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MASTER OF SCIENCE
in
(Geological Sciences)
(Vancouver)
December 2017
being developed in Canada. The flowback water from 31 wells located on 9 well pads was
sampled over time and analyzed for major ions, key minor ions, and δ 18O and δ2H isotopes. The
injected hydraulic fracturing fluids and produced waters, if available, were analyzed for the same
parameters. The results of the study are used to compare the flowback water chemistry between
wells and investigate the variables that have a significant influence on the chemistry. When
comparing the flowback water chemistry between multiple wells, consideration must be given to
the length of the flowback period, as the major ion concentrations typically increase over time.
The dominant influence on the increasing concentrations is mixing between hydraulic fracturing
fluid and formation water. Cl and stable water isotopes were used as conservative tracers to
calculate the increasing proportions of formation water. These proportions were used with
geochemical models to determine that mixing explains the Na and K concentrations, while
mixing with ion exchange is influencing Ca, Mg, and Sr concentrations. Sulfate concentrations
are influenced by pyrite oxidation and sulfate reduction. The rate of increase of the major ions
varies between wells, although it is often, but not always, similar between wells completed at the
same site, due to similarities in reservoir properties and well completion. The inconsistency is
due to the many variables that may impact the flowback water chemistry. A multiple regression
analysis identified shut-in time as an important variable, with longer shut-in correlating to higher
concentrations. The chemistry of hydraulic fracturing fluids and formation waters were found to
be important variables for some ions. The minor ions included in the study are Ba, B, and Li.
Ba concentrations are likely related to barite dissolution/precipitation and are highest where
ii
sulfate concentrations are low. B and Li concentrations are both dominantly influenced by
mixing and may vary due to differences in formation water chemistry. Overall, the results are
expected to contribute to the growing knowledge on flowback water chemistry and its use in
iii
Lay Summary
After hydraulic fracturing and before production, high salinity water flows from oil and
gas wells for a period of time ranging from days to weeks. The salinity of the water increases
over time and can be used to investigate processes that are occurring in the subsurface. The main
influence on the chemistry of the water is mixing between the injected fluid and the water in the
formation. This has been found in previous studies and was supported by the results from the
study wells, located in northeastern British Columbia and northwestern Alberta. The amount of
time that the injected fluid remains in contact with the rock was also found to increase the
salinity. Looking at the chemistry in more detail and using statistical methods and geochemical
models assisted in understanding the complexity of the system, identifying the variability
between different sites, and determining what this means for future studies.
iv
Preface
This thesis is based on research conducted by the author, Jennifer Owen. The
development of the specific research questions were determined with input from Dr. R. Marc
Bustin (supervisor). The fluid samples used in the study were collected and sent to The
University of British Columbia (UBC) by several companies – ARC Resources Ltd., Black Swan
Energy Ltd., Unconventional Gas Resources, and other companies that wish to remain
anonymous.
The majority of the sample analyses were conducted in laboratory facilities at UBC, in
the Department of Earth, Ocean, and Atmospheric Sciences, by the author with assistance from
Scott Hazell for sample preparation and general chemistry tests, Maureen Soon for ICP-OES
analysis, and Vivian Lai for ICP-MS analysis. Vivian Lai also provided input on the sample
preparation method for the dissolved metals analysis. Fluid samples for the anion analysis and
rock samples for cation exchange capacity were sent to the BC Ministry of Environment and
Climate Change Strategy Analytical Chemistry Services Laboratory in Victoria, BC. Publically
available XRD data was compiled by Daniel Laird. Rock chip and core samples were obtained
from the BC Oil and Gas Commission Core Research Facility in Fort St. John, BC. These
samples were prepared for X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM)
at UBC by the author. The quantitative XRD analysis was conducted by Dr. Marc Bustin.
Assistance for developing the linear fixed effects models was provided by the Statistical
Opportunity for Students (SOS) program through the Department of Statistics at UBC.
Parts of the research were presented as a poster at the American Geophysical Union
(AGU) Fall Meeting in San Francisco, California in December 2016, on which Dr. Marc Bustin
v
was a co-author. Initial findings of the research were included in a paper in Geoscience BC
Summary of Activities 2016 [Owen, J.N. and Bustin, R.M. (2017): Implications of the inorganic
geochemistry of flowback water from the Montney Formation, northeastern British Columbia
Geoscience BC, Report 2017-1, p. 49–54.] I was the lead author for both the poster and the paper
I was responsible for writing the manuscript for all chapters of this thesis, with
manuscript suggestions and edits from Supervisor Dr. Marc Bustin, Committee Members Dr.
Roger Beckie and Dr. Uli Mayer, and External Examiner Dr. Ken Hickey.
vi
Table of Contents
Abstract .......................................................................................................................................... ii
Lay Summary ............................................................................................................................... iv
Preface .............................................................................................................................................v
Table of Contents ........................................................................................................................ vii
List of Tables ................................................................................................................................ xi
List of Figures ............................................................................................................................. xiii
Acknowledgements ................................................................................................................... xvii
Chapter 1: Introduction ................................................................................................................1
1.1 Introduction ..................................................................................................................... 1
1.2 Background Information ................................................................................................. 2
1.2.1 Hydraulic Fracturing Fluids ........................................................................................ 2
1.2.2 Formation Water ......................................................................................................... 4
1.2.3 Flowback Water .......................................................................................................... 6
1.2.3.1 Inorganic chemistry ............................................................................................ 6
1.2.3.2 Organic chemistry ............................................................................................... 7
1.2.3.3 Influences on flowback water chemistry ............................................................ 7
1.2.3.3.1 Mixing between hydraulic fracturing fluid and formation water .................. 8
1.2.3.3.2 Water-rock interactions ............................................................................... 10
1.3 Organization of thesis ................................................................................................... 12
Chapter 2: Investigating the Montney Formation flowback water chemistry through
mixing calculations and geochemical modelling .......................................................................14
2.1 Introduction ................................................................................................................... 14
2.2 Methods......................................................................................................................... 20
2.2.1 Sample collection ...................................................................................................... 20
2.2.1.1 Hydraulic fracturing fluid ................................................................................. 20
2.2.1.2 Flowback water ................................................................................................. 20
2.2.1.3 Produced water.................................................................................................. 20
vii
2.2.2 Sample analysis ......................................................................................................... 21
2.2.2.1 Major ion chemistry .......................................................................................... 21
2.2.2.2 Oxygen and hydrogen isotopes ......................................................................... 22
2.2.3 PHREEQC mixing model ......................................................................................... 23
2.3 Montney Formation flowback water chemistry ............................................................ 25
2.4 Flowback water mixing ratios ....................................................................................... 32
2.5 Variability in mixing ratios ........................................................................................... 40
2.5.1 Mixing ratio variability between tracers used ........................................................... 40
2.5.2 Mixing ratio variability over the flowback period for individual wells.................... 41
2.5.3 Mixing ratio variability between sites....................................................................... 43
2.5.3.1 Potential complications with the different tracers used .................................... 45
2.6 Insight from major ion chemistry ................................................................................. 47
2.6.1 Sodium and potassium .............................................................................................. 50
2.6.2 Calcium, magnesium, and strontium ........................................................................ 53
2.6.3 Sulfate ....................................................................................................................... 60
2.7 Discussion and Conclusions ......................................................................................... 64
Chapter 3: Flowback water chemistry from the Montney Formation: Part I - Stratigraphic
and areal variability.....................................................................................................................69
3.1 Introduction ................................................................................................................... 69
3.2 Methods......................................................................................................................... 75
3.2.1 Hydraulic Fracturing Fluid Chemistry ...................................................................... 75
3.2.2 Flowback Water Chemistry ...................................................................................... 76
3.2.3 Produced Water Chemistry ....................................................................................... 77
3.2.4 Linear Regression and Linear Mixed Effects Models .............................................. 77
3.3 Challenges of comparing flowback data from different wells ...................................... 79
3.4 Montney Formation flowback water chemistry ............................................................ 83
3.4.1 Overview of Montney Formation flowback water chemistry ................................... 88
3.4.2 Flowback water chemistry by formation member .................................................... 91
3.4.2.1 Upper Montney member ................................................................................... 91
3.4.2.2 Middle Montney member ................................................................................. 93
viii
3.4.2.3 Lower Montney member................................................................................... 94
3.4.3 Causes of variability in flowback water.................................................................... 94
3.4.4 Comparison of upper and middle Montney member Flowback Water..................... 99
3.5 Flowback water trend analysis .................................................................................... 102
3.5.1 Linear regression and linear mixed effects models................................................. 102
3.5.2 Results of flowback water chemistry trend analysis ............................................... 104
3.5.3 Results of flowback water volume trend analysis................................................... 106
3.5.4 Implications of the trend analyses........................................................................... 108
3.6 Conclusions ................................................................................................................. 113
Chapter 4: Flowback water chemistry from the Montney Formation: Part II – Controls on
variability ....................................................................................................................................115
4.1 Introduction ................................................................................................................. 115
4.2 Methods....................................................................................................................... 119
4.2.1 Fluid chemistry ....................................................................................................... 119
4.2.3 Montney Formation Mineralogy ............................................................................. 121
4.3 Montney Formation flowback water chemistry .......................................................... 122
4.4 Dominant variables on flowback water chemistry...................................................... 126
4.4.1 Initial sample flowback water chemistry ................................................................ 131
4.4.2 Intermediate to late flowback water chemistry ....................................................... 136
4.4.3 Important variables influencing flowback water chemistry.................................... 140
4.4.3.1 Shut-in time..................................................................................................... 140
4.4.3.2 Hydraulic fracturing fluid chemistry .............................................................. 140
4.4.3.3 Formation water chemistry ............................................................................. 142
4.4.3.4 Additional variables ........................................................................................ 145
4.4.3.5 Montney Formation Mineralogy ..................................................................... 146
4.4.3.6 Overall correlation .......................................................................................... 148
4.5 Conclusions ................................................................................................................. 149
Chapter 5: Key minor elements in Montney Formation flowback water: Barium, boron,
and lithium..................................................................................................................................152
5.1 Introduction ................................................................................................................. 152
ix
5.2 Methods....................................................................................................................... 155
5.2.1 Hydraulic fracturing fluid, flowback water, and produced water chemistry .......... 155
5.2.2 Montney Formation mineralogy ............................................................................. 157
5.3 Major ion chemistry of the Montney Formation flowback water ............................... 158
5.4 Key Minor Elements in Flowback Water ................................................................... 162
5.4.1 Barium..................................................................................................................... 163
5.4.2 Boron....................................................................................................................... 176
5.4.3 Lithium .................................................................................................................... 182
5.5 Conclusions ................................................................................................................. 186
Chapter 6: Conclusions and Recommendations .....................................................................189
6.1 Conclusions ................................................................................................................. 189
6.2 Recommendations ....................................................................................................... 193
References ...................................................................................................................................195
Appendices ..................................................................................................................................208
Appendix A Detailed sample preparation method .................................................................. 208
Appendix B Example of code used for PHREEQC geochemical mixing model ................... 211
Appendix C Percentages of formation water for all analyzed samples using δ 2H isotopes, δ18O
isotopes, and Cl concentrations as conservative tracers ......................................................... 213
x
List of Tables
Table 1.1: List of categories of chemical additives used in hydraulic fracturing fluids (modified
from FracFocus, 2017). ................................................................................................................... 4
Table 2.1: Summary of the four PHREEQC mixing models used for the analysis. ..................... 24
Table 2.2 (following page): Summary of pH, conductivity, total alkalinity, TDS, and major ion
concentrations in the flowback waters collected in the study. ...................................................... 26
Table 2.3: Summary of the δ2H values, δ18O values, and Cl concentrations of the hydraulic
fracturing fluids and formation water used for the mixing model. ............................................... 36
Table 2.4: Range of the δ2H values, δ18O values and Cl concentrations over the flowback period
for flowback waters collected from the study wells. .................................................................... 37
Table 2.5: Summary of proportions of formation water contributing to the flowback water for the
conservative tracers used in the study. .......................................................................................... 39
Table 2.6 (following page): Summary of the hydraulic fracturing fluid chemistry and the
formation water chemistry. ........................................................................................................... 48
Table 2.7: Summary of CEC and mineralogy of selected Montney Formation samples. ............ 53
Table 3.1: Summary of some of the variables that may influence flowback water geochemistry.
....................................................................................................................................................... 80
Table 3.2 (following page): Summary of conductivity, TDS, and the major ion concentrations for
each of the 9 study sites. ............................................................................................................... 86
Table 3.3: Groups of sites based on similarities in slope coefficient.......................................... 105
Table 4.1: List of several of the variables that may potentially be impacting the flowback water
chemistry.. ................................................................................................................................... 116
Table 4.2 (following page): Summary of the flowback water TDS and major ion chemistry for
the sampled wells. ....................................................................................................................... 123
Table 4.3: Summary of data for the variables considered in the regression analysis. ................ 128
Table 4.4(following page): Summary of hydraulic fracturing fluid chemistry and formation water
chemistry for each of the wells. .................................................................................................. 129
Table 4.5: Summary of the Montney Formation mineralogy used in the regression analysis.... 131
xi
Table 4.6: R2 values for the initial sample flowback water chemistry and the variables of interest.
..................................................................................................................................................... 133
Table 4.7: Summary of the datasets used in the step-wise regression analysis in order to
considered all sites and all variables of interest. ......................................................................... 134
Table 4.8: R2 values for the intermediate-late flowback water chemistry and the variables. ..... 137
Table 4.9: Cation exchange capacity (CEC) of samples from the Montney Formation. ............ 142
Table 5.1(following page): Summary of the general chemistry and the major ion, Ba, B, and Li
concentrations for the study wells............................................................................................... 160
Table 5.2: Summary of the hydraulic fracturing fluid Ba, B, and Li concentrations for each of the
study wells. ................................................................................................................................. 163
Table 5.3: Summary of produced water Ba, B, and Li concentrations compiled as part of the
study. ........................................................................................................................................... 168
Table 5.4: Summary of the compiled mineralogy for the study sites. ........................................ 181
xii
List of Figures
xiii
Figure 2.11: Modelled and measured results for (a) Ca; (b) Mg; and (c) Sr concentrations for
well I-1. ......................................................................................................................................... 56
Figure 2.12: The modelled Mg concentrations for different ion exchange values in the
geochemical model using well I-1 as an example. ....................................................................... 58
Figure 2.13: Modelled and measured results for (a) Ca; and (b) Mg concentrations with the
modelled results for mineral dissolution.. ..................................................................................... 60
Figure 2.14: Sulfate concentrations in the injected hydraulic fracturing (HF) fluid, the flowback
water, and the formation water for each of the sites. .................................................................... 62
Figure 2.15: The SO4 concentrations over the flowback period at the site I wells.. ..................... 63
Figure 3.1: Schematic cross-section of the Montney Formation showing divisions between the
lower, middle, and upper informal members. ............................................................................... 73
Figure 3.2: Location of the sites (A-I) included in the study.. ...................................................... 74
Figure 3.3: Different potential variables for graphical representation of flowback water chemical
data from one well (data from well I-1). a) Na concentrations versus flowback day; b) Na
concentrations versus cumulative flowback volume; c) Na concentrations versus percent
recovered3; d) Na concentrations versus percent of total flowback water 4; e) Na concentrations
versus Cl concentrations; f) Na/Cl mass ratio versus percent recovered. ..................................... 82
Figure 3.4: TDS at the study wells over the flowback period as cumulative flowback volume. a)
Site A wells – upper Montney Formation; b) Site B wells – upper Montney Formation; c) Site C
wells – upper (wells 1-5) and middle (wells 6 & 7) Montney Formation; d) Site D wells – upper
(wells 1 & 2) and middle (wells 3 & 4) Montney Formation; e) Site E wells – middle Montney
Formation; f) Site F wells – middle Montney Formation; g) Site G well – middle Montney
Formation; h) Site H well – upper Montney Formation; i) Site I wells – lower Montney
Formation. ..................................................................................................................................... 85
Figure 3.5: Different sources of variability in the studied Montney Formation flowback water.
TDS is used as an example, as the major ions show similar trends to TDS. a) All data are
grouped into early (day 1-2), middle (day 2-7), and late (> day 7) flowback water and produced
water; b) The results for all wells are grouped by the Montney Formation member where
hydraulic fracturing occurred; c) The results are grouped by site; d) The results for all wells are
grouped by region. ........................................................................................................................ 90
xiv
Figure 3.6: The flowback water results as TDS for all samples from all wells divided based on a)
the percent of total flowback and b) the percent recovered. ......................................................... 91
Figure 3.7: a) Na-Cl plot separated by site; b) Ca-Cl plot separated by site. ............................... 96
Figure 3.8: Na concentrations over the flowback period for (a) site C; and (b) site D wells. .... 101
Figure 3.9: An example of the linear fixed effects model with data from site E. ....................... 103
Figure 3.10: Slope coefficients with confidence intervals for a) TDS; and b) Sr concentrations
over flowback time. .................................................................................................................... 106
Figure 3.11: Summary of the slope coefficients for the cumulative flowback volume as a
function of flowback time for each of the wells for the early (day 0-3), mid (day 3-15), and late
(> day 15) portions of the flowback period. ............................................................................... 108
Figure 3.12: Sr concentrations in produced water samples, used to approximate the formation
water chemistry.. ......................................................................................................................... 111
Figure 4.1: Location of the 31 study sites in BC and Alberta, Canada....................................... 118
Figure 4.2: Schematic cross-section through the Montney Formation from the western margin in
BC to the eastern margin Alberta................................................................................................ 119
Figure 4.3: Relationship between the initial sample flowback water TDS values and (a) the HF
(hydraulic fracturing) fluid TDS; (b) the shut-in time; and (c) the breakdown pressure for the
study wells. ................................................................................................................................. 132
Figure 4.4: Relative importance of variables found to be significant (p-value < 0.05) in the step-
wise regression analysis. a) Results based on dataset I. Results using dataset II are similar; b)
Results based on dataset III when hydraulic fracturing (HF) fluid was excluded in order to
include the site C samples. Results from dataset IV are similar. ............................................... 135
Figure 4.5: Relative importance of variables for intermediate to late flowback water. a) Dataset I
– site C and breakdown pressure excluded; b) Dataset II – sites C, F, and H excluded; c) Dataset
III – HF fluid chemistry and breakdown pressure excluded; d) Dataset IV – Site F, site H, and
HF fluid chemistry excluded. ...................................................................................................... 139
Figure 4.6: Relative importance of parameters, including the last sample chemistry as a proxy for
the formation water chemistry for a) the initial flowback water samples; and b) the intermediate-
late flowback water samples. ...................................................................................................... 145
xv
Figure 4.7: Correlations between (a) Na concentrations; (b) Ca concentrations; (c) Na/Cl; and (d)
Ca/Cl with median clay. .............................................................................................................. 148
Figure 5.1: Schematic cross-section of the Montney Formation in BC and Alberta. ................. 154
Figure 5.2: Location of the study sites in northeastern BC and northwestern Alberta. .............. 155
Figure 5.3: Ba concentrations over the flowback period plotted as cumulative flowback volume
for a) Site A wells; b) Site B wells; c) Site C wells; d) Site D wells; e) Site E-H wells; and f) Site
I wells. ......................................................................................................................................... 165
Figure 5.4: Ba concentrations in produced water samples from wells completed in the Montney
Formation and located up to 20 km from the study sites. ........................................................... 167
Figure 5.5: The relationship between Ba and SO4 concentrations for the sampled wells. ......... 170
Figure 5.6: Barite in a core sample from a well located near site A. .......................................... 170
Figure 5.7: a) Ba and SO4 concentrations for well I-1 and well I-2. b) The saturation indices (SI)
for barite for well I-1 and well I-2. ............................................................................................. 175
Figure 5.8: Boron concentrations over the flowback period, plotted as cumulative flowback
volume. a) upper Montney member wells; b) middle and lower Montney member wells. ........ 177
Figure 5.9: Correlation between the maximum B concentration in flowback water for each of the
wells and the total vertical depth (TVD) of the well. ................................................................. 179
Figure 5.10: Boron concentrations across the formation plotted as cumulative flowback volume.
..................................................................................................................................................... 179
Figure 5.11: Li-B plot showing the three regions where the sampled wells plot. ...................... 186
xvi
Acknowledgements
Many people have provided support during my time at UBC and made this research
possible. First of all, I would like to thank my supervisor, Dr. Marc Bustin, for making this
project possible by arranging access to the samples, allowing me to have firsthand experience on
several analytical instruments at UBC, and reviewing the draft versions of the thesis chapters
many times. The recommendations have greatly improved this thesis. I am also thankful for
feedback provided by my committee members, Dr. Roger Beckie and Dr. Uli Mayer, and
This thesis would not have been possible without the willingness of several companies to
provide the samples. The sample collection and shipment conducted by ARC Resources Ltd.,
Black Swan Energy Ltd., Unconventional Gas Resources, and other companies that wish to
remain anonymous was appreciated. Financial support from Trican, Encana Corporation, Husky
Energy, Canadian Natural Resources (CNRL), Chevron Corporation, and Geoscience BC made
I am thankful for the assistance provided by many people, including Maureen Soon,
Vivian Lai, and Dirk Kirste, for training me to use various analytical instruments and helping run
samples. I also appreciate Mati Raudsepp stopping in at my office sometimes to check that I am
working. I would like to thank the undergraduate research students who helped with the sample
preparation and the basic analytical tests, in particular Scott Hazell. Without them I would not
have been able to analyze all of the samples in a reasonable amount of time.
I am grateful for the encouragement from my parents and their unfailing belief that I
could complete this thesis. I am also thankful for my sister, her new husband, and my friends for
Finally, I would like to thank my fiancé, Sean Stevenson, for supporting me in so many
xvii
Chapter 1: Introduction
1.1 Introduction
The combined technologies of hydraulic fracturing and horizontal drilling are used to
develop oil and gas reservoirs in low permeability rock. The injection of the hydraulic fracturing
fluids in multiple stages under high pressures causes fractures to form in clusters in targeted
locations along the horizontal portion of the well to access the hydrocarbons in the formation.
Of the injected fluid volume, which is typically between approximately 5,000 to 50,000 m 3 of
water in total per well (Vidic et al., 2013; Alessi et al., 2017), approximately 75% remains in the
subsurface (Haluszczak et al., 2013). However, this varies between wells and between
formations and in some cases a volume of fluid equivalent to 100% of the injected fluid volume
is returned to surface (Rivard et al., 2014). The fluid collected at surface is referred to as
flowback water. Flowback water is typically high in total dissolved solids (TDS) and various
other ions and compounds both from the hydraulic fracturing process and from the formation,
including inorganic ions (e.g., Chapman et al., 2012; Barbot et al., 2013; Haluszczak et al., 2013;
Rowan et al., 2015), organic ions (e.g., Abualfaraj et al., 2014; Akob et al., 2015; Lester et al.,
2015), and naturally occurring radioactive material (NORMS) (e.g., Nelson et al., 2014, 2015,
2016). The TDS of the flowback water generally increases over the flowback period due to the
increasing concentrations of the major ions, although in some wells the TDS can stabilize in later
samples (e.g., Haluszczak et al., 2013; Zolfaghari et al., 2016). Characterization of the chemistry
of this water is important as it provides insight into geochemical processes that are occurring in
the reservoir, and in addition, can assist with flowback water management at future wells to
minimize impacts on the freshwater resources around oil and gas development.
