal lithologies: evidence from zircon in metaconglomerates from Shetland
T.J. Dempster and F. Macdonald
518 Freezing and melting behaviors of H2O-NaCl-CaCl2 solutions in fused silica capillaries and glass-sandwiched films:
implications for fluid inclusion studies
H. Chu, G. Chi and I.-M. Chou
533 Stress-dependent transport properties of fractured arkosic sandstone
M.E. French, F.M. Chester, J.S. Chester and J.E. Wilson
552 Cyclic loading of an idealized clay-filled fault: comparing hydraulic flow in two clay gouges
R.J. Cuss, C.C. Graham, A.C. Wiseall and J.F. Harrington
565 Geochemical fingerprinting of hydraulic fracturing fluids from Qusaiba Hot Shale and formation water from Paleozoic
petroleum systems, Saudi Arabia
P. Birkle
585 Effect of salinity on mass and energy transport by hydrothermal fluids based on the physical and thermodynamic
properties of H2O-NaCl
Yu.I. Klyukin, T. Driesner, M. Steele-MacInnis, R.P. Lowell and R.J. Bodnar
604 Long-term chemical evolution and modification of continental basement brines – a field study from the Schwarzwald,
SW Germany
B.F. Walter, M. Burisch and G. Markl
624 A comprehensive review of hydrocarbons and genetic model of the sandstone-hosted Dongsheng uranium deposit, Ordos
Basin, China
B.F. Cao, G.P. Bai, K.X. Zhang, L.K. Zhang and B. He
651 Book Review

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