1
The subject of this thesis is the inorganic flowback water chemistry from wells completed
in the Lower Triassic Montney Formation in northeastern British Columbia and northwestern
Alberta. This formation includes shale, dolomitic-siltstone and fine grained sandstone
lithologies (Edwards et al., 1994; Dixon, 2000). Conventional oil and gas exploration in the
Montney Formation targeted turbidite deposits, sandstone units, and coquina dolomite units
(Bird et al., 1994); however, current exploration is focused on the unconventional resources in
the fine grained deposits (Zonneveld et al., 2011). There is no Montney Formation flowback
water chemistry available in the literature as the majority of the previous work has been
completed in other formations, most notably the Marcellus Shale Formation in the eastern United
States (e.g., Barbot et al., 2013; Capo et al., 2013; Haluszczak et al; 2013; Marcon et al.; 2017).
The present study characterizes the major ion and selected minor ion chemistry of the Montney
Formation flowback water from nine well pads located across the formation. The variability
between sites and the dominant factors impacting the flowback water chemistry are investigated.
fracturing fluids, formation water, and flowback water. Hydraulic fracturing fluid and formation
water are discussed as the chemistry of these fluids likely impact the flowback water chemistry
through mixing in the reservoir. This summary is designed to provide an initial background
understanding of these fluids to support the more detailed discussion in the subsequent papers.
Hydraulic fracturing fluids are composed of water, proppant, and chemical additives.
The water and proppant make up approximately 99.5% of the volume of the fracturing fluid,
with the additives making up the remaining 0.5-1% (Gregory et al., 2011; McLaughlin et al.,
2
2016). The volume of water required to hydraulically fracture a well varies between wells and
formations. For the Montney Formation, the average volume used per well is between about
8,000 and 11,000 m3 (Alessi et al., 2017). The base fluid used to make up the hydraulic
fracturing fluid can be surface water, groundwater, or a mixture of freshwater and treated
flowback water from previously fractured wells (Shipman et al., 2013). If flowback water is
recycled, the high salinity and presence of organic matter need to be taken into consideration for
hydraulic fracturing fluid performance (Esmaeilirad et al., 2016). There is ongoing research on
chemical additives that can be used with higher salinity water, including recycled flowback
water, to improve the water management related to hydraulic fracturing operations (e.g.,
In addition to the makeup water, the other components of the hydraulic fracturing fluid
are the proppants and the chemical additives. Proppants are sand sized grains of quartz with or
without a resin coat or can be made of a synthetic material including ceramic, bauxite, resin, or
plastic. The purpose of these grains is to keep the fractures created during the hydraulic
fracturing process ‘propped’ open once the pressure in the well has been decreased through
production. The proppant is approximately 9% of the fracturing fluid, by weight (Vidic et al.,
2013). There are a multitude of chemical additives that can be used in hydraulic fracturing fluid.
Additives can include acids, friction reducers, surfactants, salts, scale inhibitors, pH adjustors,
iron controls, corrosion inhibitors, and biocides (Gregory et al., 2011; Table 1.1). In general, not
all additives listed are required at each hydraulic fracturing site (Gregory et al., 2011). In
general, between 4 and 28 additives are used in the hydraulic fracturing fluid for a well
(McLaughlin et al., 2016). The composition of the hydraulic fracturing fluid is based on site-
specific characteristics, including the water chemistry used to make up the hydraulic fracturing
3
fluid, the formation water chemistry, and the formation lithology. In some wells, chemical
tracers, such as tritiated water and thiocyanates, are injected with the hydraulic fracturing fluid to
study the extent of the fractures and potential hydraulic communication between nearby wells
(Salman and Kurtoglu, 2014). These studies show that different hydraulic fracturing stages are
contributing to the flowback water at different times throughout the flowback period (Sullivan et
al., 2004).
Table 1.1: List of categories of chemical additives used in hydraulic fracturing fluids (modified from
FracFocus, 2017).
Formation water can have TDS greater than 300,000 mg/L (Bagheri et al., 2014) and is
classified as Na-Cl, Cl-Ca or Na-Ca-Cl type water (Connolly et al., 1990; Stueber and Walter,
1991). The TDS range of the formation water from the Montney Formation investigated to date,
ranges from about 50,000 to 250,000 mg/L TDS and it is classified mainly as Na-Cl type (Kirste
et al., 1997). The formation water chemistry can change over time compared to the chemistry of
4
the original connate water deposited with the formation due to mixing with meteoric water or
other formation waters and from water-rock interactions, such as albitization, dolomitization,
interactions with clay minerals, and mineral precipitation or dissolution (e.g., Bagheri et al.,
2014; Connolly et al., 1990). In order to determine if the elevated concentrations are due solely
to evaporation or if other processes are occurring to alter the formation water chemistry, the ion
concentrations in the formation water can be compared to the seawater evaporation pathway
(Dresel and Rose, 2010). Seawater evaporation curves have been developed for the major ions
and account for several stages of mineral precipitation during the evaporation process, including
calcite precipitation, gypsum precipitation, and halite precipitation (e.g., Carpenter et al., 1978;
McCaffrey et al., 1987). The Cl/Br ratio is often used in studies on the formation water
chemistry of sedimentary basins as this ratio remains constant until halite saturation is reached at
which point Cl is preferentially incorporated over Br into the halite crystal lattice while the
aqueous Br concentrations continue to increase (Carpenter et al., 1978; McCaffrey et al., 1987,
Freeman 2007; Stueber and Walter 1991). The Alberta Basin formation waters generally plot on
or near the seawater evaporation curve indicating that the elevated salinity is due to the
evaporation of seawater rather than halite dissolution (Connolly et al., 1990). However,
numerical models indicate that there may be some contribution to the Alberta basin brines from
halite dissolution in addition to contributions from evaporated seawater and freshwater (Gupta et
al., 2012). Minor depletions in the Na and Cl concentrations in formation water can result from
Kirste et al. (1997) plotted major cation concentrations with Br concentrations for
formation water brines from the Montney, Halfway, and Doig Formations. They found that the
Montney Formation waters had Na concentrations that plotted close to the seawater evaporation
5
curve while K and Mg concentrations were depleted and Ca concentrations were enriched
concentrations relative to seawater evaporation was observed by Dresel and Rose (2010) for
western Pennsylvanian brines, by Haluszczak et al. (2013) for brines from the Marcellus Shale
and by Michael et al. (2003) for brines in Devonian aquifers in the Alberta Basin. This was
increase due to albitization (Michael et al., 2003). The depletion in K relative to evaporated
seawater may be due to the conversion of smectite to illite during diagenesis (Chaudhuri and
Clauer, 1993; Cooley and Donnelly, 2012) or due to adsorption on clay minerals (Chan et al.,
2002).
Flowback water is generally highly saline although concentrations vary over the
flowback period and between wells and formations. TDS values can be as high as 345,000 mg/L
(Kolesar Kohl et al., 2014) and Cl concentrations can be greater than 100,000 mg/L (Haluszczak
et al., 2013). Of the major cations, Na concentrations are highest (commonly greater than 30,000
mg/L), while Ca, Mg, and K concentrations are lower (e.g., Gregory et al., 2011; Haluszczak et
al., 2013). Additional ions that are often elevated in flowback water include Ba and Sr (Barbot et
al., 2013). In general, the TDS and the concentrations of the major ions typically increase over
the flowback period, in some wells reaching a plateau and in other wells showing a continual
increase over the flowback period (e.g., Blauch et al., 2009; Haluszczak et al., 2013). The
variable response may be due to the complexity of the fracture system, with the continuous
increase being associated with more secondary fractures and a greater surface area for exposure
6
to formation water (Bearinger, 2013; Ghanbari et al., 2013; Zolfaghari et al., 2015a). In contrast
to Cl and the major cations, sulfate (SO4) concentrations typically decrease (Haluszczak et al.,
Organic compounds and their degradation products are found in flowback water (Lester
et al., 2015). The majority of the organic compounds can typically be characterized as aliphatic
organics, followed by cycloaliphatic and aromatic organics, and only a small proportion (<5%)
Shale flowback water can include volatile organic carbon, 1,2-dichloroethane, benzene,
toluene, tetrachloroethylene, vinyl chloride, and xylenes (Abualfaraj et al., 2014; Strong et al.,
2014; Ziemkiewicz and He, 2015). Some of these compounds are additives in hydraulic
fracturing fluid; however, others, such as benzene and toluene, can be found naturally near oil
and gas reservoirs (Lester et al., 2015). Acetate, formate, and pyruvate have also been detected
in flowback water and indicate that organic compounds in the hydraulic fracturing fluid are being
degraded by bacteria (Akob et al., 2015). In their study, they found that the organic chemistry of
the flowback water varied between wells even within the same formation.
Different hypotheses have been proposed to explain the changes in the inorganic ion
concentrations over the flowback period. These include mixing of the formation water with the
hydraulic fracturing fluid (e.g., Haluszczak et al., 2013; Engle and Rowan, 2014; Olsson et al.,
2013; Vengosh et al., 2017), diffusion into the fractures followed by mixing (Balashov et al.,
2015), and water-rock interactions (e.g., Barbot et al., 2013; Marcon et al., 2017; Seales et al.,
7
2016; Zolfaghari et al., 2016). The processes influencing the flowback water chemistry may
vary between sites and over the flowback period. In addition, the processes affecting the ion
Several studies suggest that the increase in the ion concentrations observed in flowback
water is due to mixing between the relatively low salinity injected hydraulic fracturing fluid and
the higher salinity formation water (e.g., Haluszczak et al., 2013; Engle and Rowan, 2014;
Olsson et al., 2013; Vengosh et al., 2017). Other potential sources of high salinity water include
nearby units and higher porosity lenses or fractures within the low permeability unit (Stewart et
al., 2015). The elevated ion concentrations in flowback water are not related to the hydraulic
fracturing fluid chemistry as these fluids typically have much lower concentrations of the
majority of ions relative to flowback waters, indicating that the high concentrations are not
related to the chemical additives (Ziemkiewicz and He, 2015). In wells where recycled water is
used to make up the hydraulic fracturing fluid, the major ion concentrations are higher in the
injected fluid and may be similar to the initial flowback water from the well. Inorganic
Haluszczak et al. (2013) compiled water chemistry from several sources within
the Marcellus Shale, including flowback water samples and formation water brine
samples. Based on their dataset, they concluded that as flowback progressed, the
effect of the formation water chemistry on the chemistry of the flowback water
increased. This is based on the observation that the flowback water chemistry
approaches that of the formation water chemistry over the flowback period;
8
Haluszczak et al. (2013) also compared the Cl and Br concentrations to the
seawater evaporation curves and found that the source of salinity could be
explained as evaporated seawater that has been evaporated past the point of halite
saturation and has been subsequently diluted with fresher water, rather than a
mixed with the lower salinity hydraulic fracturing fluid can be used to explain the
Stewart et al. (2015) found that the ion ratios measured during sequential
extractions of shales were not consistent with the ion ratios observed in flowback
water samples, indicating that the water-rock interactions were not the dominant
Kondash et al. (2017) used a mass balance calculation for TDS based on mixing
Isotopic data provides additional support for the mixing hypothesis. A study examining
the stable isotopes found that the δ18O values of flowback water increase and move away from
the meteoric water line, indicating a hydraulic fracturing fluid derived from freshwater and an
increasing proportion of formation water derived from evaporated seawater (Rowan et al., 2015).
Sr isotopic ratios can also be used to look at fluid mixing between the formation water and
hydraulic fracturing fluid (Chapman et al., 2012). The 87Sr/86Sr ratio is low in the injected fluid
and the ratio initially increases in the flowback water before reaching stable values (Stewart et
al., 2015).
9
Rather than mixing between the formation water and the hydraulic fracturing fluid,
another possibility is diffusion of the salts in the formation water brine into the hydraulic
fracturing fluid (Balashov et al., 2015). They developed a model that shows that only 2% of the
shale, by volume, is required to have brine as either free brine or capillary bound brine in order
to explain the elevated ion concentrations observed in flowback water. The model estimates the
stimulated reservoir volume at 1.5 x 107 m3 based on typical values for hydraulic fracturing in the
Marcellus Shale. Salt diffusion out of the formation and towards the fractures was also modelled
by Wang et al. (2016, 2017). They found that diffusion of ions acts in the opposite direction to
water osmosis, a process which should be taken into consideration as a mechanism for reducing
the flowback water chemistry. If only mixing were involved in the increasing ion
concentrations, there would be a 1:1 correlation between all ions, whereas there is often an
enrichment or depletion of certain ions at different times throughout the flowback period (Barbot
et al., 2013). The additional geochemical processes impacting the flowback water chemistry
Halite dissolution has been suggested as a potential source of salinity in flowback water
and halite has been observed in Marcellus Shale core (Blauch et al., 2009); however, there has
been some discussion on if halite is only found in some locations in the Marcellus Shale or if it
was present as a precipitate formed during the drilling process (e.g., Haluszczak et al., 2013). A
numerical model developed for Na and Cl concentrations indicates that some halite dissolution is
10
necessary to explain the elevated concentrations of Na and Cl measured in flowback water and
that mixing alone does not adequately predict the Na and Cl concentrations (Seales et al., 2016).
Other mineral reactions can involve precipitation and dissolution of carbonate, sulfate,
and phosphate minerals. Several laboratory experiments have observed the dissolution of
carbonates in shale samples in synthetic hydraulic fracturing fluids under elevated temperature
and pressure conditions (Wilke et al., 2015; Dieterich et al., 2016; Marcon et al., 2017; Lu et al.,
2017). Clay dissolution was also observed in one of the experiments (Marcon et al., 2017). The
oxidation of pyrite by the oxic hydraulic fracturing fluid was observed by Wilke et al. (2015) and
Harrison et al. (2017), which resulted in a decreased pH if sufficient carbonate was not available
to buffer the system. Buffering by carbonate was found to be an important control on the release
of trace metals from the shale samples (Wilke et al., 2015). Various secondary mineral phases
were observed to precipitate on the core samples in the experiments. These included gypsum,
barite, strontianite, celestite, apatite (Dieterich et al., 2016), smectite, anhydrite (Marcon et al.,
Ion exchange may also have an impact on flowback water chemistry. For flowback water
samples collected from wells in the Horn River Basin in BC, the Na and K to Cl ratios were
initially high while these ratios decreased later in the flowback period (Zolfaghari et al., 2016).
This was interpreted as ion exchange early on in the flowback period releasing Na and K ions
concentrations (Zolfaghari et al., 2016). Na and K ions may be released from clays as these ions
are the interlayer cations for smectite and illite, respectively (Zolfaghari et al., 2015b). The
sources of the halite and potassium chloride salts could be evaporated pore water in the pore
spaces (Ghanbari et al., 2013). Sequential extraction experiments show that the monovalent
11
cations are more loosely bound to the rock and are likely from ion exchange or formation water
or salts, while divalent cations are more tightly bound and may have a greater impact later in the
flowback period (Zolfaghari et al., 2015b). Barium (Renock et al., 2016), boron, and lithium
(Warner et al., 2014) may also be released through ion exchange facilitated by the injection of
the low salinity hydraulic fracturing fluid into the formation which is in equilibrium with the
information and previous work completed on flowback water chemistry from other formations.
The aim of the present series of studies is to characterize the Montney Formation flowback water
to provide information on the variability and controls on the flowback water chemistry from this
formation. Although the results of this study are specific to the Montney Formation, the overall
conclusions can be applied to other formations where hydraulic fracturing is occurring. Chapters
2 through 5 are a series of four separate, standalone research papers. The research papers are
designed to each cover different aspects of the study as a whole. Chapter 2 focusses on
determining the mixing ratios between the injected hydraulic fracture fluid and the formation
water. The mixing ratios are then used with geochemical models to determine if the major ion
concentrations can be explained by mixing alone or if other geochemical processes also have a
significant effect. Chapters 3 and 4 present related aspects of a larger study. Chapter 3 is part I
of the study and discusses comparing the flowback water chemistry between different sites and
presents a method for making a comparison. Chapter 4 is part II of the study and investigates the
dominant variables influencing the flowback water chemistry. Chapter 5 includes a discussion
on selected minor elements, including barium, boron, and lithium, present at elevated
12
concentrations in flowback water. Chapter 2 uses the geochemical results from 24 wells, as the
hydraulic fracturing fluids were not collected for the wells from one site (7 wells) and the
hydraulic fracturing fluid chemistry was required for the analysis. Chapters 3 through 5 use the
results from 31 wells. The four papers are followed by the major conclusions of the studies and
13
Chapter 2: Investigating the Montney Formation flowback water chemistry
2.1 Introduction
Production of oil and gas from unconventional reservoirs involves the combination of
formations. The hydraulic fracturing process entails the injection of large volumes of fluid into
the target formation in order to fracture the rock and increase the permeability to allow for the
production of oil and/or gas from the reservoir. The volume of fluid required is on the order of
1,000's to 10,000's of cubic meters (m3) per well (Vidic et al., 2013; Alessi et al., 2017). Prior to
the production stage, a large volume of variably saline water is recovered at the surface. This
water, referred to as flowback water, is volumetrically approximately 25% of the injected fluid
volume (Haluszczak et al., 2013); however, there is a large amount of variability and the volume
of flowback water can equal (or exceed) the volume of fluid that was injected into the reservoir
(Rivard et al., 2014). The flowback water, even initially, is chemically different than the injected
fluid. The total dissolved solids (TDS) of the flowback water generally increases over the
flowback period and can reach levels greater than 300,000 mg/L (Barbot et al., 2013). In several
previous flowback water studies, the increasing TDS has been attributed, at least in part, to
mixing between the injected hydraulic fracturing fluid and the connate formation water (e.g.,
Haluszczak et al., 2013; Olsson et al., 2013; Capo et al., 2014; Engle and Rowan, 2014; Kolesar
Kohl et al., 2014; Kondash et al., 2017). Mixing is considered since the major ion concentrations
and isotopic values (e.g., δ18O, δ2H, and 87Sr/86Sr) approach those in formation water over the
14
flowback period, indicating an increasing proportion of formation water over time (e.g., Rostron
and Arkadakskiy, 2014). Examining the change in the major ions and the isotopes can be used to
determine if mixing alone can adequately explain the major ion concentrations and the isotopic
In order to determine mixing ratios between different water sources, conservative tracers
are required. A conserved tracer is one that is not involved in any chemical or biological
reactions in the studied system and consequently any changes observed in the tracer
tracers, such as tritiated water and methanol, can be injected with the hydraulic fracturing fluid
and are used to look at the extent of the fracture network (Salman and Kurtoglu, 2014).
However, there are also ions (e.g., chloride [Cl]) and stable isotopes (e.g., δ 18O and δ2H) that are
naturally found in flowback water and act as conservative tracers in the system. Cl is the
dominant ion in flowback water and increases over the flowback period, often reaching
concentrations greater than 100,000 mg/L (Haluszczak et al., 2013). Cl is a suitable conservative
tracer in flowback water studies where halite dissolution is not occurring and where the water
remains undersaturated in halite. The stable water isotopes1 are also useful tracers for the mixing
proportions in flowback water as the formation temperature and length of time for water-rock
interactions between the injected hydraulic fracturing fluid and the rock are not sufficient to
significantly change the isotopic signature of water in the system (Anderson and Chai, 1974;
1
Isotopic values are reported as delta values (δ) which are calculated as:
The water isotopic values are measured relative to Vienna Standard Mean Ocean Water (VSMOW).
15
O'Neil and Kharaka, 1975; Rowan et al., 2015). Water produced from deep formations typically
has elevated δ18O and δ2H values relative to meteoric water and results that plot to the right of
the Global Meteoric Water Line (GMWL) (e.g., Sharma et al., 2014; Rowan et al., 2015). This
shift in the isotopic signature of the formation water may be due to water-rock interactions, such
as gypsum dehydration and exchange between water and carbonates, which have occurred since
the time of deposition (Sharma et al., 2014). Simple mixing calculations using conservative
tracers can be completed to calculate the percentages of the endmember source waters (i.e., the
hydraulic fracturing fluid and the formation water) in the mixed flowback water. The expected
concentrations of different elements based on mixing alone can be compared to the measured
The current study focusses on flowback water from the Lower Triassic Montney
Formation in northeast British Columbia (BC) and northwest Alberta, Canada. The formation
unconformably overlies the Permian Belloy Formation and is overlain by the Doig Phosphate
Zone of the Middle Triassic Doig Formation (Edwards et al., 1994). The Montney Formation
consists of fine grained sediments, principally composed of carbonate, quartz, and feldspar, with
minimal clay, and is dominated by dolo-quartz-siltstone and very fine grained quartz sandstone
(Zonneveld et al., 2011; Zonneveld and Moslow, 2014). The formation generally varies from
shale in the west-northwest to interbedded sandstone and shale in the east-southeast (Edwards et
al., 1994), representing distal shelf to deltaic and shoreline environments (Chalmers and Bustin,
2012). Very fine grained sandstone deposits of the Montney Formation located mainly in the
region near the BC-Alberta border, are interpreted as turbidite deposits (Zonneveld et al., 2010).
Past studies on the Montney Formation have focused in either BC or Alberta. In Alberta, the
16
formation has been divided into a lower very fine grained sandstone and siltstone member, a
middle coquina dolomite member and an upper siltstone member (Davies et al., 1997). In BC,
the coquina dolomite member is absent and there is an overlying shale member (Dixon, 2000).
A recent stratigraphic study of the Montney Formation by Davies and Hume (2016) applied
across the basin divides the formation based on a combination of stratigraphy and biostratigraphy
(Fig. 2.1). The upper member in this framework includes the siltstone unit, which is sometimes
referred to as the Lower Doig siltstone, and is located below the Doig Phosphate Zone. The
present study follows Davies and Hume's (2016) recent subdivision of the Montney Formation
17
Figure 2.1: Schematic cross-section of the Montney Formation. This division into lower, middle, and upper
Montney Formation is used in the present study. Each of these members represents a Third-Order sequence.
The upper Montney Formation includes the lower Doig siltstone unit which is below the Doig Phosphate Zone
The study area includes wells completed in the Montney Formation in both BC and
Alberta. Fluid samples were obtained from 24 wells located at 8 sites (Fig. 2.2). The wells were
completed in the upper (13 wells), middle (9 wells), and lower (2 wells) Montney Formation.
Both the Cl concentrations and δ18O and δ2H isotopes are used to determine mixing proportions
between the injected hydraulic fracturing fluid and the formation water. Geochemical mixing
models are also used to determine if mixing alone can be used to explain the major ion
concentrations in the flowback water or if there are additional process such as ion exchange or
mineral precipitation and dissolution occurring to produce the observed flowback water
18
chemistry. The major ions included in the analysis are sodium (Na), potassium (K), calcium
Figure 2.2: Location of the 8 study sites (A, B, and D-I). Wells completed in the upper Montney Formation
are located at site A (8 wells), site B (2 wells), site D (2 wells), and site H (1 well). Middle Montney Formation
wells are located at site D (2 wells), site E (4 wells), site F (2 well), and site G (1 well). The two wells located at
site I were completed in the lower Montney Formation. The extent of the Montney Formation is shown in
green (modified from Edwards et al., 1994). The map area in relation to British Columbia and Alberta is
19
2.2 Methods
Hydraulic fracturing fluids, as the base fluid with additives, were collected at each site in
500 mL or 1 L containers. For the majority of wells, a separate sample used in each of the
hydraulic fracturing stages was collected (14 to 26 samples per well). The fluids used in the
different stages were combined into two or more composite samples per well based on similar
electrical conductivity readings. Overall values for the major ion concentrations in the hydraulic
fracturing fluid were derived for each well using the relative volumes of fluid injected in each
stage. For example, if two composite samples were analyzed for a well and one represents 75%
of the injected fluid volume, the chemistry of this sample will represent ¾ of the chemistry in the
overall values for the well, while the other sample will represent ¼ of the chemistry. A single
representative hydraulic fracturing fluid sample was collected for the site F wells and each of the
site I wells.
flowback period at each of the 24 sites. A higher sampling frequency of 2 to 3 samples per day
was used in the first week and then the frequency was reduced to 1 sample per day for the
remainder of the flowback period. The variable frequency was used in order to capture the higher
variability in chemistry earlier in the flowback period when the flowrate is higher.
For our study, the produced water is considered to be the water that is collected after the
well has begun producing oil or gas. The chemistry of the produced water is used to
20
approximate the formation water chemistry for the study wells with the recognition that the
impact of the injected fluid on the produced water chemistry may extend well into the productive
life of a well. Several produced water samples were collected from the wells at site A and site B
following the beginning of production. The formation water for the two site I wells is
approximated based on a single produced water sample collected from a producing well
approximately 20 km away from site I. No produced water samples were obtained for the wells
from sites D through H. The formation water chemistry for these wells was derived from the
major ion concentrations from publically available data for produced water from nearby wells
completed in the Montney Formation. Samples with anomalously low TDS or potential
contamination, were removed from consideration and the median values of the remaining results
were used to approximate the formation water chemistry for the remaining wells on sites D
through to H. The isotopic values for the formation water for all sites were estimated based on
the analysis of the produced water samples collected as part of the present study as isotope
values were not included in the publically available geochemical results used for the major ion
chemistry.
All samples were stored at 4°C prior to analysis. As the samples were purposely not
preserved or filtered on site, the flowback water and produced water samples were heated in 120
mL acid-washed Teflon® containers in a hot water bath to reservoir temperature (75-80°C) for a
24 hour period. After heating, the samples were filtered through 0.45µm filters and divided into
three sub-samples for analyses of: 1) pH, conductivity, and total alkalinity; 2) anions; and 3)
dissolved metals. The hydraulic fracturing fluid samples were also filtered and sub-divided but
21
were not heated. The anion samples were sent to a laboratory in Victoria, BC and analyzed by
ion chromatography. The remaining analyses were conducted at The University of British
Columbia in Vancouver, BC. The pH was measured with an OMEGA ® PHB21 portable pH
probe and conductivity was measured with a HACH ® CDC401 conductivity probe. Total
alkalinity was measured by titration with sulfuric acid (H2SO4) using a HACH® digital titrator
(model 16900). The dissolved metal samples were preserved to pH < 2 with trace metal grade
For dissolved metal analyses, the preserved samples were acid digested to remove
organics prior to analysis, as the presence of organics may interfere with the analysis. The first
step in the digestion was adding concentrated trace metal grade HNO 3 and concentrated trace
metal grade hydrochloric acid (HCl) in a 2:1 ratio to each sample and evaporating the mixture on
a hot plate. This step was followed by adding additional HNO 3 to the sample and re-evaporating
the remaining fluid. The evaporated residue was re-diluted with a 1% HNO 3 deionized water
solution. The digested samples were analyzed for the major cations by inductively coupled
plasma-optical emission spectrometry (ICP-OES) with a Varian 725-ES ICP-OES using indium
(In) as the internal standard. The ICP-OES analysis included Na, K, Ca, Mg, and Sr ions. TDS
was calculated by summing the ion concentrations. This TDS value was compared to an
estimated TDS value based on the conductivity measurement as a method to check the result.
The isotope samples were prepared by taking a sub-sample of unheated, filtered fluid and
mixing it with activated charcoal for a minimum of 48 hours. The activated charcoal acts to
remove organic compounds through adsorption, as the organics may interfere with the isotopic
measurements. Following the mixing period, the sample was filtered a second time to remove
22
the activated charcoal. The stable oxygen and hydrogen isotopic analysis was completed using
an LGR® DLT-100 with an LC-PAL liquid autosampler. High salinity samples were diluted
with deionized water prior to the analysis in order to prevent the salts present in the sample from
precipitating and plugging the instrument tubing. The dilution factor was recorded and the
isotopic values of the deionized water were determined with the instrument in order to complete
(Parkhurst and Appelo, 2013). Each of the models used the Pitzer database due to the high ionic
strength of the formation water. Four models increasing in complexity were run with the addition
of different geochemical processes at each stage (Table 2.1). The modelled results were
compared to the measured flowback water results in order to determine which geochemical
processes are impacting the flowback water chemistry. An understanding of the Montney
Formation mineralogy to support the geochemical model was obtained through a combination of
publically available X-Ray Diffraction (XRD) results and additional samples collected at the BC
Oil and Gas Commission core research facility in Fort St. John, BC and analyzed at UBC. The
additional samples were analyzed by XRD following the modified smear mount method
(Munson et al., 2016) and the results were interpreted using the Rietveld method (Rietveld, 1967,
1969).
23
Table 2.1: Summary of the four PHREEQC mixing models used for the analysis. The model results were
compared to the measured concentrations and the calculated proportions of formation water to provide an
understanding of the geochemical processes that are impacting the flowback water major ion concentrations.
Model I is a simple mixing model between the injected hydraulic fracturing fluid and the
other geochemical processes are considered in the initial model, the resulting ion concentrations
show a linear increase. Model II adds possible secondary mineral precipitation and allows the
mixed fluid to reach equilibrium (i.e., if a secondary mineral is oversaturated in the fluid, it is
allowed to precipitate until the saturation index (SI) is equal to 0). This model represents the
maximum amount of precipitation that would occur when the two fluids are mixed, as it does not
consider the kinetics of mineral precipitation. Model III adds ion exchange to the model based
on the exchange sites being in equilibrium with the formation water. Setting the exchange sites
to be in equilibrium with the formation water determines which ions are on the exchange sites so
they do not need to be entered into the model manually. The amount of exchangeable ions was
24
estimated at 0.5 mole per kilogram of water. This value is a reasonable estimate based on an
average density (2.65 g/cm3) and the median cation exchange capacity (CEC) for 15 Montney
Formation samples that were analyzed for CEC. The 15 samples were selected for varying clay
content. A median value is used for all wells since there was limited correlation with mineralogy
and a more precise value is not available. Model IV adds carbonate dissolution to the model.
Based on the ions considered at the level of detail in the model and the mineralogy of the
formation, only the carbonate minerals are both abundant in the Montney Formation and
comprised solely of the major ions included in the model. The inclusion of quartz, feldspar, and
clay would require the addition of silicon (Si) and aluminum (Al) (Al for feldspar and clay only)
to the model and in addition, due to the stability of these minerals, they would not be expected to
dissolve significantly during hydraulic fracturing. Up to 1% (by wt.) of calcite and 1.8% (by wt.)
of dolomite are permitted to dissolve if the fluid is undersaturated in these minerals, which is
only a fraction of the amount of calcite and dolomite that are available in the Montney
Formation. These percentages were selected to represent a small amount of dissolution and are
The Montney Formation flowback waters collected in the study had elevated
concentrations of the major ions with TDS up to approximately 228,000 mg/L (Table 2.2),
similar to what has previously been reported for flowback waters from other formations where
hydraulic fracturing is occurring (e.g., Marcellus Shale – Barbot et al., 2013; Haluszczak et al.,
2013; Ziemkiewicz and He, 2015). Together Cl and Na ions account for 75 to 95% (median:
92%) of the TDS in the sampled Montney Formation flowback water. The other ions that are
elevated in the flowback water are Ca, K, Mg, Sr, and, in some wells, SO 4 (Table 2.2). The
25
concentrations of the major ions, and therefore TDS, increase over the flowback period, since all
of the study wells used injected fluids with major ion concentrations that were lower relative to
those in formation water (Fig. 2.3, Fig. 2.4). In contrast, the SO 4 concentrations do not show a
continuous increase and are often constant over the duration of the flowback period that the
fluids were sampled. The pH remains neutral for the majority of the flowback water samples
(median: 7.2) and most samples have moderate total alkalinity (median: 184 mg CaCO 3/L),
although both the pH and the total alkalinity show a decreasing trend over the flowback period.
The organic compounds were not analyzed in the flowback water from the study wells. The
exclusion of these molecules may contribute to the higher charge balance error (generally ±15%)
seen in some of the samples. The necessity to dilute the samples for the analysis to reach the
range of the standards may introduce additional error and contribute to higher charge balance
errors.
Table 2.2 (following page): Summary of pH, conductivity, total alkalinity, TDS, and major ion concentrations
in the flowback waters collected in the study. Data for wells at the same site and completed within the same
member of the Montney Formation are grouped together for this summary. For the TDS and the major ions,
lower values for all wells are from earlier in the flowback period, while higher values are from later in the
flowback period.
26
Montney Formation
upper middle lower
member
A B D H D E F G I
Site
(8 wells) (2 wells) (2 wells) (1 well) (2 wells) (4 wells) (2 wells) (1 well) (2 wells)
Parameter n 22 30 19 18 22 26 12 8 28
min 7.5 6.3 2.3 6.1 6.6 6.0 3.4 6.8 6.4
pH median 7.8 7.0 6.9 6.3 7.2 7.4 6.3 7.3 7.1
max 8.1 7.9 9.2 8.1 9.5 7.8 6.7 7.6 7.7
min 60.8 47.6 50.4 33.8 7.12 22.1 29.1 27.9 11.1
Conductivity
median 102 123 86.4 113 36.1 35.7 37.5 64.8 56.1
(mS/cm)
max 131 190 107 135 74.6 51.8 50.4 95.4 130
27
There is variability in the flowback water chemistry between the different wells (Table
2.2, Fig. 2.3, Fig. 2.4). For example, the TDS in the initial flowback water samples from the
study wells range from 3,610 mg/L (well D-4) to 123,000 mg/L (well C-7) while TDS of the
final samples range from 23,800 mg/L (well E-2) to 228,000 mg/L (well B-1). In general, the
TDS and major ions are higher in the initial flowback water from the upper Montney Formation
wells relative to the initial flowback water from both the lower and middle Montney Formation
wells. In the late flowback period water, the major ion concentrations reach similar levels in the
samples from the upper and lower Montney Formation wells whereas the major ion
concentrations in the middle Montney Formation flowback water remain lower (Table 2.2,
Fig. 2.3, Fig. 2.4), although there is overlap in the results for flowback water from the different
members. The wells completed on the same site and within the same member of the Montney
Formation most commonly have similar flowback water chemistry (e.g., well D-3 and well D-4;
well E-1 and well E-2), although there are exceptions (e.g., well I-1 and well I-2). Comparisons
between the flowback water chemistry produced from the different members of the formation or
even between wells completed in the same member are complicated as the chemistry is impacted
by variables related to well completion, including the hydraulic fracturing fluid chemistry, the
number of stages, and shut-in time, in addition to the properties of the formation, the response of
the well to hydraulic fracturing, and the length of the flowback period. Longer shut-in periods in
particular were found to correlate with higher TDS and major ion concentrations in the flowback
water (see Chapter 4) which would contribute to the variability between wells, unrelated to the
The rate of increase in TDS and the major ion concentrations during the flowback period
can vary between different wells. For some wells the flowback water major ion concentrations
28
do not reach a stable plateau concentration by the end of the sampled flowback period as has
been observed in the flowback water from other formations (e.g., Marcellus Shale – Blauch et
al., 2009; Haluszczak et al., 2013; Horn River Basin – Zolfaghari et al., 2016). The increase in
ion concentrations over the full length of the flowback period for some wells has been attributed
to the development of a more extensive fracture network due to the access to a greater volume of
formation water (Bearinger, 2013; Ghanbari et al., 2013; Zolfaghari et al., 2015a). However, the
major ion concentrations must eventually reach a plateau as the formation water acts as an
29
a. b.
c. d.
e. f.
Figure 2.3: Flowback water TDS for the study sites plotted as a function of the cumulative volume of
flowback collected. a) Site A wells – upper Montney Formation; b) Site B wells – upper Montney Formation;
c) Site D wells – upper (well D-1 and well D-2) and middle (well D-3 and well D-4) Montney Formation; d)
Site E and Site F wells – middle Montney Formation; e) Site G and Site H wells – middle (well G-1) and upper
(well H-1) Montney Formation; f) Site I wells – lower Montney Formation. These plots do not include the
c. d.
e. f.
Figure 2.4: Flowback water TDS plotted as a function of percent recovered. The overall trend of the TDS vs.
percent recovered is comparable to the trend in TDS vs. cumulative flowback volume (Fig. 2.3). a) Site A
wells – upper Montney Formation; b) Site B wells – upper Montney Formation; c) Site D wells – upper (well
D-1 and well D-2) and middle (well D-3 and well D-4) Montney Formation; d) Site E and Site F wells – middle
Montney Formation; e) Site G and Site H wells – middle (well G-1) and upper (well H-1) Montney
Formation; f) Site I wells – lower Montney Formation. These plots do not include the produced water samples
Mixing between the injected hydraulic fracturing fluid and the formation water is the
most probable mechanism for the increasing TDS over the flowback period. The approximately
linear relationship between the major ion concentrations provides support for mixing as a
dominant influence since a linear relationship suggests mixing between higher concentration and
lower concentration fluid sources (Fig. 2.5). Although the Montney Formation generally has low
water saturation (e.g., Wood, 2015), the high surface area accessed by the created fracture
network and any natural fractures in the formation increases the area of contact and thus
increases the accessible formation water. Mixing between the formation water and the hydraulic
fracturing fluid would occur in the fracture space. Additional access to formation water may be
Dehghanpour et al., 2013; Rokhforouz and Amiri, 2017). When the hydraulic fracturing fluid is
injected into the formation, a large portion of the fluid is imbibed into the formation (Engelder et
al., 2014). Imbibition experiments have shown that shale samples placed in deionized water
result in an increase in conductivity in the water over the length of the experiment (e.g.,
the movement of formation water, in addition to oil and/or gas, out of the rock through
countercurrent imbibition. Physical mixing would occur between the formation water and the
remaining hydraulic fracturing fluid in the fractures. Other potential sources of the high TDS are
diffusion of the ions in the formation into the injected fluid and osmosis, where water would
move into the formation and the ions in the remaining fluid in the fractures would become more
concentrated (Balashov et al., 2015; Zolfaghari et al., 2016; Wang et al., 2016; 2017). Based on
32
the available data, the influence of diffusion and/or osmosis cannot be separated from the
influence of mixing with formation water accessed in the fracture spaces and through
countercurrent imbibition.
a. b.
Figure 2.5: Examples of the linear relationship between selected major ions in the Montney Formation
flowback water. a) Na-Cl plot; b) Ca-Mg plot. The relationship between the major ions supports mixing
between two endmembers – the injected hydraulic fracturing fluid with relatively low TDS and the high TDS
formation water. The three samples with elevated Cl concentrations at site B are from well B-1 at the end of
the flowback period, following a 24 day shut-in period. The flowback water results are grouped by site
although the site D wells are divided into the upper (u) and middle (m) Montney Formation wells. ▲- upper
Montney Formation wells; - middle Montney Formation wells; - lower Montney Formation wells.
In order to calculate the relative percentages of hydraulic fracturing fluid and formation
water contributing to the flowback water over time for the study wells, the Cl concentrations,
δ18O values, and δ2H values are used as conservative tracers. The use of the Cl concentrations
and the isotopic values as conservative tracers for mixing between the injected hydraulic
33
fracturing fluid and the formation water endmembers is supported by cross plots of these
parameters plotting along a straight mixing line (Fig. 2.6). The mixing between the hydraulic
fracturing fluid and the formation water to produce flowback water can be represented by the
𝐶 𝑓 = 𝐶 𝑓 + 𝐶 𝑓 (1)
Where CFB is the value in the flowback water, f FB is the proportion of flowback water, C HF is the
value in the hydraulic fracturing fluid, fHF is the proportion of the hydraulic fracturing fluid, CFW
is the value in the formation water, and f FW is the contribution of formation water as a
percentage. For the equation, the term 'value' represents either the Cl concentration in mg/L, or
the δ18O and δ2H values in per mille (‰). As the conservative tracers can be explained through
mixing between two fluid sources, without any influence from mineral precipitation and/or
dissolution, it can be assumed that f FB = fFW + fHF = 1. Equation 1 can then be transformed to
𝑓 = × 100% (2)
The use of Cl concentrations in combination with the isotopic values to calculate the mixing
ratios allows for some verification of the results and can indicate where variability in the data is
real or due to potential analytical errors. Mixing percentages calculated using conservative
tracers can be used to determine if other potentially non-conserved ions are being influenced by
geochemical processes other than mixing by comparing the analytical results to the modelled
results.
34
a. b. c.
Figure 2.6: Cross plots between the conservative tracers used to calculate the mixing ratios for this study.
The linear trend between the injected hydraulic fracturing fluid and the formation water indicates mixing
between the two endmembers. Data from Site I (well I-1 and well I-2) are provided as an example. a) Cl
concentrations versus δ18O values; b) Cl concentrations versus δ2H values; and c) δ2H values versus δ18O
values.
The input parameters for calculating mixing include the Cl concentrations and isotopic
values for the hydraulic fracturing fluid and the formation water (Table 2.3). These parameters
are measured in the flowback water (Table 2.4) and can be compared to the mixing model.
Based on the TDS of the injected hydraulic fracturing fluid, both freshwater-based fluids (TDS <
2,000 mg/L) and blended fluids composed of a mixture of freshwater and recycled flowback
water (TDS > 3,000 mg/L) were used for the study wells. Freshwater-based fluids were used for
well A-3, the site D wells (1 to 3), well H-1, and the site I wells. Blended fluids were used for
the remaining site A wells, well D-4, and all wells on sites B, E, F, and G.
35
Table 2.3: Summary of the δ2H values, δ18O values, and Cl concentrations of the hydraulic fracturing fluids
Notes:
Isotopic values for the hydraulic fracturing fluids are averages of several samples for all
except site F and site I wells, which are based on one sample for each of these sites.
Cl concentrations for the hydraulic fracturing fluids are calculated based on the volumetric
proportions of the composite samples.
Isotopic values for the formation water for well A-7, site D-G wells, and well H-1 are
average values based on the produced water samples collected at nearby sites in this study.
Cl concentrations for the formation water for site A and site B wells are averages of the
produced water samples collected at each of these sites. Cl concentrations for other sites are
based on publically available data for nearby wells.
36
Table 2.4: Range of the δ2H values, δ18O values and Cl concentrations over the flowback period for flowback
Overall, the Cl concentrations and the stable isotopes used as conservative tracers in the
study show that the percentage of formation water increases approximately linearly over the
flowback period at each of the wells, although the rate of increase varies between wells. The
37
range in the contribution of formation water at the beginning of the flowback period for the study
wells is generally approximately 10 to 35% and increases to approximately 40 to 60% at the end
of the flowback period (Table 2.5). Each of these ranges represent the 25 th to 75th percentiles of
the proportion of formation water calculated for the initial and final flowback water samples,
respectively, for the study wells. Well A-1, well A-6, well B-1, and well D-1 show over a 100%
contribution from formation water, depending on which conservative tracer is used, indicating
that the late flowback water is in some cases similar to produced water and that the values for the
formation water endmember were underestimated or that the linear mixing model does not
account for all the variance due to other geochemical processes such as mineral dissolution.
38
Table 2.5: Summary of proportions of formation water contributing to the flowback water for the
conservative tracers used in the study. The minimum value is early in the flowback period, while the
39
2.5 Variability in mixing ratios
The variability in the mixing ratios between the different conservative tracers, over the
flowback period at individual wells, and between sites provides insight to the reservoir
mechanics. In the following section each of these sources of variability are discussed and the
The mixing ratios show some variability depending on whether Cl concentration or δ 18O
and δ2H isotopic values are used to calculate the percentage of formation water (see Table 2.5
above). There is no indication that one of the tracers is consistently over- or under- estimating
mixing as the calculated mixing percentage is not regularly higher or lower when using a
particular isotope or the Cl concentrations. However, when examining the data for a single well,
one of the parameters used to calculate the mixing ratios often estimates the highest or lowest
ratio for all of the samples from the well. Part of the variability in determining the mixing ratios
may be due to the uncertainty in estimating the values to use for the formation water, as the exact
values are unknown, and potentially due to variations in formation water chemistry within the
fractured zone which is not taken into account as a constant value is used to represent the
formation water chemistry at each well. In some cases, the isotopic values may be representative
of the true formation water chemistry values whereas the Cl concentrations may be inaccurate
resulting in variability in the ratios calculated with the different tracers. Geochemical processes
such as carbonate dissolution or leaching of clays could potentially have some influence on the
Cl concentrations but not the isotopic values. Produced water samples were not available for the
majority of the study wells and even when available are not expected to represent 100%
formation water as complete mixing would likely not occur. In general, using the produced
40
water chemistry for the formation water chemistry should underestimate the TDS in formation
water as the produced water is likely somewhat diluted by the injected fluids from pure
formation water. However, the produced water Cl concentrations and isotopic values used in this
study are within the range expected for formation water (e.g., Wei et al., 2010 [Cl]; Rostron and
Holmden, 2000 [isotopes]) and are considered reasonable estimates given the difficulty of
directly sampling formation water from the Montney Formation as it is near irreducible water
saturation (e.g., Wood, 2015). Calculating the mixing ratios using Cl concentrations, δ 18O
values, and δ2H values provides a method to evaluate the calculated ratios three times for the
same data point. The range in the proportion of formation water using the three tracers generally
falls within a standard deviation of 5% and 15%, based on the 25 th and 75th percentiles for all
standard deviations in the studied samples. In cases where the three mixing ratios show some
disagreement, the results can be used to provide a range of mixing ratios for the sample.
2.5.2 Mixing ratio variability over the flowback period for individual wells
approximately linearly over the time sampled, there are occurrences where the fraction of
formation water shows a brief positive or negative spike (Fig. 2.7). Positive spikes indicate an
increase in the proportion of formation water as reflected by an increase in TDS and major ion
concentrations. The increases and decreases in the contributions from formation water are
consistent for all 3 tracers (Fig. 2.7) indicating that they are due to mixing inasmuch as Cl
concentrations and the isotopes would not both be affected by the same analytical errors or the
same geochemical reactions. Halite dissolution is one example of a potential reaction which
would only cause an increase in Cl concentrations and not affect the isotopes.
41
Figure 2.7: Fraction of formation water calculated for well D-4 using the three conservative tracers – Cl
concentrations, δ18O, and δ2H. The ratios show good agreement early in the flowback period, with lower
ratios calculated using the two isotopes later in the flowback period. The discrepancy later in the flowback
period may be due to the error around estimating the values of the formation water or a source of Cl from
another geochemical process. The brief increase in the contribution from formation water near 800m3 of
cumulative flowback is recorded in all three tracers; however, the magnitude of the change in mixing ratio is
not consistent for all three tracers. This well shows an increase from 9.9 to 16.3% formation water in the
sample collected at approximately 630 m3 of cumulative flowback water to 22.9 to 38.4% formation water in
the sample collected near 800 m3 of cumulative flowback water. This increase in the percentage of formation
studies where chemical tracers are used (e.g., Sullivan et al., 2004). This variability may be due
to opening or closing of the induced fracture systems at different times during flowback as the
pore pressure declines. For example, an increase in the overall proportion of formation water
would represent the contribution of flowback water from a stage where fracturing was more
extensive and there is a higher surface area exposed resulting in a greater input from formation
water relative to other stages. Variability in formation water chemistry along the lateral could
42
also contribute to the brief changes in the flowback water chemistry as different areas begin to
flow back. Another potential explanation for the spike in concentrations is a brief shut-in period
during the flowback period, which would be expected to cause an increase in TDS and the
percentage of formation water due to more time for mixing, as shown by an increase in the
contribution from formation water. An example of an increase in TDS following a shut-in period
occurs near the end of the flowback period at well B-1 when there was a shut-in period of 24
days near 3,000 m3 cumulative flowback volume, which corresponds to the spike late in
flowback period of this well (see Fig. 2.3b above). There were short periods of flow of up to 2
days for the first 15 days of the 24 day shut-in period, followed by no flow over the final 9 days.
Sites where the increase in formation water is more constant may have more constant mixing for
the different stages or the sampling frequency may miss the pulses of water from certain stages.
In addition to variability in the mixing ratios over the flowback period of a single well,
the percentage of formation water contributing to flowback water throughout the flowback
period as well as the rate of increase in the proportion of formation water fluctuate between
wells. Since the proportion of formation water is expected to increase over the flowback period,
wells with longer flowback periods would be anticipated to have a higher proportion of
formation water at the end of the flowback period as more time would allow for more mixing to
occur in the newly created fractures. However, the maximum percentage of formation water for
a well and the length of the flowback period only show low to moderate correlations, depending
on if the Cl concentrations (R2 < 0.1) or the isotopes (R2 ≈ 0.3) are used to calculate the
proportion of flowback water. The low to moderate correlations indicate that the amount of
formation water contributing to flowback water does not increase at the same rate for all wells.
43
Factors that could be contributing to the inconsistency include the shut-in time prior to flowback,
and the complexity of the fracture network. There is a moderate positive correlation (R 2: 0.68)
between the length of the shut-in period and the TDS in the initial flowback water (Fig. 2.8a). A
longer shut-in time prior to the commencement of the flowback period allows for more time for
mixing within the reservoir and produces an initial liquid with a higher proportion of formation
water and therefore higher major ion concentrations (Fig. 2.8b). In addition to mixing during the
shut-in period, there would be more time for imbibition, diffusion, and/or osmosis which would
all increase the TDS of the flowback water. Another important variable is the complexity of the
fracture network. A more complex fracturing network would also allow for more mixing and
thus a higher proportion of formation water in the flowback due to the greater surface contact
area (Bearinger, 2013; Ghanbari et al., 2013; Zolfaghari et al., 2015a). The extent of the fracture
network, or the stimulated reservoir volume, was not quantified in the present study since no
44
a. b.
Figure 2.8: a) Correlations between the TDS of the initial flowback (FB) water samples from each well and
the shut-in time following hydraulic fracturing and before the beginning of the flowback period. There is a
moderate correlation which indicates that a longer shut-in time is associated with higher TDS in the early
flowback samples. This may be related to a higher percentage of formation water; b) Correlation between
the minimum percent of formation water at a well and the shut-in time using the proportion calculated with
all three of the tracers. The moderate correlation indicates that wells with a longer shut-in time have a higher
The majority of the mixing proportions show some variability in the percentages
calculated using the different tracers; however, greater inconsistencies are seen in the samples
from wells from sites B, E, and F. The reason for the greater differences observed for the wells
from these sites are unknown but one of the possibilities is that the presence of organic
contaminants in some samples were not removed effectively by the activated charcoal treatment,
interfering with the isotopic values and producing anomalous mixing ratios. Sites B and E have
unexpectedly high mixing ratios when the δ18O values were used in the calculations. At site F,
45
the mixing ratios calculated using the isotopic values were relatively invariant or decreasing.
The flowback water samples from the site F wells were treated with a sodium hypochlorite
(NaClO) solution to remove hydrogen sulfide (H2S) prior to sampling. This solution contains
water; however, the volume of the NaClO solution used in the treatment only represents
approximately 1% of the total fluid flowback volume and would thus not be expected to impact
the isotopic values significantly. The isotopic values are therefore likely contaminated. The Cl
ions produced as part of the reaction between NaClO and H 2S did not have a detectable influence
on the overall Cl concentrations as increasing concentrations were still measured over the
flowback period from the site F wells. The percentages of formation water calculated using the
Cl concentrations for the potentially contaminated samples provide a check for the isotope data
An additional potential source of variability in the mixing ratios is the addition of a third
fluid endmember. Only one of the study wells shows some potential indication of another water
source. The site H well initially shows good agreement between the ratios calculated using the
different tracers until approximately 400 m3 of flowback water had been recovered from the
well. Later samples show a higher proportion of formation water when Cl concentrations are
used (55-86% formation water) relative to the ratios calculated with the isotopic values (15-51%
formation water). The inconsistency may be due to a third source of water with higher Cl
concentrations and lower isotopic values. The other source of water could be due to fracturing
out of zone or accessing high permeability lenses with a different formation water chemistry.
The isotopes show some indication of an additional water source as the trend of the flowback
samples does not follow a mixing line from the injected hydraulic fracturing fluid to the
the estimated formation water values is shown as a dashed line. The later flowback samples begin to plot
Further to mixing between the injected hydraulic fracturing fluid and the formation water,
(Blauch et al., 2009; Wilke et al., 2015; Dieterich et al., 2016; Harrison et al., 2017; Marcon et
al., 2017) and ion exchange (Renock et al., 2016; Zolfaghari et al., 2016), may influence the
concentrations of some of the major ions over the flowback period. In order to determine if the
concentrations of the major ions can be explained based solely on mixing, the major ion
concentrations of the analyzed flowback water samples are plotted with the calculated mixing
ratios and compared to the major ion concentrations predicted by the geochemical models.
Model I looks only at mixing between the injected fluid and the formation water, using the
chemistry results summarized in Table 2.6. In wells where only mixing between these two fluid
sources does not explain the measured concentrations of the major ions in flowback water, more
47
complex models including secondary mineral precipitation (Model II), ion exchange (Model III)
and/or carbonate dissolution (Model IV) are used to determine other factors influencing the
Table 2.6 (following page): Summary of the hydraulic fracturing fluid chemistry and the formation water
chemistry. The hydraulic fracturing fluid chemistry includes a summary of the calculated chemistry from
the composite samples for each well. The formation water chemistry is based on the median values for the
produced water samples collected in the present study (sites A, B, and I) and the produced waters from
nearby wells with publically available results (sites D-H). The temperature used in the model for the
hydraulic fracturing fluids was 25°C and the temperature used for the formation water was 75°C. Units are
mg/L.
48
Total
Site Well pH TDS Cl Na Ca Mg K Sr SO4
Alkalinity
Hydraulic Fracturing Fluid
1 6.8 108 15,285 10,276 3,212 1,004 162 181 161 8.5
2 6.5 96 16,802 10,423 3,873 1,428 227 226 245 25
3 7.3 76 239 71 69 42 22 21 <10 18
4 6.7 86 25,297 18,108 4,555 1,566 256 255 309 15
A
5 6.7 94 28,072 19,850 5,365 1,791 274 273 332 18
6 6.7 89 16,824 11,365 3,486 1,052 205 224 217 15
7 7.2 81 3,386 966 1,733 420 59 63 59 20
8 6.7 110 25,382 17,495 5,046 1,724 261 280 295 4
1 7.5 157 22,018 6,276 11,973 2,828 299 379 160 45
B
2 7.3 134 23,459 6,432 12,980 3,067 284 417 175 41
1 7.3 64 549 160 208 46 10 11 1 78
2 7.1 87 1,284 639 398 58 12 46 2 98
D
3 7.2 66 711 289 209 50 10 10 1 104
4 7.1 258 4,717 2,044 1,605 142 29 241 6 273
1 6.5 171 11,246 6,414 3,659 608 96 187 59 129
2 6.6 107 5,052 3,150 1,237 322 53 96 28 95
E
3 6.4 152 6,059 3,842 1,546 323 53 89 16 111
4 6.8 161 8,464 4,740 2,788 453 79 150 47 112
F 1, 2 7.0 83 12,218 7,448 3,948 372 60 105 25 165
G 1 7.2 150 5,604 1,841 3,047 305 64 137 40 74
H 1 4.9 3 786 5.1 573 42 16 11 <1 28
1 7.7 242 1,849 1,204 66 74 16 8 <1 <0.1
I
2 7.7 258 1,863 760 67 77 16 8 <1 <0.1
Formation Water
A 7.1 201 125,443 90,395 25,191 7,638 1,073 1,365 1,297 82
B 5.1 84 181,321 128,802 32,591 14,835 1,469 1,982 1,037 155
D-F 6.9 238 97,354 60,215 29,050 5,375 778 1,575 869 73
a
G 6.8 166 67,172 47,585 18,850 3,897 600 578 119 1,320
H 6.2 116 129,744 77,735 34,800 5,635 1,100 2,010 115 489
I 5.9 63 91,254 89,168 54,000 10,000 1,140 2,040 1,620 <0.1
Note:
a – The formation water Cl concentration for site G uses the 75th percentile instead of the median since the median
Cl concentrations from the produced waters from nearby wells was lower than the measured Cl concentrations in the
last flowback water sample from this well.
49
2.6.1 Sodium and potassium
Model I provides a moderate to good fit for the measured Na and K concentrations in
flowback water, indicating that mixing is the dominant process influencing these ions (Fig. 2.10).
There are some sites where the concentration of Na and/or K still follow a linear increase but are
slightly lower or higher than those predicted by the mixing model indicating that the
concentration used for formation water is over- or under-estimated in the model. Since a linear
increase is apparent, the changing concentrations are in most cases not interpreted to be
The site B wells in particular have high Na concentrations in late flowback water with the
last three samples having higher major ion concentrations relative to the formation water
endmember. The percentage of formation water calculated based on the δ 2H values and the Cl
concentrations are not in agreement for the well B-1 samples, indicating other geochemical
processes (e.g., mineral dissolution) impact the flowback water chemistry. The elevated Na
concentrations in the later samples at well B-2 are higher than predicted by the mixing model;
however, the percentage of formation water is generally in agreement between the δ 2H values
and the Cl concentrations, supporting mixing between endmembers. Such results indicate that
there was an increase in the contribution from formation water rather than mineral dissolution, as
both the Cl concentrations and the δ2H values were similarly impacted.
Well A-1, well D-2, well E-2, well E-3, and well H-1 have a good fit between the
modelled Na and K concentrations and the mixing ratios based on Cl concentrations but not the
isotopes. The difference in model fit for different ions may be related to the uncertainty in the
formation water chemistry and/or potential changes in the formation water over the flowback
Figure 2.10: Modelled and measured results for (a) Na; and (b) K concentrations for well I-1, provided as an
example. There is little difference in the modelled results with only mixing (Model I) compared to mixing and
ion exchange (Model III) for these parameters. The initial mixing ratios calculated using Cl concentrations
are lower than the mixing ratios calculated using the isotopes; however the mixing ratios near the end of the
flowback period show good agreement. The mixing ratios calculated using Cl concentrations show a better fit
for Na concentrations, while the mixing ratios calculated using the isotopes show a better fit for K
concentrations.
The addition of secondary mineral precipitation in Model II does not influence the Na or
K concentrations as no Na or K bearing mineral phases are included in the model nor anticipated
based on chemistry. In Modell III, the addition of ion exchange changes the modelled
concentrations slightly for these two ions (Fig. 2.10). The CEC of the Montney Formation was
estimated from a series of 15 samples with varying clay content (Table 2.7). The results indicate
that the CEC is low. There is some indication that lower CEC is associated with lower clay
content; however, the overall correlation is weak (R 2 = 0.01) due to the limited range in both clay
and CEC in the Montney Formation. This makes it difficult to estimate the CEC without
51
conducting a CEC analysis for samples in each of the study areas. A median value was selected
for the model, which may overestimate the CEC for some wells and underestimate it in other
wells. The addition of ion exchange to the model increases the Na concentrations slightly
relative to mixing alone. The increase in Na concentrations in the model when ion exchange is
added is likely related to the addition of the relatively low TDS hydraulic fracturing fluid into the
formation which causes Na ions to desorb from the cation exchange sites on clays present in the
formation. This process would be similar to ion exchange which occurs when injecting
freshwater into a saline aquifer, which shows characteristic breakthrough curves as the Na ions
are initially mobilized in exchange for the less mobile divalent ions (e.g., Appelo, 1994). The
effect of ion exchange on K concentrations in the flowback water varies with the site. Ion
mixing alone although the change in K concentrations is often minimal and not discernable when
graphically comparing models with mixing only and with mixing coupled with ion exchange.
52
Table 2.7: Summary of CEC and mineralogy of selected Montney Formation samples. These samples were
selected to represent a range in clay contents. The results are presented with increasing CEC.
The measured Ca, Mg, and Sr concentrations in flowback water are predominantly lower
than predicted by mixing alone indicating that these divalent ions are removed from solution
(Fig. 2.11). Potential processes that could remove Ca, Mg, and Sr ions from solution are
secondary mineral precipitation and adsorption through ion exchange. When only mixing is
considered in Model I, calcite, dolomite, and aragonite are generally oversaturated (SI > 0) in the
fluid produced by mixing the hydraulic fracturing fluid and the formation water. The
oversaturation of these minerals is in agreement with what is observed in the sampled flowback
water. When the percentage of formation water is low (< 15%) in the model, calcite, dolomite,
and aragonite are undersaturated (SI < 0) in the mixed fluids for many of the wells. These
minerals are undersaturated due to the chemistry of the injected fluid. Initially, calcite has a
negative SI for modelled results from wells A-2, A-3, A-6, D-1, D-2, D-3, the site E wells, the
53
site F wells, and well H-1, while dolomite and aragonite are initially undersaturated in the model
precipitate during the flowback period, and in doing so, will decrease the SI of dolomite and
aragonite causing the mixed fluids to be undersaturated in these two minerals for all wells. The
addition of calcite precipitation does not cause a significant decrease in the modelled Ca
concentrations and the concentrations generally continue to remain above the Ca concentrations
observed in the flowback water samples. The relative Ca concentrations decrease by up to 12%
when comparing the results of Model I (mixing only) and Model II (calcite precipitation), with
the vast majority of Ca concentrations decreasing by less than 5% (median: 0.8% relative
decrease) when calcite precipitation is added. The minor change in Ca concentrations due to
calcite precipitation indicates that secondary precipitation does not have a large effect on Ca
concentrations in flowback water even when calcite precipitates to equilibrium. The flowback
water samples are generally oversaturated with respect to calcite (SI > 0) which indicates that the
mixed fluids have not reached equilibrium with calcite and that there would be less calcite
precipitation occurring in the reservoir than predicted in the Model II which was set to reach
equilibrium and does not take the reaction kinetics into consideration.
Ca/Mg molar ratio over the flowback period. A decreasing Ca/Mg molar ratio indicates that
calcite is precipitating (Barbot et al., 2013). In our study, a decrease in the Ca/Mg ratio is only
observed in the flowback water from two of the wells – well B-1, which shows only a slight
decrease, and well H-1. The calcite saturation indices for well B-1 indicate that calcite is
oversaturated in the flowback water although the saturation indices are relatively stable over the
54
flowback period, while well H-1 flowback water shows an increase in calcite SI over the
flowback period from near equilibrium to slightly oversaturated under reservoir temperature.
The increasing calcite saturation indices may indicate that equilibrium through calcite
precipitation was reached in the initial samples but not later in the flowback period. The Ca/Mg
ratios for the remaining study wells are generally constant or show an increase over the flowback
In addition to calcite, celestite is oversaturated (SI > 0) for the mixed fluids for well G-1
when the proportion of formation water contributing to the flowback water reaches 75% or
decrease in Sr concentrations is not observed in the late flowback water samples from well G-1
(approximately 50-85% formation water) indicating that celestite is not precipitating in the well
due to the kinetics of the reaction. Celestite is slightly oversaturated (0.1 < SI < 0.3) at reservoir
temperature (75°C) in the flowback water samples obtained from this well; however, the SI
decreases at lower temperatures and is close to equilibrium (-0.1 < SI < 0.1) at 15°C.
The addition of ion exchange in Model III predicts a decrease in Ca, Mg, and Sr
concentrations in the flowback for the majority of sites (Fig. 2.11). The relative decrease in the
concentrations of the divalent ions is greatest when the proportion of formation water is low.
Model III shows the process of the hydraulic fracturing fluid coming into contact with the ion
exchange sites in the formation. As discussed in Section 2.6.1, the divalent cations would adsorb
on ion exchange sites in place of the more mobile Na ions, causing a decrease in the aqueous
concentrations of the divalent ions. The addition of ion exchange improves the fit of the
geochemical mixing model to the experimental results for the divalent major ions in most wells
(Fig. 2.11). The site B wells are the only wells which do not show a significant decrease in the
55
modelled Ca, Mg, and Sr concentrations when ion exchange is added to the geochemical model.
The hydraulic fracturing fluid used for the two wells at site B includes a high proportion of
recycled flowback water with elevated TDS (> 15,000 mg/L) as well as higher δ 18O and δ2H
values compared to those measured in the hydraulic fracturing fluids used at other sites (see
Table 2.5). The higher TDS and isotopic values are attributed to a greater proportion of recycled
water. As the injected fluid shows a greater degree of similarity to the formation water, less ion
Figure 2.11: Modelled and measured results for (a) Ca; (b) Mg; and (c) Sr concentrations for well I-1. The
modelled results are represented by the lines, while the measured results with the percentages of formation
water calculated with Cl, δ18O, and δ2H are represented as data points. The results from Model I and Model
II show very little difference for Ca concentrations. When mineral precipitation is included, calcite
precipitates until SI = 0 in order to represent the maximum amount of precipitation that could occur. There
is no difference between Model I and Model II for Mg and Sr concentrations as no minerals containing Mg or
Sr were predicted to precipitate for this well. The addition of ion exchange in Model III decreases the Ca,
Mg, and Sr concentrations. As was observed for Na and K, the proportions of formation water are initially
lower when calculated with Cl concentrations compared to δ18O and δ2H isotopes. The Sr concentrations
show the best fit to the modelled concentrations. The calculated proportion of formation water for the Ca
and Mg concentrations are higher than those predicted by the geochemical model, possibly relating to
56
The Ca, Mg, and Sr concentrations predicted by Model III remain higher than the
measured concentrations in flowback water from some wells. Some sites also show differences
in the fit of the model depending on if Cl concentrations or one of the stable isotopes are used to
calculate mixing. For example, for well I-1 the mixing ratios based on the Cl concentrations
show a better fit to the model than the mixing ratios calculated with the isotopic values for the
early flowback period (Fig. 2.11a). Over- or under-estimating the formation water chemistry or
isotopic values in the model would change the slope of the mixing line, causing an offset in the
modeled and the measured values. The uncertainties in the values for formation water are
derived from not being able to directly obtain formation water samples from the study wells as
well as from the possibility of changes in the formation water chemistry as different zones of the
fractured area are accessed during the flowback period. One example where the formation water
value appears to be too low is for the Sr concentrations used for well H-1. The measured values
for Sr concentrations at this well are higher than the modelled values for the percentage of
formation water calculated using both the Cl concentrations and the stable isotopes. Only one
produced water sample from a well nearby site H included Sr concentrations in the analysis. The
concentrations of the other major ions in this produced water sample were below the 25 th
percentile for produced water results from the southeast region, indicating that the Sr
concentration in this sample would underestimate the concentration in formation water. Further
studies are necessary to characterize the variability in formation water chemistry across the
Montney Formation.
explanations for a model that does not accurately calculate the divalent ion concentrations
include uncertainty in the amount of ion exchange, the exclusion of organics in the model, or a
57
combination of these factors. The ion exchange value of 0.5 moles of exchangeable ions per kg
of water included in the model may be underestimated for some sites and overestimated for
others. A constant value was used to approximate the median CEC of 17.3 cmol (+)/kg. As
there was limited variability in the CEC for the 15 Montney Formation samples, the values for
exchange in the model would only vary from 0.25 to 0.55 moles of exchangeable ions per kg of
water, hence the use of the median value is not expected to influence the fit of the model
significantly (Fig. 2.12). A change in the ion exchange value in the model would impact all three
of these ions and in some circumstances, one of the ions may show a good fit with the current
model parameters (e.g., Sr concentrations in Fig. 2.11 above) whereby changing the ion
Figure 2.12: The modelled Mg concentrations for different ion exchange values in the geochemical model
using well I-1 as an example. Using 0.25 moles of exchangeable ions per kg of water presents the lower limit
based on the CEC results, while the upper limit (0.55) is close to the median value (0.5). A value of 1 mole of
exchangeable ions per kg of water is presented as a comparison above what is expected based on the CEC
measurements. There is not a great amount of variability between the different values for ion exchange.
58
Organic molecules can influence the mineral saturation indices in geochemical modelling
(Marcon et al., 2017) and have been shown to be involved in ion exchange in soils (e.g., Droge
and Goss, 2012). The organic compounds present in the hydraulic fracturing fluid and the
formation water were not considered in the present study but may influence the flowback water
geochemistry. More complex geochemical models with a greater understanding of the formation
water chemistry, the CEC, and the effect of organics on the CEC may further improve the model
fit.
potential process that may improve the fit of the model for the Ca and Mg concentrations.
Calcite has the potential to dissolve in some wells when the proportion of formation water is low,
due to the chemistry of the injected fluid. Negative calcite SI values were modelled for wells A-
2, A-3, A-6, D-1, D-2, D-3, the site E wells, the site F wells, and well H-1. As dolomite was
found to be undersaturated in the fluid following mixing and calcite precipitation, the chemistry
indicates that dolomite has the potential to dissolve in all wells. When both calcite and dolomite
are permitted to dissolve in the model, there is a significant increase in the Mg concentrations
above the observed flowback water concentrations due to dolomite dissolution (Fig. 2.13). In
this scenario, additional calcite precipitation occurs which causes a further decrease of the Ca
concentrations in the mixed fluid. If only calcite is permitted to dissolve, the Ca concentrations
do increase slightly when there is a negative calcite SI; however, the contribution of Ca ions
from calcite dissolution to bring the system to equilibrium (SI = 0) is minor relative to the
contribution from mixing with formation water. For example, at well H-1, the maximum amount
of calcite dissolution occurs in the fluid with 25% formation water. The difference in Ca
concentrations for a fluid with this mixing proportion between the models with and without
59
calcite dissolution is 18 mg/L, which is < 5% of the Ca concentration measured for a fluid with
Figure 2.13: Modelled and measured results for (a) Ca; and (b) Mg concentrations with the modelled results
for mineral dissolution. The addition of mineral dissolution results in dolomite dissolution, which causes an
precipitation. For the flowback water from this well, the Ca concentrations show a better fit; however, the
Mg concentrations show a significant increase which is not seen in the experimental results.
2.6.3 Sulfate
the Montney Formation flowback water do not show a consistent increasing trend over the
flowback period for the majority of the study wells, indicating geochemical processes other than
mixing. The measured SO4 concentrations are generally higher than the concentrations used to
approximate formation water in the model (Fig. 2.14). The elevated SO 4 concentrations may be
due to oxidation of pyrite (Wilke et al., 2015; Harrison et al., 2017) or the oxidation of H 2S, if
present, both processes potentially stimulated by the injection of the oxic hydraulic fracturing
60
fluid into the anoxic formation. Laboratory experiments have observed pyrite oxidation on time
scales relevant to hydraulic fracturing (Wilke et al., 2015; Harrison et al., 2017). Pyrite is
based on the XRD results compiled for samples from the areas near the study wells. H 2S gas is
found in elevated concentrations in some regions of the Montney Formation (Kirste et al., 1997;
Desrocher et al., 2004). H2S in the flowback water was not measured as part of the study,
although, the flowback waters from site A and site F contain detectable H 2S. The samples from
site A were collected prior to treatment for H2S. The SO4 concentrations in the site A flowback
waters are relatively stable over the flowback period and range from 51 to 234 mg/L for the
different wells. The SO4 concentrations are greater than the SO4 concentrations in the hydraulic
fracturing fluids (median: 18 mg/L) and often greater than the estimated value for formation
water at site A (82 mg/L). The site F samples were collected following treatment with NaClO to
remove H2S. Both site F wells show increasing SO4 concentrations over the flowback period up
to 824 mg/L, which is likely related to the production of H2SO4 during treatment with NaOCl.
The presence of the acid is supported by the decreasing pH in the flowback waters from these
61
Figure 2.14: Sulfate concentrations in the injected hydraulic fracturing (HF) fluid, the flowback water, and
the formation water for each of the sites. The SO4 concentrations in the flowback water are often higher than
the SO4 concentrations estimated for formation water, indicating that mixing is not the dominant process on
SO4 concentrations in flowback water. For sites with multiple wells, a median value is presented for the HF
fluid and the minimum, median, and maximum values for flowback water are calculated for the combined
dataset.
The SO4 concentrations in the flowback waters from site I are lower than almost all other
flowback water samples collected as part of the study (< 50 mg/L) and decrease over the
flowback period (Fig. 2.15). The relatively elevated SO 4 concentrations in the early flowback
waters are not related to SO4 concentrations in the injected hydraulic fracturing fluid which
remain below the detection limit (< 0.1 mg/L) but may be due to pyrite oxidation (Wilke et al.,
2015; Harrison et al., 2017). Bacterial SO 4 reduction likely contributes to the decreasing SO4
62
concentrations in the flowback water from the site I wells. The injection of the relatively fresh
hydraulic fracturing fluid, containing organic additives, reduces the salinity in the formation
making a more favorable environment for the bacteria (Engle and Rowan, 2014). The reduction
of SO4 could in turn increase the solubility of barite which would result in higher barium (Ba)
concentrations in areas where SO4-reducing bacteria are more active. The highest Ba
concentrations among the study wells were measured in the late flowback samples from well I-1
(215 mg/L) and well I-2 (467 mg/L), supporting this possibility. The Ba concentrations in the
Montney Formation flowback water from the study wells are presented elsewhere (see Chapter
5).
Figure 2.15: The SO4 concentrations over the flowback period at the site I wells. The elevated SO 4
concentrations measured earlier in the flowback period may be due to pyrite oxidation (Harrison et al., 2017;
Wilke et al., 2015), as they are not related to the SO4 concentrations in the injected hydraulic fracturing fluid,
which were less than 0.1 mg/L. The decreasing SO4 concentrations are interpreted to be due to bacterial SO4
reduction which may vary between wells due to the differences in the bacterial assemblage found in the
63
The SO4-bearing mineral celestite is slightly oversaturated (0 < SI < 1) in the flowback
water from only a few wells, including the well G-1 samples and some samples from the site A
wells. The potential for precipitation of celestite was considered in the geochemical model and
was discussed above in relation to the flowback water Sr concentrations. The geochemical
model predicts celestite precipitation in the later flowback water samples from well G-1 when
the model reaches equilibrium, which should correspond to a decrease in both Sr and SO 4
concentrations. However, the SO4 concentrations at well G-1 remain relatively constant (range:
1308 to 1407 mg/L) over the flowback period. The lack of a decrease in concentrations in the
flowback water results indicates that equilibrium has not been reached in the flowback water and
The major ion chemistry of the Montney Formation flowback water from the study wells
provides insight into the geochemical processes that are occurring in the reservoir. The overview
of the major ion flowback water chemistry showed that the major ion concentrations, and
therefore the TDS, increase over the flowback period, while the SO 4 concentrations are generally
invariant. These results are in agreement with studies on flowback water chemistry in other
formations (e.g., Haluszczak et al., 2013; Ziemkiewicz and He, 2015; Rosenblum et al., 2017).
There is some variability in the ion concentrations between wells; however, wells completed at
the same site and within the same member of the Montney Formation generally show greater
similarity in flowback water chemistry relative to those completed at different sites, which is
interpreted to be due to the wells on the same site having comparable completion parameters and
reservoir properties.
64
The increasing major ion concentrations in the flowback water over the flowback period
indicate that mixing between the relatively low TDS hydraulic fracturing fluid and the high TDS
formation water is the dominant geochemical process that is influencing the flowback water
chemistry. In addition to physical mixing between the injected fluid and formation water
accessed in the fracture network and through countercurrent imbibition, other potential
contributors to high TDS are ion diffusion (Balashov et al., 2015; Zolfaghari et al., 2016; Wang
et al., 2016; 2017), and/or osmosis (Wang et al., 2016; 2017). With the current data, it was not
possible to differentiate between these processes and all may be adding to the increasing TDS.
Through the use of Cl, δ18O, and δ2H as conservative tracers, the proportion of formation water
contributing to flowback water was calculated for each of the samples analyzed for the study
wells. There was variability in the proportion of formation water in the flowback water at
different wells over the flowback period. For the initial flowback water samples, the
contribution from formation water generally was in the range of 10-35%, while for the final
flowback water samples the formation water proportion was generally 40-60%. Since there is a
significant contribution from formation water, the actual volume of the injected hydraulic
fracturing fluid recovered during the flowback period is much less than the volume of total fluid
recovered. For the study wells, the calculated volume of hydraulic fracturing fluid recovered
based on the mixing proportions is typically < 10% of the injected fluid.
Studies conducted with flowback water in other formations have used the increasing Cl
concentrations (Olsson et al., 2013; Vengosh et al., 2017) and TDS (Kondash et al., 2017;
Rosenblum et al., 2017) to calculate the proportion of formation water in flowback water. The
percentage of formation water calculated in these studies for a flowback time similar to the late
flowback water in our study wells show either a comparable percentage of formation water at
65
approximately 50% (Kondash et al., 2017; Vengosh et al., 2017) or a higher percentage of
formation water (>90%; Olsson et al., 2013; Rosenblum et al., 2017). In the Rosenblum et al.
(2017) study, the higher proportion of formation water was attributed to a 30 day shut-in period
Our study also shows that the proportion of formation water is impacted by additional
factors. The low correlation between the highest proportions of formation water and the length
of the flowback period indicates that many variables are influencing mixing, including the length
of the shut-in period and the extent and complexity of the fracture system. The uncertainty in the
formation water chemistry due to not being able to directly sample the Montney Formation
flowback water may lead to some variability in the mixing ratio calculated with the different
tracers, as the values used may be accurate for one of the tracers but not others. Using three
tracers provided a method to check the results through a comparison of the three mixing ratios
obtained and allowed for a representative range in ratios to be determined for each flowback
water sample. In the site B, site E, and site F wells, the comparison between the mixing ratios
calculated with the three tracers indicated that some of the isotopic results were contaminated. In
well H-1, the use of multiple tracers allowed for the identification of potential mixing with a
third fluid source with a different geochemical signature, in addition to the hydraulic fracturing
fluid and the formation water. Potential fluid sources in addition to the injected fluid and the
The second portion of the study used geochemical modelling to determine if processes
other than mixing were required to explain the flowback water major ion chemistry. The Na and
K concentrations in the studied flowback water can be explained by mixing for the vast majority
of the study wells, while the Ca, Mg, and Sr concentrations were influenced by a combination of
66
mixing and ion exchange. Ion exchange causes the concentrations of the divalent ions to be
lower over the course of the flowback period, relative to if only mixing was occurring.
Sequential extraction experiments completed with Marcellus Shale samples by Stewart et al.
(2015) found that although Ca, Mg, and Sr ions were primarily associated with carbonates, these
ions were also present on the exchange sites indicating the potential for ion exchange. Ion
exchange has also previously been suggested as a contributing source of Na ions to flowback
flowback water may be minimally impacted by calcite precipitation; however, the majority of
wells do not show any evidence that calcite is precipitating in the formation, even though the
mixed fluids generally have a SI above 0. Experimental evidence from laboratory experiments
conducted by others does not support calcite precipitation in the reservoir and has demonstrated
that calcite dissolution is occurring (Lu et al., 2017). These experiments examined shale samples
by SEM before and after placing the sample in saline fluids under reservoir temperature and
pressure over a three week period. The geochemical models for wells A-2, A-3, A-6, D-1, D-2,
D-3, the site E wells, the site F wells, and well H-1 support the potential for calcite dissolution
when the hydraulic fracturing fluid is injected into the formation and the proportion of formation
water in the mixed fluid is low since the calcite SI is below 0. In the scenario which permitted
calcite dissolution without dolomite dissolution, the contribution of Ca ions from calcite
dissolution remained minor relative to the contribution from formation water, indicating that
even if calcite dissolution is occurring in the reservoir, mixing with formation water remains the
The SO4 concentrations were not accurately modelled by mixing and are often higher
than the values predicted in the mixing model. The elevated SO 4 concentrations may be related
67
to the oxidation of pyrite or H2S due to the injection of the hydraulic fracturing fluid as proposed
by Wilke et al. (2015) and Harrison et al. (2017). The decreasing SO 4 concentrations seen in the
flowback water from the site I wells may be related to SO4 reduction by bacteria as suggested
Overall, the results for the current study support mixing between the injected hydraulic
fracturing fluid and the formation water as the dominant process affecting the flowback water
chemistry. A more thorough examination of the flowback water chemistry; however, provides
show that the flowback water chemistry is influenced by processes in addition to mixing,
including ion exchange, pyrite oxidation, and SO4 reduction, through comparison of the
chemistry and the geochemical models. Further, more detailed studies looking at the variability
in the formation water chemistry, the effect of organics, and the importance of ion exchange
between different sites would improve the fit of the geochemical models and contribute to their
68
Chapter 3: Flowback water chemistry from the Montney Formation: Part I -
3.1 Introduction
Economic production of gas and liquid from ultralow permeability strata has been made
possible due to horizontal drilling and completions through hydraulic fracturing. Hydraulic
fracturing involves the injection of a large volume of hydraulic fracturing fluid (range:
approximately 2,000 to 50,000 m3 in total [Vidic et al., 2013; Alessi et al., 2017]) over up to 50
isolated intervals (stages) in order to create a complex fracture network thereby increasing the
system permeability of the reservoir. Following well completion, the well is put on production
resulting initially in the flow back of liquids (the flowback water 2) that are a mixture of the
injected fluids and the reservoir fluids. The total volume of the flowback water for most
unconventional reservoirs is approximately 25% of the injected fluid volume (Haluszczak et al.,
2013) but the volume is highly variable between wells and formations. Flowback water is
generally high in total dissolved solids (TDS) from the order of 1,000's to 100,000's of
milligrams per liter (e.g., Haluszczak et al., 2013; Kolesar Kohl et al., 2014). In addition to
major ions and trace metals, flowback water can also contain organics (e.g., Strong et al., 2014;
Lester et al., 2015) and radium (e.g., Nelson et al., 2016). Most commonly the TDS and the
major ion concentrations in flowback water increase during the flowback period, although this
depends on the chemistry of the injected water. Over time the concentrations in flowback water
2
In this paper, flowback water refers to water produced by a well prior to production, while the water returned to the
surface during production will be considered produced water. The transition from flowback water to produced water
is not necessarily distinct.
69
approach those in formation water (e.g., Blauch et al., 2009; Haluszczak et al., 2013). The
current explanation for the source of the TDS and the major ions is that the flowback water
chemistry is a product of mixing between the injected hydraulic fracturing fluid and the
formation water (e.g., Haluszczak et al., 2013; Olsson et al., 2013; Engle and Rowan, 2014;
Vengosh et al., 2017), and potentially influenced by water-rock interactions (e.g., Barbot et al.,
2013; Seales et al., 2016; Zolfaghari et al., 2016; Marcon et al., 2017).
environmental implications of hydraulic fracturing (e.g., Cooley and Donnelly, 2012; Vengosh et
al., 2013, 2014; Vidic et al. 2013; Connor et al., 2015; Reible et al., 2016; Ward et al., 2016) and
understanding the processes that are occurring in the reservoir (e.g., Barbot et al., 2013;
Bearinger, 2013; Ghanbari et al., 2013; Zolfaghari et al., 2015a). The environmental effects
studies often look at water management associated with hydraulic fracturing operations including
water use, flowback water disposal, and flowback water treatment for reuse (e.g., Fontenelle et
al., 2013; Vidic et al., 2013; Goss et al., 2015; Alessi et al., 2017). Geochemical studies that
identify unique chemical tracers (e.g., strontium isotopes, Cl/Br ratio) in flowback water have
been used to differentiate between the sources of the salinity between flowback water and other
saline water sources (e.g., Chapman et al., 2012; Capo et al., 2014; Johnson et al., 2015; Kolesar
Kohl et al., 2014; Ziemkiewicz and He, 2015; Zheng et al., 2017). Mineral precipitation and
dissolution in the reservoir can be inferred by examining ion ratios and the change in mineral
saturation indices in flowback water over time (Barbot et al., 2013). Laboratory observation of
both mineral precipitation (e.g., gypsum, barite, and anhydrite) and carbonate dissolution have
been recorded in studies with synthetic hydraulic fracturing fluids and shale samples under
70
elevated temperatures and pressures (Wilke et al., 2015; Dieterich et al., 2016; Marcon et al.,
2017).
The rate of increase of TDS and the major ion concentrations in flowback water over
time has been used to infer the complexity of the fracture system (Bearinger, 2013; Ghanbari et
al., 2013; Zolfaghari et al., 2015a). A continuous increase in TDS during flowback has been
higher surface area exposed to hydraulic fracturing fluid whereas a plateau in TDS in the late
Flowback water chemistry can vary even between wells completed in the same
formation. The study of the source of TDS in flowback water and the causes for variability in
chemistry between different sites is an important area of research since the flowback water
chemistry and rheology can provide insight on processes taking place in the subsurface during
hydraulic fracturing, including the nature of the stimulated reservoir volume (SRV), relative
merits of flowback control (i.e., slow-back vs fast-back), and propensity for scaling or corrosion
of tubulars or reservoir salting. A comparison of the flowback water chemistry between wells is
important in order to determine if there are trends in how the flowback water chemistry varies
water can assist in optimizing storage and/or treatment strategies and determining if recycling
(reuse) of completion fluid for future wells is practical and if so optimizing liquid blends. The
use of appropriate treatment and disposal methods is essential to minimize the risk of surface and
groundwater contamination related to incorrect storage and accidental spills of flowback water
71
In our study the flowback water from the Lower Triassic Montney Formation in
northeastern British Columbia and northwestern Alberta, Canada is investigated. The Montney
Formation is the most important producing unconventional hydrocarbon reservoir in Canada and
is currently being actively developed. The Montney Formation varies in lithology and reservoir
properties both aerially and stratigraphically. This formation is composed of fine grained
sediments including shale, dolo-siltstones, and fine-grained sandstone and overall becomes
coarser grained from BC to Alberta (Edwards et al., 1994; Dixon, 2000; Zonneveld et al., 2011;
Zonneveld and Moslow, 2014). Turbidite deposits are prominent near the BC-Alberta border
(Zonneveld et al., 2010) and dolocoquina subunits are found in the eastern regions in Alberta
(Davies et al., 1997; Davies and Hume, 2016). Overall, the Montney Formation becomes slightly
coarser with increasing depth, varying from siltstone to very fine grained sandstone-siltstone
(Davies et al., 1997; Dixon, 2000). Past stratigraphic studies on different regions of the Montney
Formation have focused on either BC (Dixon, 2000) or Alberta (Davies et al., 1997) but did not
cover the whole formation. The most recent subdivision of the Montney Formation into
(informal) lower, middle, and upper members is based on lithostratigraphy and biostratigraphy
(Davies and Hume, 2016). This subdivision is used in the present study (Fig. 3.1).
72
Figure 3.1: Schematic cross-section of the Montney Formation showing divisions between the lower, middle,
and upper informal members. Each member represents a Third-Order sequence. The lower Montney
Formation (Griesbachian-Dienerian stage) unconformably overlies the Permian Belloy Formation and
extends to the base of the lowstand wedge. The middle Montney Formation (Smithian stage) extends from
this lowstand wedge to the base of a second lowstand wedge. The upper Montney Formation (Spathian stage)
includes the second lowstand wedge and the lower Doig siltstone. This member thins to the east and is absent
In the study we collected and analyzed flowback water from 9 sites that include 31 wells
completed in the upper (18 wells), middle (11 wells), and lower (2 wells) members of the
Montney Formation (Fig. 3.2) as defined in figure 3.1. The study wells were completed at total
vertical depths between 1,775 and 3,230 m with the horizontal laterals of the wells ranging from
between 1,720 and 3,330 m long. The TDS and major ion concentrations of the flowback water
from the study wells are the focus of this paper. The major ions include chloride (Cl), sodium
73
(Na), potassium (K), calcium (Ca), magnesium (Mg), and strontium (Sr). The major ion
chemistry of the flowback water collected from the upper, middle, and lower Montney
Formation study wells is summarized and potential issues that may arise in comparing flowback
water chemistry between different locations are discussed. A method to compare the flowback
water chemistry from different wells using linear regression and linear mixed effects models is
presented.
Figure 3.2: Location of the sites (A-I) included in the study. Wells completed in the upper Montney
Formation are located at sites A through D, and site H, wells completed in the middle Montney Formation are
located at sites C through G, and wells completed in the lower Montney Formation are located at site I. The
lateral extent of the Montney Formations is shown in green (modified from Edwards et al., 1994).
74
3.2 Methods
Samples of hydraulic fracturing fluid (base liquid plus additives) were collected for the
majority of the wells sampled for flowback water. For wells completed on site A, site B, site D,
site E, site G, and site H, several hydraulic fracturing fluid samples were collected that are
representative of the fluids used in completing the multiple stages along the lateral. The samples
from the different stages of a well were combined into composite samples based on similar
electrical conductivity readings used as quick proxy for total dissolved solids. For the site F and
site I wells, one sample of the hydraulic fracturing fluid was collected to represent the fluids used
for each of these wells. The composite samples and the samples from site F and site I were
filtered through a 0.45 µm filter and analyzed for pH, conductivity, total alkalinity, anions, and
dissolved metals. All analyses were conducted at The University of British Columbia (UBC) in
Vancouver, BC, excluding the anion samples which were sent to a laboratory in Victoria, BC for
the ion chromatography analysis. The pH and conductivity were measured using an Omega ®
PHB21 potable pH meter and a HACH® CDC401 conductivity probe, respectively. The total
alkalinity was measured by titrating the solution with sulfuric acid (H 2SO4) using a HACH®
digital titrator (Model 16900). The dissolved metals samples were initially preserved with trace
metal grade nitric acid (HNO3) to pH < 2. In order to remove organic compounds that may
interfere with the inductively coupled plasma-optical emission spectrometry (ICP-OES), the
dissolved metal samples were then acid digested using trace metal grade HNO 3 and hydrochloric
acid (HCl) in a 2:1 ratio and evaporated in an acid-washed glass beaker on a hot plate. The
digested samples were treated a second time with concentrated HNO 3, re-evaporated, and then
re-diluted to the initial volume with a 1% HNO3 solution. The ICP-OES analysis was performed
75
on a Varian® 725-ES ICP-OES with indium (In) as the internal standard. The ion concentrations
The overall hydraulic fracturing fluid chemistry for the wells with composite samples
was calculated from the geochemical analysis of the composite samples and the relative
proportion of the fluid volumes used in each stage. For example, if 4 composite samples were
analyzed for a well and the hydraulic fracturing stages combined in each sample each represent
25% of the total fluid volume, then the chemistry of the 4 composite samples are given equal
weight in the overall fluid chemistry calculation. No hydraulic fracturing fluid samples were
Flowback water samples were collected from the 31 study wells. Two to three samples
were collected each day for the first week of the flowback period then sampling was decreased to
one sample per day in wells where the flowback period extended beyond one week. The
sampling schedule allowed for more sampling at the beginning of the flowback period when the
recovered fluid volume is typically greater and the fluid chemistry is expected to change more
rapidly. The samples were stored at 4°C and were then heated to reservoir temperature (75-80°C)
for 24 hours prior to analysis to re-dissolve any precipitates that formed due to cooling of the
flowback water after sampling. The heating step was included since it was logistically
impractical for the samples to be filtered and preserved with acid at the time of sample
collection. The samples were filtered and the same suite of analyses completed for the hydraulic
fracturing fluids were completed for the heated flowback water samples.
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3.2.3 Produced Water Chemistry
Produced water samples were included in the water sampling at site A, site B, and a well
nearby to site I. The produced water samples were prepared and analyzed following the same
steps as the flowback water samples. The results for the produced water samples were used to
provide a measure of formation water chemistry for the wells from these three sites. For the
remaining wells an approximation of the formation water chemistry was acquired from
publically available data3 from nearby wells with produced water results from the Montney
Formation. The publically available fluid data was evaluated and samples with anomalously low
conductivity values or with noted errors (e.g., contaminated sample) were removed. The suite of
parameters available typically includes calculated TDS, and measured pH, Cl, Na, K, Ca, and
Simple linear regression and linear mixed effects models were combined to conduct a
trend analysis as a method to investigate the relationship of both flowback water chemistry and
flowback water volume with flowback time for the different sites. All regression analyses in
support of this work were completed in R using the base package for linear regression (R Core
Team, 2017) and the lme4 package for the linear mixed effects models (Bates et al., 2015). The
initial step in the analysis was looking at the simple linear regression between the parameters of
interest for each of the individual wells. The simple linear regression with one covariate is in the
form of:
3
The publically available data is from data compiled by the BC Oil and Gas Commission and accessed through
geoSCOUT®.
77
𝑦 = 𝑥𝛽 + 𝜀
Where, y is the response variable, x is a covariate, β is the slope coefficient, and ε is the error
term. In our analysis, y is either the TDS, the concentration of one of the major ions, or the
flowback volume, while x is flowback time. If the slope coefficients in the linear regression are
sufficiently similar and the data contains a categorical variable, data can be combined and a
linear mixed effects model can be used in the analysis. A linear mixed effects model includes an
additional term which is used to group the results within a given category in order to look at
another level within the data (Bates, 2010). In its simplest form it includes one covariate for the
fixed effects:
𝑦 = 𝑥𝛽 + 𝑢𝛾 + 𝜖
Where, y is the response variable, x is a covariate for the fixed effects, β is the slope coefficient
for the fixed effects, u is a covariate for the random effects, γ is the coefficient for the random
To further explain how these models apply to the flowback water dataset, consider an
example where TDS results are available over the flowback period for 4 wells completed at the
same site. If a simple linear regression was conducted for TDS over time, the slope coefficient
(β) could be determined either for each individual well or for all results from the site combined:
This notation indicates that TDS is determined as a function of flowback time. When the goal of
the analysis is to examine the data at the site level, including the results for all the wells together
does not take into account that the TDS results for each individual well are related and are
expected to differ somewhat from the results from other wells at the site. Linear mixed effects
models will take the differences between wells into account while allowing the data for the site
78
to be examined together. In order to determine if a linear mixed effects model is appropriate for
grouping the wells at a site, a simple linear regression needs to be completed for each individual
well to verify that the slope coefficients show a high enough degree of similarity. For our
analysis, the slope coefficients were taken to be comparable when the slope coefficients with
their confidence intervals have overlapping values. A linear mixed effects model provides a
method to divide the combined results for the site using an additional level in the data, which in
This representation shows that TDS is determined as a function of flowback time for the site but
that the data are also grouped together by well. The linear mixed effects model is in the form to
allow for each well to have both a different slope and intercept from the other wells at the site
based on the TDS as a function of the flowback time. Using the linear mixed effects model will
give the overall fixed effects slope coefficient for the site, as well as the random effects
coefficient to take the differences between the individual wells into account. The random effects
are the differences within the data for each well that are not explained by the fixed effects term.
The fixed effects slope coefficient can then be used to compare the study sites, by grouping sites
which are correlated, which complicates comparisons between different wells and interpretation
of the geochemistry of the fluids. The variables include those that are dependent on the
properties of the reservoir, the completion design, and the response of the reservoir to the
completion (Table 3.1). The factors that are not directly related to the properties of the reservoir
79
can create variability between different wells, even at the same site, thus making it difficult to
Table 3.1: Summary of some of the variables that may influence flowback water geochemistry. Many of the
Response of reservoir to
Reservoir properties Completion design
completion
Due to the multiple variables that have the potential to alter flowback water
geochemistry, different methods of presenting and interpreting the results must be utilized and
are discussed in this paper. The parameter selected for the graphical representation of flowback
water geochemical results is an important consideration in flowback water studies as this can
impact the interpretation of the data (Fig. 3.3). Flowback water results are often plotted as the
80
concentration of the element of interest versus the number of days (i.e., time) since the beginning
of flowback (i.e., flowback day; e.g., Haluszczak et al., 2013; Capo et al., 2014; Ziemkiewicz
and He, 2015). However, flowback day cannot be studied independently of the shut-in time prior
to flowback, or percentage of flowback per day, to name a few of the plethora of parameters that
need be considered. Examples of different parameters for plotting flowback water chemistry
illustrate how the interpretation of the variation in the flowback water results can vary depending
on the parameter selected. For example, a plot of Na concentrations from one of the study wells
appear to approach a stable maximum value near 20,000 mg/L when cross plotted against
flowback day (Fig. 3.3a). However, when Na concentrations are plotted against cumulative
flowback volume, the percent recovered 4, the percent of the total flowback5, or Cl
concentrations, the Na concentrations continue to increase through to the end of the flowback
period (Fig. 3.3b-e). Ion ratios can also be used to look at geochemical results (Fig. 3.3f), where
in the presented example the Na/Cl ratio shows a slight decrease and then stabilizes.
4
The percent recovered is defined as the percentage of the injected fluid volume that has been recovered from the
well as flowback water. This does not represent recovery of only hydraulic fracturing fluid as there is mixing with
formation water occurring in the reservoir.
5
The percent of total flowback is the relative percentage of flowback water collected over the flowback period (i.e.,
the volume at the end of the flowback period is 100% of the total flowback volume).
81
a. b. c.
d. e. f.
Figure 3.3: Different potential variables for graphical representation of flowback water chemical data from
one well (data from well I-1). The parameters selected to represent the data influences the interpretation of
the flowback water chemistry. a) Na concentrations versus flowback day; b) Na concentrations versus
percent of total flowback water4; e) Na concentrations versus Cl concentrations; f) Na/Cl mass ratio versus
percent recovered.
Yet further complications in comparing flowback water geochemistry are that the studied
wells were flowed back for variable lengths of time prior to being put on production and that the
cumulative flowback volumes vary. As the major ions typically increase with both time and
cumulative flowback volume, any differences in these variables can impact the comparison
between wells. Wells with longer flowback periods and greater volumes of fluid recovered tend
to have higher concentrations of the major ions, relative to wells with a shorter flowback period
or lower flowback water recovery, everything else being equal. Due to the variability in the
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length of the flowback period, using minimum, median, or maximum concentrations is not an
effective way to characterize the flowback water chemistry for different wells. A well to well
comparison could be made by picking an arbitrary flowback day or flowback volume and
comparing the concentrations of the closest sample for each well. This method would require
the selection of a sample early on in the flowback period or with low cumulative flowback
volume in order to select a flowback time or volume that was represented by all wells in the
study.
Due to the factors summarized above, in-depth statistical analysis is required in order to
compare the flowback water geochemistry from different wells. Of the statistical methods tested
in our study, linear regression and linear mixed effects models proved to be the most promising
method and will be used in the present study to compare the different sites and wells.
The flowback water chemistry in the studied wells varies over the flowback period. In
general, the concentrations of the major ions, and therefore TDS, increase over the flowback
period (Fig. 3.4). The magnitude of the increase in TDS over the flowback period and the
maximum major ion concentrations attained are different between wells. Even though the
concentrations of the major ions vary, in all sampled waters Cl is the dominant ion, followed by
Na, Ca, and K (Table 3.2). Mg and Sr concentrations, although important, are lower than the
other major ions. The flowback water pH remains near neutral in the majority of samples (5 th to
95th percentiles: 6.1 to 8.0, median: 7.0) and generally shows a slight decrease over the flowback
period in the study wells. The site F flowback waters show a greater decrease in pH to slightly
acidic values at the end of the flowback period (pH < 4), due to the production of H 2SO4 during
the treatment of the flowback water for hydrogen sulfide (H2S) with sodium hypochlorite
83
(NaClO). The site D flowback waters show more variability in pH relative to other wells in the
study with values ranging from 2.3 to 9.5. The total alkalinity also generally decreases over the
flowback period for the flowback water from the study wells, with the majority of samples
remaining above 100 mg/L as CaCO3 (range: < 10 to 685 mg/L as CaCO3, median: 149 mg/L as
CaCO3). In general, the charge balance error for the flowback water samples was within ±15%.
The higher charge balance error relative to low TDS waters may be due to not measuring the
organic molecules in the flowback water as well as the higher error introduced by the high
84
a. b. c.
d. e. f.
g. h. i.
Figure 3.4: TDS at the study wells over the flowback period as cumulative flowback volume. a) Site A wells –
upper Montney Formation; b) Site B wells – upper Montney Formation; c) Site C wells – upper (wells 1-5)
and middle (wells 6 & 7) Montney Formation; d) Site D wells – upper (wells 1 & 2) and middle (wells 3 & 4)
Montney Formation; e) Site E wells – middle Montney Formation; f) Site F wells – middle Montney
Formation; g) Site G well – middle Montney Formation; h) Site H well – upper Montney Formation; i) Site I
85
Table 3.2 (following page): Summary of conductivity, TDS, and the major ion concentrations for each of the 9
study sites. Site C and site D are divided into upper and middle Montney Formation wells. Lower
concentrations are associated with earlier flowback times and higher concentrations are from later in the
flowback period. The data from multiple wells are combined in cases where flowback water samples were
86
Conductivity TDS Cl Na Ca K Mg Sr
Site n
mS/cm mg/L mg/L mg/L mg/L mg/L mg/L mg/L
upper Montney Formation
min 60.8 41,358 25,722 8,264 1,616 553 296 298
A
22 median 102 61,220 43,437 12,759 3,059 796 547 630
(8 wells)
max 131 92,731 65,777 17,818 5,389 1,239 941 1,220
min 47.6 30,135 18,541 9,162 1,789 284 154 60
B
30 median 123 89,949 55,235 25,609 5,950 1,035 619 404
(2 wells)
max 190 228,259 164,018 51,027 11,705 1,920 1,369 924
min 56.1 34,137 21,344 9,932 1,360 569 191 194
C
52 median 102 70,449 44,439 19,779 3,088 1,025 402 477
(5 wells)
max 157 147,839 104,897 33,212 7,333 1,500 681 916
min 50.4 31,522 19,303 9,960 1,169 466 171 123
D
19 median 86.4 62,520 38,355 18,489 2,874 860 418 264
(2 wells)
max 107 80,944 50,963 23,974 4,058 1,172 611 358
min 33.8 20,713 12,308 6,451 629 414 102 30
H
18 median 113 83,807 49,006 28,509 2,798 1,534 650 141
(1 well)
max 135 112,226 66,998 37,637 3,677 1,806 809 195
middle Montney Formation
min 120 82,519 52,570 23,802 3,638 1,065 441 573
C
20 median 147 110,450 71,218 30,960 5,310 1,461 669 893
(2 wells)
max 171 140,538 93,007 38,460 7,332 1,865 945 1,263
min 76 3,609 1,893 1,344 13 49 10 4
D
22 median 99 21,631 12,510 7,884 628 257 79 55
(2 wells)
max 123 56,800 34,565 18,872 2,112 466 223 268
min 22.1 11,105 6,671 2,787 350 187 62 38
E
26 median 35.7 18,672 12,252 5,256 641 295 107 72
(4 wells)
max 51.8 32,864 21,611 9,119 1,126 474 220 161
min 29.1 18,655 10,295 6,849 560 166 93 33
F
12 median 37.5 24,009 14,455 9,066 702 196 117 44
(2 wells)
max 50.4 34,139 21,495 10,575 795 251 136 69
min 27.9 13,972 8,186 3,896 174 186 74 29
G
8 median 64.8 38,963 24,790 10,999 845 410 273 73
(1 well)
max 95.4 65,052 41,783 18,244 2,229 650 586 101
lower Montney Formation
min 11.1 4,587 2,260 1,991 110 105 32 13
I
28 median 56.1 31,998 17,678 12,112 1,032 558 166 206
(2 wells)
max 130 90,178 51,038 33,782 4,081 1,296 524 1,011
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3.4.1 Overview of Montney Formation flowback water chemistry
Different methods of grouping the TDS and major ion results are used to provide a high
level overview of the flowback water data from the current study. In the following section a
series of plots are provided to summarize and compare the flowback water results. The flowback
day (time), the formation member where the well was completed, and the well location all have
an influence on the flowback water chemistry and are some of the factors that need to be
considered when interpreting flowback water geochemistry. The total flowback and percent
Flowback time: The importance of flowback time is investigated by dividing the data
into early (day 1-2), middle (day 2-7), late (> day 7), and produced water samples (Fig. 3.5a).
An increasing trend in TDS is apparent over the flowback period; however, there is overlap
between the different groups of data due to the variability between the different wells that is not
Stratigraphy: On average, the wells completed in the upper Montney Formation have
higher major ion concentrations in the flowback water relative to the wells completed in either
the middle or the lower Montney Formation (Fig. 3.5b). The higher concentrations in the upper
Montney Formation flowback water are most apparent in the early time flowback water
chemistry.
Aerial distribution: Grouping the results by site shows that the flowback water TDS
varies considerably between different sites and that the variation is not linked solely to the
member of the Montney Formation where the well was completed (Fig. 3.5c). There is also
variation across the study region, with the overall TDS values appearing slightly higher in the
88
southeastern region (Fig. 3.5d); however, data is limited to the results from only one well in this
region.
Total flowback and Percent recovered: There is limited variation in TDS over the
flowback period when the flowback water results for all the wells are compiled and divided
based on the percent of total flowback water (Fig. 3.6a). The division does not take the length of
the flowback period or the volume of flowback water produced from a well into consideration.
The low variability in this case is due to the data for all wells being averaged out over the
flowback period for all wells. By dividing the results by the percentage of flowback water, the
last sample for a well with a shorter flowback period would be included as 90-100% flowback
and decrease the overall value, for example. Grouping the data based on the percent recovered
(Fig. 3.6b) shows that the range in flowback water TDS is similar up to 25% recovered,
comparable to the low variability in the total percent recovered plot. The TDS in flowback water
for samples with a higher percent recovered (25-35%) appear to be higher; however, these results
89
a. b.
c. d.
Figure 3.5: Different sources of variability in the studied Montney Formation flowback water. TDS is used as
an example, as the major ions show similar trends to TDS. a) All data are grouped into early (day 1-2),
middle (day 2-7), and late (> day 7) flowback water and produced water; b) The results for all wells are
grouped by the Montney Formation member where hydraulic fracturing occurred; c) The results are
grouped by site. Sites with multiple wells have all data from those wells grouped together. Sites C and D
include wells from both the upper and the middle Montney Formation; d) The results for all wells are
grouped by region. The northwest region includes sites A and I (upper and lower Montney Formation), the
central region includes sites B through G (upper and middle Montney Formation) and the southeast region
includes site H (upper Montney Formation). Note: b-d summarize all flowback water results from early to
late flowback combined but do not include the produced water results. The box portion of the boxplot shows
the 25th percentile, the median, and the 75th percentile. The whiskers show the interquartile range (IQR).
The points represent potential outliers which fall outside the IQR.
90
a. b.
Figure 3.6: The flowback water results as TDS for all samples from all wells divided based on a) the percent
of total flowback and b) the percent recovered. When the results are considered as percent of total flowback,
there is no significant variability when the results are averaged out for all wells combined. The results for
percent recovered do not vary significantly up to 25% recovered. The variability for samples with a higher
percent recovered (> 25%) is due to the data being from four wells (25-30%: well D-2 [n=1], well B-1 [n=5],
and well B-2 [n=2]; 30-35%: well B-1 [n=2] and well A-2 [n=1]). These higher TDS results would mainly
reflect the chemistry of the flowback water results from site B and do not indicate that there is a significant
increase in TDS after 25% recovery is reached. The box portion of the boxplot shows the 25 th percentile, the
median, and the 75th percentile. The whiskers show the interquartile range (IQR). The points represent
Eighteen of the study wells were completed in the upper Montney member. These wells
are located in the northwestern (site A), central (sites B through D), and southeastern (site H)
regions of the study area. The flowback water TDS, major ion concentrations, and rate of
91
increase in TDS during flowback for the upper Montney member study wells all fall within a
similar range of values over the flowback period; there is no significant variation in the flowback
water chemistry between the different regions of the study area for the majority of the major
ions. The exception is the concentrations in the flowback water from well H-1 initially increased
at a more rapid rate relative to the other wells (see Fig. 3.4h). Overall, the flowback water TDS
ranges from a minimum of 20,700 mg/L in the initial flowback water samples from well H-1 to a
maximum of 228,000 mg/L in the late flowback water samples from well B-1 (see Table 3.2).
The upper Montney member wells were completed with freshwater-based hydraulic fracturing
fluids for wells A-3, D-1, D-2, and H-1 (TDS < 1,500 mg/L) and fluids composed of a blend of
freshwater and recycled flowback water for the remaining site A wells and the site B wells (TDS
> 3,000 mg/L). The hydraulic fracturing fluids for the site C wells were not sampled but
The flowback water major ion concentrations for the upper Montney member wells are
similar when samples collected at a similar flowback volume are compared. There are
exceptions: low Ca and Sr concentrations occur for well H-1 and high Sr concentrations occur
for the site A wells. The maximum major ion concentrations occur in flowback water from well
B-1 in the samples following a 9 day shut-in period preceded by a 15 day low flow period. The
one exception is the maximum Sr concentration (1,220 mg/L), which is measured in well A-6 in
the northwestern region of the study area. The overall lowest Sr concentrations in late flowback
water were measured at the southeastern site (well H-1). Accepting these data at face value
suggests the Sr concentrations in upper Montney member flowback water show an increasing
trend across the study area from the southeast (site H) to the northwest (site A). In sequential
extraction experiments completed on shale samples by Stewart et al. (2015), a large proportion of
92
Sr was found in the carbonate fraction, therefore, the variability in Sr concentrations may be due
to dissolution of carbonate with differing amounts of Sr. Some carbonate dissolution may occur
during hydraulic fracturing however, dissolution could also occur over the depositional history of
the formation thus influencing the formation water chemistry which would in turn influence the
flowback water chemistry through mixing. Further flowback water sampling of upper Montney
member wells in the southeastern and northwestern regions is required to further investigate the
trend.
All wells completed in the middle Montney member (n=11) are located in the central
region of the study area. The site D through F wells generally have similar major ion
concentrations although the major ion concentrations in flowback water from the site D wells
increase at a more rapid rate and reach higher concentrations by the end of the flowback period
relative to the site E and site F wells (see Fig. 3.4d-f). Within the site E wells, wells E-1, E-2,
and E-4 have similar TDS while well E-3 has higher TDS at a lower flowback volume. The
major ion concentrations are higher for flowback water from well E-3 except for Na
concentrations which are similar to the Na concentrations in flowback water from other site E
wells. The one well located at site G has slightly higher major ion concentrations and the two
wells at site C have significantly higher major ion concentrations relative to flowback water from
the site D-F wells. The two site C wells have higher major ion concentrations relative to the
flowback from the other middle Montney member wells throughout the flowback period. The
hydraulic fracturing fluids for the middle Montney member wells are interpreted to be a blend of
freshwater and recycled water based on the elevated TDS (> 4,500 mg/L), excluding the
hydraulic fracturing fluid for the site C wells and well D-3 which are dominantly freshwater.
93
3.4.2.3 Lower Montney member
Only two studied wells were completed in the lower Montney member. These wells are
located at a site in the northwestern region of the study area (site I). The initial flowback water
major ion concentrations for the two lower Montney Formation wells are low. The major ion
concentrations increase more rapidly for well I-2 than well I-1 and higher concentrations are
recorded for the flowback water from well I-2 for all times. For example, the TDS increases
from 4,590 to 53,800 mg/L for well I-1 and from 9,370 to 88,700 mg/L for well I-2 (Fig. 3.4i).
Both of these wells were sampled over 22 days, although, well I-1 had a greater total cumulative
flowback water volume. The major ion concentrations in the flowback water from the two site I
wells reach similar concentrations to those seen in the flowback water from the upper and middle
In a companion paper (Chapter 4) we show the most probable cause of the increasing
major ion concentrations is mixing between the normally low salinity hydraulic fracturing fluid
and more saline formation water, with an increasing proportion of formation water over the
flowback period. Mixing between two end members is illustrated by the linear relationship
observed with ion-ion plots (Fig. 3.7). More efficient mixing between the hydraulic fracturing
fluid and the formation water and possible variability in formation water chemistry between
wells would contribute to differences in the rate of increase in TDS in flowback water. Potential
variables that result in more mixing are a more complex fracture network and a higher SRV,
which would result in more fractures and a more extensive fracture network. The complexity of
the fractures would in turn expose a greater surface area for water-rock interactions between the
injected hydraulic fracturing fluid and the reservoir, as well as increase the access to formation
94
water. Many of the study wells do not reach a plateau by the end of the flowback period and
continue to show increasing ion concentrations for the full flowback period. This behavior in
flowback water from other formations has been attributed to a greater fracture complexity with a
greater surface area exposed to the hydraulic fracturing fluid (Bearinger, 2013; Ghanbari et al.,
2013; Zolfaghari et al., 2015a). The smaller diameter of the secondary fractures would result in
a more drawn out contribution from the fractures due to slower flow, while the higher surface
area of these fractures would result in higher TDS, thus contributing to a continual increase in
the TDS in flowback water. A 100% contribution from formation water presents an upper limit
to the major ion concentrations that can be attainted; however, based on the calculations using
conservative tracers the majority of the study wells do not reach concentrations that are
95
a. b.
Figure 3.7: a) Na-Cl plot separated by site; b) Ca-Cl plot separated by site. The approximately linear
relationship between the major ions indicates mixing between two endmembers – the injected hydraulic
fracturing fluid and the formation water. These plots show that ion concentrations in flowback water do not
increase at a constant rate at all sites. The 3 site B samples with high concentrations were collected from well
B-1 following a shut-in period within the flowback period. ▲- upper (u) Montney Formation wells; -
In addition to the formation water accessed directly in the fractures created during
hydraulic fracturing, formation water produced through countercurrent imbibition, as well as the
processes of diffusion and osmosis (Balashov et al., 2015; Zolfaghari et al., 2016; Wang et al.,
2016; 2017), may contribute to the high TDS. The production of formation water through
countercurrent imbibition is inferred from the increasing salinity in the water used in laboratory
imbibition experiments with core samples, such as those conducted by Zolfaghari et al. (2016).
Imbibition undoubtedly is the main mechanism accounting for the low fluid recovery from
hydraulically fractured wells (also see Roychaudhuri et al., 2013; Engelder et al., 2014). A
greater imbibed volume is correlated to longer shut-in times, higher clay content, and lower total
96
organic carbon content (Lan et al., 2014). These variables are expected to vary between sites and
potentially between wells, depending on the heterogeneity of the reservoir. At sites where more
imbibition occurred, a higher proportion of the injected hydraulic fracturing fluid would be
sequestered in the formation and the flowback water would have a higher TDS due to the greater
contribution from formation water accessed through countercurrent imbibition. Mixing would
occur in the fractures between the fluid that was not imbibed and the formation water that was
drawn out of the formation. The influence of diffusion, osmosis, and countercurrent imbibition
cannot be separated based on the current results and may all be contributing to the increasing
The results from the present study show that there is similarity between the flowback
water chemistry of wells located at the same site and within the same member of the Montney
Formation (e.g., wells D-3 and D-4 or wells E-1 and E-2; Fig. 3.4 d and e above). Similarity in
flowback water chemistry between nearby wells has previously been observed in Marcellus
Shale flowback water (Barbot et al., 2013). This result is likely due in large part to similarities in
the reservoir properties between nearby wells, including formation water chemistry and
formation mineralogy, which impact the flowback water chemistry through mixing and water-
rock interactions. In addition, wells from the same site are more likely to have similar
completion design parameters, such as shut-in time, which influence the time and fluid volumes
available for mixing. It is intuitive that wells from the same site should have similar flowback
water chemistry; however, based on the results from the study wells this is not always the case
One notable example of where wells located at the same site show significant differences
in flowback water chemistry is site I. The two site I wells were completed at the same site within
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the lower Montney member with similar injected fluid chemistry and injected fluid volume. The
TDS and major ion concentrations increase more rapidly at well I-2 and reach higher
concentrations by the end of the flowback period. Well I-2 had 30 hydraulic fracturing stages
and a 5 day shut-in period compared to well I-1 which had only 24 stages and was shut-in for 1
day. The higher concentrations at well I-2 are interpreted to be primarily due to more extensive
mixing between the hydraulic fracturing fluid and the formation water, relating to the longer
shut-in time, additional hydraulic fracturing stages, and a more complex fracture network at this
There are several examples in the study in addition to the site I wells which support the
correlation between a longer shut-in period and a higher initial flowback water TDS. The two
middle Montney member wells at site C had high initial TDS in the flowback water (> 80,000
mg/L) and shut-in periods of 22 and 24 days, relative to the lower TDS (< 25,000 mg/L) and <
10 day shut-in periods for the other middle Montney member wells in our study. The initial high
concentrations at site C cannot be related to the injected fluid, which is made up of relatively low
TDS freshwater with chemical additives. Within the site E wells, the higher major ion
concentrations in well E-3 flowback water may be due to the slightly longer shut-in period (8
days relative to 5 or 6 days for the other site E wells) and the lower flowback water recovery for
this well, which was 600 m3 relative to > 1,000 m3 cumulative flowback water for the other three
site E wells. A longer shut-in period would result in more time for mixing to occur within the
formation. A greater amount of time would also allow for more diffusion, osmosis, and
The increase in major ion concentrations is not always constant and there are occurrences
at some sites where there is a spike in major ion concentration or TDS (e.g., well C-4; Fig. 3.4c).
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The spike in concentration tends to be consistent for all major ions. One possible explanation for
an increase in major ion concentrations is a shut-in period within the flowback period, as was
observed near the end of the flowback period for well B-1 and during the flowback period for
well C-4. Other possible factors causing a brief change in the major ion concentrations are
changes in the flowrate, where an increase in the flowrate can be related to a decrease in the
major ion concentrations (e.g., well C-1), and changes in pH, where a decrease in pH correlates
with a decrease in major ion concentrations (e.g., well D-1). In some wells the cause of the spike
in concentration is not apparent (e.g., well D-4) and presumably due to factors that were not
quantified in the present study. The additional variables not measured as part of our study
include the type of fracture network, fracture surface area, the SRV, and the rate of imbibition,
Due to the lateral variability in flowback water chemistry across the study area, it is
difficult to compare or isolate the variation in flowback water between the different Montney
members. Of the sites included in the study, only sites C and D have wells completed in both the
upper and middle Montney members and can be used to directly compare the flowback water
from these members of the formation. For site C wells, there is some overlap between the major
ion concentrations in the flowback water of the different wells but the flowback water from the
middle Montney member generally has higher concentrations of the major ions than that from
the upper Montney member (Fig. 3.8a). However, the major ion concentrations for flowback
water from well C-5 (upper Montney member) are within the range of or higher than the major
ion concentrations measured at the two site C middle Montney member wells, well C-6 and well
C-7. The longer shut-in time for well C-5 of 30 days may contribute to the higher major ion
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concentrations in the flowback water from this well. The shut-in times for the remaining site C
wells are between 21 and 28 days. The other completion parameters (e.g., number of stages,
volume of injected fluid) are similar for wells at site C. Site D shows a more distinct difference
in chemistry between flowback waters collected from the wells completed in the upper and
middle Montney members (Fig. 3.8b). Conversely to the site C wells, the upper Montney
member flowback water from wells D-1 and D-2 have higher TDS and higher major ion
concentrations relative to the middle Montney member flowback water from wells D-3 and D-4.
The two upper Montney member wells at site D have slightly longer shut-in times of 4 and 7
days relative to the middle Montney member wells at this site, which have 1 and 2 day shut-in
periods. The difference in the length of the shut-in period likely contributes to the variability in
flowback water chemistry, making it difficult to discern if the member of the formation where
A comparison of the upper Montney member flowback water major ion chemistry
between sites C and D shows that the chemistry is similar between the wells at these sites, with
the site D TDS and major ion concentrations generally being slightly lower overall (see
Table 3.2). In addition, the rate of increase of the major ion concentrations over the flowback
period is similar for these wells. The middle Montney member flowback water major ion
chemistry, as well as the rate of increase in major ion concentrations, is notably different
between the two sites, indicating lateral variability in the flowback water chemistry from the
middle Montney member. The site C middle Montney member wells have higher major ion
concentrations and a slower rate of increase over the flowback period, while the site D wells
have lower major ion concentrations but show a more rapid increase over time. The comparison
between the site C and site D wells indicates that there is variability in flowback water chemistry
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between sites even from the same formation member, thus making it difficult to make
predictions on flowback water chemistry based on the member where the well is completed.
None of the study sites have wells completed in both the lower member and either the upper or
the middle member of the Montney formation so a similar comparison with the lower Montney
Figure 3.8: Na concentrations over the flowback period for (a) site C; and (b) site D wells. TDS and the other
major ions follow a similar pattern of increasing concentrations over the flowback period. Wells C-1 through
C-5, well D-1, and well D-2 are completed in the upper Montney member. Wells C-6, C-7, D-3, and D-4 are
completed in the middle Montney member. The wells completed in the upper Montney member have similar
Na concentrations (site C median: 19,800 mg/L, site D median: 18,500 mg/L), while the Na concentrations for
the wells completed in the middle Montney member are significantly different (site C median: 31,000 mg/L,
site D median: 7,880 mg/L). Note the difference in the y-axis scales.
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3.5 Flowback water trend analysis
required to provide an overall comparison of the flowback water results between sites due to the
differences in the lengths of the flowback periods and the variable rate of increase of TDS and
the major ion concentrations for different wells. A combination of linear regression and linear
mixed effects models were selected to complete a trend analysis of the results for the study wells
in order to provide a method for the comparison. The first analysis investigates the increase in
TDS or the major ion concentrations over time since the beginning of the flowback period. The
increasing major ion concentrations do not always fit an exact linear increase; however, a linear
model does provide a reasonable approximation over the duration of the flowback period for
which the wells were sampled. For example, the results for the correlation between TDS and
flowback day show an overall moderate positive correlation for the study wells (median R 2 =
0.85). The major ion concentrations in later samples would be expected to eventually reach a
plateau as the flowback chemistry approaches the formation water chemistry unless mixing is not
the dominant influence on the chemistry. If water of condensation is the dominant liquid source
later in the production life of the well the slope would theoretically become negative. A non-
linear relationship would require a different model. An examination of the slope coefficients
derived from the linear regressions of TDS or the major ion concentrations as a function of
flowback time showed enough similarity to group the wells by site and use a linear mixed effects
model to derive an overall fixed effects slope coefficient for each site (Fig. 3.9). The one
exception was the two site I wells which were found to have significantly different slopes for the
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parameters of interest as a function of time and are thus considered separately for the analysis
using the slope coefficients from the linear regression for each of the wells.
Figure 3.9: An example of the linear fixed effects model with data from site E. The fixed effects line
represents the overall fixed effects for the 4 wells at this site and the slope of this line can be used to compare
different sites. The differences in the slope for the individual wells can be described by the random effects.
The second analysis looks at the increase in flowback volume over time. Some of the
wells (e.g., site C wells) show a linear increase in volume over the sampled flowback period;
however, other wells show an increase in flowback that is more rapid early in the flowback
period and begins to slow down over time. Due to the change in behavior of the increasing
cumulative flowback volume over the flowback period and the lack of either a consistently linear
or non-linear trend for the study wells, the results were divided into three periods for the
analysis: 1) early (day 0-3); 2) mid (day 3-15); and 3) late (> day 15) flowback. Each of these
segments was treated as a linear regression to derive the slope coefficient for the flowback
volume as a function of time. The differences in slope coefficient when each well was examined
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individually did not allow for the wells to be grouped by site as the variation was too great.
Simple linear regression was therefore used for the analysis. The site A wells were the only
wells that were grouped together and analyzed with a linear mixed effects model to obtain a
single value for the site, although the use of this model was due to limited samples available for
each well.
The slope coefficients derived from the linear regressions for the two site I wells and
from the linear mixed effects models for the remaining sites are used to compare the different
sites by considering the change in TDS or the concentration of a particular major ion as a
function of time. The analysis does not directly consider other variables, such as differences in
injected fluid chemistry or shut-in time, and it is only used to provide a method to compare the
sites based on the increase in TDS and the major ion concentrations over the flowback period.
For some of the sites similarity in the overall fixed effects slope coefficients indicates that TDS
and the major ions increase at the same rate over the flowback period. The similarity in slopes
are hence a variable by which the sites can be grouped (Table 3.3). The wells located in the
central region of the study area can consistently be divided based on the rate of increase into:
Group I – sites E, F, and G with a slower rate of increase; and Group II – sites B, C, and D with a
more rapid rate of increase over the flowback period for the parameters of interest (Fig. 3.10a).
There is not a distinct difference in the slope coefficients for sites B through G for Mg
concentrations, indicating that some elements can increase at relatively similar rates for all the
sites in the central region. Of the major ions included in the analysis, the Sr concentrations show
the greatest variability in the rate of increase between the wells (Table 3.3, Fig. 3.10b) and will
be discussed in Section 3.5.4. The wells located in the northwestern (sites A and I) and the
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southeastern (site H) regions of the study area do not consistently fall within one of the groups in
Table 3.3, indicating that there may be some regional effect on the flowback water chemistry.
Since the slope coefficient is based on the increase of TDS or major ion concentrations over
time, differences in the length of the flowback period do not impact this value as long as a linear
fit is observed; however, eventually the concentrations are expected to reach a plateau and a non-
Table 3.3: Groups of sites based on similarities in slope coefficient. Group I – slowest rate of increase, Group
II – intermediate rate of increase, and Group III – fastest rate of increase. No distinction could be made
between the sites for the rate of increase in Mg over the flowback period to divide the majority of wells
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a. b.
Slow
Slow
Fast Intermediate
Intermediate
Fast
Figure 3.10: Slope coefficients with confidence intervals for a) TDS; and b) Sr concentrations over flowback
time. For TDS, the sites can be divided by the rate of increase into slowest – Sites E, F, G, and I-2;
intermediate – sites A, B, C, D, and I-2; and fastest – site H. These divisions are similar for most of the major
ions (see Table 3.3). b) For Sr, the sites can be divided into slow – Sites A, E, F, and G; intermediate – Sites B,
C, D, H, and well I-1; and fast – Well I-2. The error bars show the confidence intervals of the slope
coefficients. Wells are considered to have similar slope coefficients when their confidence intervals overlap
with the calculated value of a different site. If only the confidence intervals overlap it does not indicate a
great degree of similarity between sites. The large confidence interval for the site A slope coefficient is due to
In order to complement the trend analysis of the TDS and the major ion concentrations
over flowback time, the change in cumulative flowback volume over time was investigated.
Several studies have used the production rates of flowback water to gain insight into fluid flow
and the fracture system in the reservoir (e.g., Clarkson, 2013; Kanfar and Clarkson, 2016;
Williams-Kovacs and Clarkson, 2016). An analysis using these methods to gain additional
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information from the flowback water volume is beyond the scope of this paper and the present
The results of the analysis show that the slope coefficient for the regression of the volume
of flowback water as a function of time is variable both between wells and for the different
portions of the flowback period for the same well (Fig. 3.11). For the majority of wells, the rate
of increase in flowback production is most rapid in the early flowback period (day 0-3).
However, well B-1, well C-2, well C-4, well H-1, and well I-1 are exceptions where the rate of
cumulative flowback increases more rapidly in the mid flowback period (day 3-15). In all cases
where the flowback period extends beyond 15 days, the rate of change in flowback production is
reduced, although only the site B, site G, and site I wells were sampled for longer than 15 days.
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Figure 3.11: Summary of the slope coefficients for the cumulative flowback volume as a function of flowback
time for each of the wells for the early (day 0-3), mid (day 3-15), and late (> day 15) portions of the flowback
period. A lower slope coefficient indicates a slower flowrate over the portion of the flowback period relative
to a higher slope coefficient. In general the rate of change in cumulative flowback production is most rapid in
the early flowback period. The site A wells are grouped together using a linear mixed effects model to obtain
an overall slope coefficient for this site as the data from this site was limited. The remaining wells are
presented separately as the slope coefficients (derived from a simple linear regression model) were generally
not sufficiently similar to group together to use a linear mixed effects model. Wells without a slope coefficient
for one of the periods had two or fewer data points that fell within that period.
The analysis comparing the increase of TDS and the major ion concentrations as a
function of time provided a method to group the data by site using the slope coefficients from
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linear mixed effects models. The similarity in slope coefficients for the groups of sites
summarized in Table 3.3 argues for similar changes in the rate of mixing between the injected
hydraulic fracturing fluid and the formation water for the sites within each group. The similar
change in rate could be related to a combination of the formation water chemistry, the
permeability of the formation, and the extent of both natural and induced fractures at the sites.
Greater similarity in slope coefficients would be expected between nearby wells since there
would likely be less variability in the properties of the formation over a shorter distance. Sites E,
F, and G are located in close proximity (< 15 km from each other), were completed in the middle
Montney Formation, and have comparable slope coefficients; however, site D, located within
15 km of these sites, has slope coefficients more similar to sites B and C. The difference may be
caused by variation in the fracture networks that developed at the different sites, including how
rapidly the microfractures close as reservoir pressure declines during flowback. The variability
between the site D and the sites E through G wells shows that the increase in TDS and the major
ions over the flowback period can vary even between nearby wells. It is of interest to note that
site D includes two wells each completed in the upper and middle Montney Formation. All four
wells from site D had similar slope coefficients, indicating a comparable rate of mixing which
would be consistent with a similar formation water chemistry and fracture network. The higher
concentrations in the flowback water from wells D-1 and D-2 (upper Montney member) were
interpreted to be due to a higher proportion of formation water in the initial flowback water (see
Chapter 2), likely related to the longer shut-in times of 4 and 7 days for these wells relative to the
wells completed in the middle Montney member (wells D-3 and D-4; 1 and 2 days).
As mentioned above, the major ion which showed the greatest variability in the trend
analysis is Sr. The Sr slope coefficients were highest for well I-2 (Fig. 3.10b), whereas the slope
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coefficients for the other major ions for this well were similar to the Group II wells (Table 3.3).
The inconsistency may be due to variability in the Sr concentrations in formation water. The Sr
concentrations in the formation water near sites A and I (northwestern region) are higher
(median: 1350 mg/L) relative to the central and southeastern areas in the study (Fig. 3.12),
accounting for the rapid increase in Sr concentrations for well I-2. The lower slope coefficients
indicating a slower increase in Sr concentrations at site A and well I-1, which may be due to
more limited mixing between the injected fluid and the formation water.
The Sr slope coefficient for well H-1 in the southeastern region was also notable as the
rate of increase is slower relative to the increase in TDS and the other major ion concentrations
at this well over the flowback period. The slope coefficient for Sr at well H-1 is similar to sites
B-D and well I-1 (Group II). The Sr concentrations in formation water near the site H well
(115 mg/L) are much lower than in the central and northwestern areas which may result in a
slower rate of increase over the flowback period; however, there are only results available for
one produced water sample from the southeast region. The concentrations of the other major
ions in formation water do not show as great a variation as the Sr concentrations, which likely
explains the more consistent results for the other major ions.
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Figure 3.12: Sr concentrations in produced water samples, used to approximate the formation water
chemistry. Median Sr concentrations are higher in produced water samples from wells in the northwestern
region near site A and site I. However, the Sr concentrations from site A show overlap with the Sr values in
wells nearby sites B-F. Sr concentrations are significantly lower in produced water samples nearby sites G
(central region) and H (southeastern region). Note: Only one sample was available with Sr concentrations
nearby sites H and I. The box portion of the boxplot shows the 25 th percentile, the median, and the 75th
percentile. The whiskers show the interquartile range (IQR). The points represent potential outliers which
The amount of variability in the increase in flowback volume over time at a single well
and between different wells does not lead to any obvious correlations between the flowback
water production rate and the flowback water chemistry. The initial rapid increase in the volume
of flowback water produced over time observed for most wells is likely related to the initial
flowback from the larger aperture fractures. When the production rate increases faster later in
the flowback period, as was observed for well B-1, well C-2, well C-4, well H-1, and well I-1, it
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indicates that areas of greater permeability, such as more permeable lenses, were accessed later
A higher slope coefficient for the flowback volume as a function of time would indicate a
more rapid increase in flowback water production from a well. The differences in the rate of
flowback volume produced are likely related to the permeability in the subsurface due to both the
created and existing fracture networks, which were not measured as part of the current study.
The results of the current analysis do not consistently support a correlation between a more rapid
rate of flowback water production and a faster increase in TDS as similar changes in TDS were
observed for both a more rapid and a slower rate of increase in flowback water volume over
time. During the early flowback period, for example, wells with a higher rate of production, with
slope coefficients greater than 300, were found to have TDS increase over this period by a factor
of between 1.1 and 3.0. Wells with a slower rate of production and slope coefficients between
100 and 250 had a similar increase in TDS over the same portion of the flowback water period,
with an increase by a factor of 1.0 to 3.6. A lack of a distinction in the rate of flowback water
production and the increase in TDS suggests that the relative rate of flowback water produced
over time cannot be used to predict the increase in TDS at a well. The variability between the
different wells illustrates the complexity of the hydraulic fracturing process and the numerous
variables that can impact both the flowback chemistry and the flowback volume. A further,
more detailed analysis of the data at the individual well level with consideration of the different
variables that may be impacting the flowback water volume and chemistry is needed to further
investigate the relationship between the flowback water chemistry and flowrate.
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3.6 Conclusions
The challenges surrounding the interpretation of flowback water chemistry are a result of
the changes in the TDS and the major ion concentrations over the flowback period as well as due
to the many variables that may impact the chemistry. A simple comparison of the maximum
flowback water ion concentrations between wells is therefore not possible without considering
the length of the flowback period and the volume of flowback water collected, among other
factors. Some of the variables (e.g., shut-in time) were presented here as an explanation of the
differences in flowback water chemistry between wells. A more detailed analysis of the relative
By taking the potential concerns with comparing flowback water chemistry into
consideration, we were able to analyze the Montney Formation water chemistry and present a
method to compare the changing chemistry between wells. The main conclusions from our study
are as follows:
The concentrations of the major ions increase over the flowback period, although the rate
of increase varies between different sites and sometimes between the wells on the same
site. The increasing major ion concentrations are likely due to mixing between the
relatively low TDS hydraulic fracturing fluid and the high TDS formation water with
The flowback water major ion concentrations were generally similar for wells completed
at the same site and within the same member of the Montney Formation. The two site I
wells were an exception to this with well I-2 showing a more rapid increase in major ion
concentrations over the flowback period relative to well I-1. The difference in the
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flowback water between these two wells may be due to the longer shut-in time, additional
hydraulic fracturing stages, and/or a more extensive fracture network at well I-2 causing
more efficient mixing between the injected fluid and the formation water at this well.
The trend analysis provides a method for grouping the wells based on the increase in the
major ion concentrations over flowback time. The majority of the major ions fall within
the following groups: slow rate of increase – sites E-G, well I-1, site A (Cl, Sr); moderate
rate of increase – sites B-D, well I-2, site A (TDS, Na, K); and rapid rate of increase –
site H, site A (Ca). The groups of wells based on the Sr concentrations differed from
these groups with the most rapid rate of increase observed for well I-2. This may be
related to more variability in Sr concentrations in the formation water across the study
area as well as the efficiency in mixing at different sites. When the upper Montney
wells in the southeast and northwest regions is necessary to confirm the trend. There was
no obvious correlation with the rate of production of flowback water and the flowback
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Chapter 4: Flowback water chemistry from the Montney Formation: Part II –
Controls on variability
4.1 Introduction
reservoirs are developed with a combination of horizontal drilling and hydraulic fracturing,
which requires several thousand cubic meters of fluid per well to be pumped into the formation
(Alessi et al., 2017) in order to fracture the rock and increase the permeability to access the
hydrocarbons in the formation. Prior to the production phase of the well, the well produces a
fluid with high total dissolved solids (TDS) – the flowback water 6. In some wells the flowback
period begins immediately after hydraulic fracturing; however, in many wells there is a time lag
where the well is shut-in before flowing back. The shut-in period can last for less than a day up
to several months (e.g., Makhanov et al., 2014). The volume of flowback water varies between
different formations but typically only represents a fraction (approximately 25%) of the injected
fluid volume (Haluszczak et al., 2013). The flowback water represents a mixture of the injected
hydraulic fracturing fluid and the formation water (e.g., Haluszczak et al., 2013; Engle and
Rowan, 2014; Vengosh et al., 2017), with the proportion of formation water increasing over the
flowback period. The increase in the fraction of formation water is reflected in the increase in
the TDS and the major ion concentrations in flowback water, including chloride (Cl), sodium
(Na), potassium (K), calcium (Ca), magnesium (Mg), and strontium (Sr). The chemistry, as well
6
For the purposes of this study, the flowback water includes the fluids produced from the well following hydraulic
fracturing and up until the well is placed on production.
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as the rate of increase in the TDS and the major ions, of flowback water can provide insight into
processes occurring in the reservoir. However, there are many different variables that are related
to the well completion, the formation properties, and the response of the well to hydraulic
fracturing that can impact the flowback water chemistry (Table 4.1).
Table 4.1: List of several of the variables that may potentially be impacting the flowback water chemistry.
Several of the variables listed are interrelated (modified from Chapter 3).
Response of reservoir to
Reservoir properties Completion design
completion
In order to determine the utility of flowback water as a ‘window’ into the reservoir or as a
tool for interpreting completion efficiency, it is critical to understand the numerous variables that
contribute to the composition and volume of flowback. Examining the flowback water chemistry
from several wells can help determine which variables have the greatest influence on chemistry.
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Most previous studies have considered flowback water from single wells which does not provide
the opportunity for understanding or deciphering the contribution of the plethora of variables that
contribute to the chemistry of the flowback fluids. Many variables that may impact the flowback
water chemistry should be considered, most notably the variables that influence the mixing
process (i.e., hydraulic fracturing fluid chemistry and formation water chemistry) and the water-
The following paper acts as a continuation of the work presented in Chapter 3. The study
includes flowback water samples from 31 wells completed in the Montney Formation in the
Peace River Basin in British Columbia (BC) and Alberta, Canada (Fig. 4.1). The wells are
located on 9 sites, with between 1 and 8 sampled wells per site. The Montney Formation was
deposited along the northwestern coast of Pangea during the Early Triassic epoch (Davies,
1997). The deposits represent a marine inner to distal shelf environment and are dominantly
dolomitic-siltstones and very fine grained sandstones (Chalmers and Bustin, 2012; Zonneveld et
al., 2011; Zonneveld and Moslow, 2014). The most recent informal subdivision of the Montney
Formation, which is used in our study, divides the formation into three members based on a
combination of biostratigraphy and lithostratigraphy (Davies and Hume, 2016; Fig. 4.2). Of the
study wells, 18 wells were completed in the upper member, 11 wells in the middle member, and
2 wells in the lower member. The flowback water from these wells was analyzed for the major
ions – Cl, Na, K, Ca, Mg, and Sr. Chapter 3 focused on comparing the flowback water chemistry
between the different wells. As multiple wells are sampled, the second part of the study
presented here uses the flowback water data to investigate the dominant variables that are
impacting the flowback water chemistry using regression analyses and to discuss the inferences
117
that can be made with reference to the reservoir properties, completions, and formation water
chemistry.
Figure 4.1: Location of the 31 study sites in BC and Alberta, Canada. The Montney Formation is shown in
purple (modified from Edwards et al., 1994). Site A – 8 wells, site B – 2 wells, site C – 7 wells, site D – 4 wells,
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Figure 4.2: Schematic cross-section through the Montney Formation from the western margin in BC to the
eastern margin Alberta. The Montney Formation is divided into upper, middle, and lower informal members
based on lithology and biostratigraphy. The upper Montney member includes the lower Doig siltstone
4.2 Methods
The fluids analyzed for the study wells include the injected hydraulic fracturing fluid, the
flowback water, and the produced water. Hydraulic fracturing fluids were either collected as one
sample per fracturing stage (sites A, B, D, E, G, and H wells) or as a representative sample for
the well (sites F and I wells). For the wells where several hydraulic fracturing fluid samples
were collected, composite samples were created by mixing samples with similar electrical
conductivity readings. An overall chemistry for the hydraulic fracturing fluid for a well was
calculated from the composite sample chemistry based on the volumetric proportions of the
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fluids used in the different fracturing stages along the lateral of the well. For example, if two
composite samples were analyzed and each represents an equal volume of fluid used in the
combined stages then the results from each of the samples will be given equal weight in the
overall chemistry of the hydraulic fracturing fluid for the well. The hydraulic fracturing fluid
Flowback water samples were collected at all sites. The flowback water was sampled at a
higher frequency in the initial flowback period (two to three samples per day) then the sampling
frequency was decreased to one sample per day. The sampling schedule was designed to sample
the flowback water more often at the beginning of the flowback period when the flowrate is
typically higher and the chemistry is expected to show more variability. Produced water samples
were collected at site A, site B, and a well located in the same region as site I. These samples
represent the fluids produced by the well following the flowback period once the well is in the
production stage. For the remaining wells, the produced water chemistry was estimated using
publically available data7 for nearby wells completed in the Montney Formation. The produced
water is used in our study to provide an approximation of the formation water chemistry of the
Montney Formation as it is not possible to directly sample the formation water. The produced
water does not represent 100% formation water as there would be some influence on the water
from the injected fluid as well as from potential geochemical reactions (e.g., mineral
7
The publically available data was obtained from the information accessed through the geoSCOUT ® fluid analysis
database.
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All fluid samples were stored at 4°C. The flowback and produced water samples were
heated to 75-80°C for a period of 24 hours to represent reservoir temperatures. Heating the
samples was conducted to re-dissolve any precipitate that formed after sampling as sample
filtering and preservation was not conducted at the time of sample collection. All samples were
filtered with a 0.45 µm filter and subdivided for: 1) anion analysis by ion chromatography; 2) pH
(Omega® PHB21 potable pH meter), conductivity (HACH® CDC401 conductivity probe), and
alkalinity by titration with sulfuric acid (HACH® digital titrator, Model 16900); and 3) dissolved
metal samples were preserved with trace metal grade nitric acid (HNO 3) to a pH < 2. Prior to
analysis with the ICP-OES (Varian® 725-ES) the dissolved metal samples were acid digested to
remove organics using a 2:1 ratio of HNO3 and hydrochloric acid (HCl) followed by a second
digestion step with HNO3 only. A more detailed description of the acid digestion process is
included in Chapter 3. TDS is calculated as a sum of the ion concentrations. The anion analysis
was conducted at a laboratory in Victoria, BC and the remaining analyses were conducted at
The volume of hydraulic fracturing fluid, shut-in time, number of stages, and breakdown
pressure used for each well were obtained from the completion programs for the study wells
None of the completed wells in our study were cored and hence mineralogy was not
directly obtainable from the completed zones. An estimate for the mineralogy of the completed
strata for each well was made by compiling publically available mineralogy determined by
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X-Ray Diffraction (XRD) from nearby wells which were sampled at similar depths to the
fractured zones of the study wells. In areas where public data were absent, additional samples
were obtained from the BC Oil and Gas Commission Core Research Facility in Fort St. John, BC
for XRD analyses. The supplementary samples included both drill cutting samples and core
samples and were analyzed at UBC. The samples were crushed in ethanol using a mortar and
pestle in preparation for smear mounts on glass slides for XRD analysis on a Bruker D8 Focus,
following the modified smear mount method in Munson et al. (2016). The mineralogy was
presented in Chapter 3 and will be summarized briefly here. The dominant ions in the sampled
Montney Formation flowback water are Cl and Na (Table 4.2). The concentrations of Ca, K,
Mg, and Sr are also high. The concentrations of these six major ions show an increasing trend
over the flowback period; however, the rate of increase often changes over the flowback period,
typically with a slower rate of increase as the flowback period progresses. The increase in
flowback water TDS is due in large part to mixing between the injected hydraulic fracturing fluid
and the formation water (e.g., Haluszczak et al., 2013; Olsson et al., 2013; Engle and Rowan,
2014; Vengosh et al., 2017). The rate of increase is dependent on the efficiency of the mixing
process which is likely related to the development of the fracture system, as a higher
permeability and more complex fracture network would result in a greater contribution from
formation water and a more rapid increase in TDS in the flowback water. Diffusion and/or
osmosis between the formation and the injected fluid may also contribute to the high TDS
(Balashov et al., 2015; Zolfaghari et al., 2016; Wang et al., 2016; 2017) as well as formation
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water expelled from the formation due to countercurrent imbibition. The possibility of
countercurrent imbibition is considered as imbibition of the hydraulic fracturing fluids into the
permeability reservoirs (Engelder et al., 2014). Experiments have shown that a shale placed in
water results in an increase in water salinity (Zolfaghari et al., 2016). From these results, we
infer that as the hydraulic fracturing fluid is imbibed into the rock, there is movement of the
formation water out of the rock into the fractures, in addition to the movement of oil and/or gas.
Fluid mixing would occur in the fractures between the remaining hydraulic fracturing fluid and
the formation water which was expelled from the rock. The mixing process would be ongoing
from the initial stage of hydraulic fracturing and throughout the flowback period. The impact of
diffusion and osmosis on flowback water chemistry cannot be differentiated from the imbibition
Table 4.2 (following page): Summary of the flowback water TDS and major ion chemistry for the sampled
wells. Wells at the same site and that were completed in the same member of the Montney Formation are
included together. The organic compounds were not measured in the flowback water samples which may
contribute to higher charge balance errors. The charge balance error for the majority of samples is ±15%.
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TDS Cl Na Ca K Mg Sr
Site n
mg/L mg/L mg/L mg/L mg/L mg/L mg/L
upper Montney Formation
min 41,358 25,722 8,264 1,616 553 296 298
A
22 median 61,220 43,437 12,759 3,059 796 547 630
(8 wells)
max 92,731 65,777 17,818 5,389 1,239 941 1,220
min 30,135 18,541 9,162 1,789 284 154 60
B
30 median 89,949 55,235 25,609 5,950 1,035 619 404
(2 wells)
max 228,259 164,018 51,027 11,705 1,920 1,369 924
min 34,137 21,344 9,932 1,360 569 191 194
C
52 median 70,449 44,439 19,779 3,088 1,025 402 477
(5 wells)
max 147,839 104,897 33,212 7,333 1,500 681 916
min 31,522 19,303 9,960 1,169 466 171 123
D
19 median 62,520 38,355 18,489 2,874 860 418 264
(2 wells)
max 80,944 50,963 23,974 4,058 1,172 611 358
min 20,713 12,308 6,451 629 414 102 30
H
18 median 83,807 49,006 28,509 2,798 1,534 650 141
(1 well)
max 112,226 66,998 37,637 3,677 1,806 809 195
middle Montney Formation
min 82,519 52,570 23,802 3,638 1,065 441 573
C
20 median 110,450 71,218 30,960 5,310 1,461 669 893
(2 wells)
max 140,538 93,007 38,460 7,332 1,865 945 1,263
min 3,609 1,893 1,344 13 49 10 4
D
22 median 21,631 12,510 7,884 628 257 79 55
(2 wells)
max 56,800 34,565 18,872 2,112 466 223 268
min 11,105 6,671 2,787 350 187 62 38
E
26 median 18,672 12,252 5,256 641 295 107 72
(4 wells)
max 32,864 21,611 9,119 1,126 474 220 161
min 18,655 10,295 6,849 560 166 93 33
F
12 median 24,009 14,455 9,066 702 196 117 44
(2 wells)
max 34,139 21,495 10,575 795 251 136 69
min 13,972 8,186 3,896 174 186 74 29
G
8 median 38,963 24,790 10,999 845 410 273 73
(1 well)
max 65,052 41,783 18,244 2,229 650 586 101
lower Montney Formation
min 4,587 2,260 1,991 110 105 32 13
I
28 median 31,998 17,678 12,112 1,032 558 166 206
(2 wells)
max 90,178 51,038 33,782 4,081 1,296 524 1,011
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There is considerable variability between sites and even between wells at the same site
(e.g., the site I wells). A comparison between multiple wells is difficult due to the variability in
the lengths of the flowback periods for different wells as well as the variables related to the
completion and formation properties that may be influencing the flowback water chemistry
(Table 4.3). The length of the shut-in period in particular was observed to impact the flowback
water chemistry, with longer shut-in periods correlated to higher ion concentrations in the initial
flowback water. The many factors that may be influencing the flowback water chemistry also
pose a challenge in comparing the flowback water chemistry between wells completed in the
three different members of the Montney Formation. Lateral variability in lithology within a
single member also occurs. The number of wells available for sampling as part of the present
study was not sufficient to provide a detailed analysis of lateral variability within formation
members, as the majority of sites were in the central region of the formation (6 of 9 sites).
As a direct comparison between wells was not ideal, a method to assess the rate of
increase in TDS and the major ions in flowback water was presented in Chapter 3 and is
summarized here. The method used linear regression and linear mixed effects models to
compare the flowback water chemistry at different sites using slope coefficients to group wells.
It was found that in general, the wells in the central region could be divided into two groups –
sites E, F, and G with a slower rate of increase in major ion concentrations as a function of time
and sites B, C, and D with a faster rate of increase. There was some indication that nearby sites
show greater similarity (sites E, F, and G); however, site D is near these sites and shows a more
rapid increase in the major ion concentrations. The rate of increasing concentrations of the
different ions for wells in the northwestern region (sites A and I) did not consistently fall into
either of these groups. Well H-1 in the southeastern region generally had the most rapid rate of
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increase for TDS and all ions studied except for Sr concentrations. The difference in the rate of
concentrations in formation water across the study area relative to the other major ions. A
preliminary interpretation of an increasing trend in Sr from the southeast to the northwest was
suggested which causes the rate of increase at site H (southeast) to be slower relative to the other
major ions, while the rate of increase for well I-2 (northwest) was more rapid than for other
major ions. An examination of the rate of production of flowback water over time did not reveal
Formation flowback water chemistry results; however, the additional variables which may
influence the flowback water chemistry were not taken into account. In the second part of our
study, a further assessment of selected variables is conducted. The variables that were initially
intuitively considered to have an effect on flowback water chemistry were assessed by looking at
their correlation with TDS and the major ions (Cl, Na, K, Ca, Mg, and Sr). The variables of
interest include:
Number of stages;
Breakdown pressure;
Shut-in time;
Formation mineralogy.
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The data for these variables for each of the wells are summarized in Tables 4.3, 4.4, and
4.5. The effects of imbibition on the flowback water chemistry are not included in the analysis.
The closest proxy for imbibition of the results collected in the present study is the percent of the
injected fluid recovered; however, the use of this parameter in the current analysis is not
appropriate due to the division of the data based on the cumulative flowback volume. The
division of the data in this way holds the cumulative flowback volume constant; therefore, a
sample with a higher total injected volume would have a lower percent recovered due to the
nature of the data rather than as a reflection of the amount of imbibition. A brief discussion on
the use of percent recovered as a proxy for imbibition is included in Section 4.4.3.6.
In order to examine the importance of the selected parameters on flowback water, two
sets of flowback data were examined: 1) initial samples; and 2) the samples collected closest to
1,000 m3 of cumulative flowback water for each well. The second dataset includes samples
collected between approximately 800 to 1,200 m 3 of cumulative flowback volume and includes
the majority of wells (n=26). Well A-1, well A-8, well E-3, and the two site F wells produced
less than 800 m3 of flowback water at the end of the flowback period and are not included. The
initial samples represent early flowback water while the samples collected near 1,000 m 3 of
cumulative flowback water are taken to represent intermediate to late flowback water. Many of
the wells had over 1,000 m3 of flowback water; however, only 15 wells had greater than
1,500 m3 of cumulative flowback and of the 15 wells 6 are from a single site (site C). Therefore
a robust regression analysis for the higher flowback water volumes was not possible with the
127
Table 4.3: Summary of data for the variables considered in the regression analysis.
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Table 4.4 (following page): Summary of hydraulic fracturing fluid chemistry and formation water chemistry
for each of the wells. The majority of the hydraulic fracturing fluid samples are Na-Cl type fluid, which is the
same as the flowback water, although some are Ca-Na-Cl type. Two of the hydraulic fracturing fluid samples
from site H are Na-HCO3 type. There was often a charge imbalance for the hydraulic fracturing fluid
samples which may be related to interference from the additives. The formation water results are medians
from publically available produced water data for nearby wells and produced water samples collected in our
129
Site Well pH TDS Cl Na Ca Mg K Sr
Hydraulic Fracturing Fluid
1 6.8 15,285 10,276 3,212 1,004 162 181 161
2 6.5 16,802 10,423 3,873 1,428 227 226 245
3 7.3 239 71 69 42 22 21 <10
4 6.7 25,297 18,108 4,555 1,566 256 255 309
A
5 6.7 28,072 19,850 5,365 1,791 274 273 332
6 6.7 16,824 11,365 3,486 1,052 205 224 217
7 7.2 3,386 966 1,733 420 59 63 59
8 6.7 25,382 17,495 5,046 1,724 261 280 295
1 7.5 22,018 6,276 11,973 2,828 299 379 160
B
2 7.3 23,459 6,432 12,980 3,067 284 417 175
1 7.3 549 160 208 46 10 11 1
2 7.1 1,284 639 398 58 12 46 2
D
3 7.2 711 289 209 50 10 10 1
4 7.1 4,717 2,044 1,605 142 29 241 6
1 6.5 11,246 6,414 3,659 608 96 187 59
2 6.6 5,052 3,150 1,237 322 53 96 28
E
3 6.4 6,059 3,842 1,546 323 53 89 16
4 6.8 8,464 4,740 2,788 453 79 150 47
F 1, 2 7.0 12,218 7,448 3,948 372 60 105 25
G 1 7.2 5,604 1,841 3,047 305 64 137 40
H 1 5.2 710 7 548 57 23 11 <1
1 7.7 1,849 1,204 66 74 16 8 <1
I
2 7.7 1,863 760 67 77 16 8 <1
Formation Water
A 7.1 123,912 84,352 27,713 7,715 1,088 1,347 1,365
B 5.1 181,416 128,159 33,203 15,182 1,492 1,980 1,048
C 6.4 121,840 74,512 37,467 6,260 822 1,373 1,094
D-F 6.9 100,545 61,735 27,799 6,569 917 2,211 918
G 6.7 78,323 47,476 21,764 5,186 727 1,759 128
H 6.0 153,025 95,568 42,120 10,551 1,877 2,232 115
I 5.9 91,254 89,168 54,000 10,000 1,140 2,040 1,620
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Table 4.5: Summary of the Montney Formation mineralogy used in the regression analysis. Sites with
multiple wells completed at different depths are divided in this table. Carbonates include ankerite, calcite,
dolomite, ferrodolomite, and siderite. Clays include chlorite, illite/mica, and kaolinite. Feldspars include
albite, microcline, and orthoclase. Other minor minerals not included in the regression analysis are
fluorapatite (present in wells nearby sites C-F <2%) and pyrite (present at all sites ~2%).
Sampling was initiated within a day of the beginning of the flowback period for the study
wells; however, as the flowrate differed between wells, the initial samples were collected at
different flowback volumes. The volume of flowback water produced when the initial samples
were collected varies between 0 and 562 m3 which represents 0 to 54% (median: 14%) of the
total flowback water from the wells. The initial flowback water samples are suitable to use to
represent the initial flowback water chemistry as there is no trend (R 2 < 0.05) between the TDS
and the flowback volume for these samples which could create spurious correlations in the
analysis. Positive correlations (R2 > 0.2) were found between the flowback water TDS of the
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initial samples and the hydraulic fracturing fluid TDS, the shut-in time, and the breakdown
pressure (Fig. 4.3). The major ions in flowback water show similar relationships with these
variables (Table 4.6). The hydraulic fracturing fluid volume per stage and the number of stages
have a weak correlation (R2 < 0.2) with the initial flowback water chemistry for the parameters
Figure 4.3: Relationship between the initial sample flowback water TDS values and (a) the HF (hydraulic
fracturing) fluid TDS; (b) the shut-in time; and (c) the breakdown pressure for the study wells. TDS is
provided as an example of the parameters included in the study. The site C wells are excluded from (a) as the
HF fluid was not sampled at these wells. The site F and site H wells are excluded from (c) as the breakdown
pressure data was not available for wells from these sites.
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Table 4.6: R2 values for the initial sample flowback water chemistry and the variables of interest. R 2 values
greater than 0.2 are in bold italic text, values greater than 0.5 are shaded in grey. Negative correlations are
denoted by (-).
Parameter TDS Cl Na Ca Mg Sr K
HF fluid chemistry 0.31 0.42 0.08 0.32 0.34 0.53 0.04
HF fluid volume per stage 0.09 0.10 0.05 0.08 0.11 0.15 0.08
Shut-in time 0.59 0.55 0.59 0.57 0.47 0.55 0.69
Number of stages 0.10 0.08 0.18 0.07 0.00 0.01 0.12
Breakdown pressure 0.41 0.37 0.50 0.31 0.17 0.24 0.42
Formation water chemistry 0.11 0.03 0.01 0.00 0.00 0.21 0.55 (-)
Chemistry of last flowback sample 0.26 0.25 0.21 0.48 0.23 0.67 0.38
Median carbonate 0.47 0.47 0.34 0.53 0.67 0.57 0.52
Median clay 0.37 (-) 0.34 (-) 0.35 (-) 0.36 (-) 0.43 (-) 0.37 (-) 0.50 (-)
Median feldspar <0.01 (-) <0.01 (-) 0.01 (-) <0.01 (-) 0.01 0.01 <0.01 (-)
Median quartz 0.05 (-) 0.05 (-) 0.02 (-) 0.12 (-) 0.20 (-) 0.16 (-) 0.05 (-)
A step-wise regression was completed in order to identify the variables in the multiple
linear regression that were significantly contributing to the correlation with the flowback water
chemistry. This was completed using the step function in R (R Core Team, 2017) using the
linear equation:
𝑦 = 𝛽 𝑥 +𝛽 𝑥 +⋯+ 𝛽 𝑥 +𝜀
Where, y is the flowback water chemistry as TDS or a major ion concentration, x 1 to xn are the
values of the variables of interest, β1 to βn are the regression coefficients of the variables of
The variables included in the regression analysis are those from Table 4.6, excluding the
chemistry of the last sample and the mineralogy which are both considered in separate analyses
(see Sections 4.4.3.3 and 4.4.3.5). As a result of the lack of data for some of the variables at
different sites, the analysis was completed on four datasets (Table 4.7). Once the significant
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variables were identified for each of the datasets, the relative importance of the variables was
determined using the Lindeman et al. (1980; lmg) method in the relaimpo package in R
(Grömping, 2006). This package takes into account the different scales of the variables in order
to compare them. A similar analysis looking at the relative importance of variables impacting
Table 4.7: Summary of the datasets used in the step-wise regression analysis in order to considered all sites
and all variables of interest. For the initial flowback water samples, the results of the step-wise regression
were similar for datasets I and II as well as datasets III and IV, due in part to the inclusion of the hydraulic
The regression analysis indicates that shut-in time is the most important of the variables
considered in the study on the initial flowback water chemistry, accounting for between 38 and
69% of the variance in the flowback water chemistry (Fig. 4.4). The hydraulic fracturing fluid
chemistry was also found to be correlated with flowback water concentrations of Cl, Ca, Mg, and
Sr (Fig. 4.4a). The formation water TDS was found to have some influence on the flowback
water TDS; however, this variable was only found to be important for datasets I and II
(Fig. 4.4a). Formation water and the number of hydraulic fracturing stages were found to have
minor importance for Ca and Mg concentrations when datasets III and IV were used (Fig. 4.4b).
The number of stages has a negative coefficient in the multiple regression model for Mg and Sr
concentrations in flowback water; however, a simple linear regression with this parameter shows
no correlation with the flowback water chemistry (R2 < 0.05; see Section 4.4.3.4 for discussion).
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a. b.
Figure 4.4: Relative importance of variables found to be significant (p-value < 0.05) in the step-wise
regression analysis. a) Results based on dataset I. Results using dataset II are similar; b) Results based on
dataset III when hydraulic fracturing (HF) fluid was excluded in order to include the site C samples. Results
from dataset IV are similar. Shut-in time was determined to be the most important variable influencing the
initial sample flowback water chemistry. The change in the R2 value for Na concentrations between a and b
is due to including the site C samples which all have a longer shut-in period resulting in a strengthening of the
correlation. These results were calculated using the R package "relaimpo" (Grömping, 2006). The total
The relationship between the initial flowback water chemistry and the formation
mineralogy is complex since the mineralogical data is compositional. Spurious correlations exist
within a compositional dataset due to the data being closed (i.e. adds to 100%); resulting in a
change in one parameter causing a change in the other parameters (e.g., Chayes, 1960; Aitchison,
1982; Pawlowsky-Glahn and Egozcue, 2006). For example, in the mineralogy dataset used in
the current study, the median percentages of carbonate and clay are negatively correlated (R 2:
0.62) making it difficult to determine if the observed correlations are related to having more
135
carbonate or less clay in the formation. Since the positive correlation with percent carbonate
(Table 4.6) are seen for all of the examined parameters and not only the elements found in
carbonates (Ca, Mg), the positive correlation of the initial flowback water chemistry and the
median carbonate content is not interpreted to be due to carbonate dissolution. The correlation
between clay and the major ion concentrations in particular is influenced heavily by the results
for the two site I wells which have relatively low major ion concentrations in the initial flowback
water and the highest proportion of clay. The median quartz and feldspar values are not strongly
The flowback water sample closest to 1,000 m 3 of cumulative flowback water at each of
the wells was selected to represent intermediate to late flowback water chemistry for the
regression analysis. The R2 values for the simple linear regressions are presented in Table 4.8.
The parameters with higher R2 values (> 0.2) are generally the same as those for the initial
samples although overall the correlations are slightly lower (see Table 4.6). The correlations
with the formation water chemistry and the intermediate-late flowback water chemistry remain
low (R2 ≤ 0.30) but are higher than the correlation with the initial sample flowback water
chemistry.
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Table 4.8: R2 values for the intermediate-late flowback water chemistry and the variables. R2 values greater
than 0.2 are in bold italic text, values greater than 0.5 are shaded in grey. Negative correlations are denoted
by (-).
Parameter TDS Cl Na Ca Mg Sr K
HF fluid chemistry 0.20 0.20 0.14 0.47 0.31 0.55 0.02
HF fluid volume per stage <0.01 <0.01 <0.01 <0.01 <0.01 0.06 <0.01
Shut-in time 0.41 0.43 0.29 0.39 0.24 0.56 0.38
Number of stages 0.13 0.10 0.21 0.08 0.02 0.04 0.16
Breakdown pressure 0.29 0.27 0.32 0.21 0.14 0.34 0.38
Formation water chemistry 0.30 0.09 0.05 0.05 0.09 0.14 0.21 (-)
Chemistry of last flowback sample 0.44 0.38 0.57 0.66 0.64 0.68 0.70
Median carbonate 0.36 0.41 0.17 0.48 0.57 0.57 0.32
Median clay 0.35(-) 0.35(-) 0.25 (-) 0.32 (-) 0.44 (-) 0.39 (-) 0.45 (-)
Median feldspar <0.01 (-) <0.01 <0.01 <0.01 0.03 0.01 <0.01
Median quartz 0.03 (-) 0.04 (-) <0.01 0.12 (-) 0.12 (-) 0.16 (-) <0.01
The step-wise regression was completed following the same method that was used for the
initial sample flowback water chemistry. The same four datasets were used, without well A-1,
well A-8, well E-3, or the site F wells due to low flowback water recovery from these wells
(Table 4.7). The results of the analysis indicate that the shut-in time remains an important
variable impacting flowback water chemistry (Fig. 4.5); however, its relative importance is less
than was found with the initial flowback sample dataset. The hydraulic fracturing fluid
chemistry remains an important variable for Sr, Na, and Mg concentrations (Mg in dataset II
only) and the formation water chemistry becomes an important variable for TDS, Cl, Ca, and Mg
concentrations. There is some correlation (R2 > 0.2) between the flowback water chemistry and
breakdown pressure for most of the parameters examined but this variable was only found to be
significant (p-value < 0.05) in the multiple regression with Ca concentrations when dataset IV
was used (Fig. 4.5d). Other parameters that are significant but have a low relative importance in
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certain datasets are the number of stages and the volume of hydraulic fracturing fluid per stage
(Fig. 4.5). Both of these variables have a weak positive correlation (R 2 < 0.1) when considered
alone with the flowback water concentrations and have negative coefficients in the multiple
regressions (see Section 4.4.3.4 for discussion). The correlation between the major ion
concentrations in flowback water and the formation mineralogy for the intermediate to late
flowback water dataset is similar to the correlations for the initial sample dataset. The major ions
are positively correlated with median percent carbonate (0.17 ≤ R 2 ≤ 0.57), negatively correlated
with median percent clay (0.25 ≤ R2 ≤ 0.45) and show weak to no correlation with median
138
a. b.
c. d.
Figure 4.5: Relative importance of variables for intermediate to late flowback water. a) Dataset I – site C and
breakdown pressure excluded; b) Dataset II – sites C, F, and H excluded. The importance of the hydraulic
fracturing (HF) fluid chemistry for Mg concentrations in flowback water in this dataset may be due to some
correlation between the Mg concentration in the HF fluid and the Mg concentration in the formation water
(R2: 0.22), which changes the relative importance of these two parameters for this dataset; c) Dataset III – HF
fluid chemistry and breakdown pressure excluded; d) Dataset IV – Site F, site H, and HF fluid chemistry
excluded. The relative importance of the shut-in time is higher when the site C wells are included (c, d) which
is likely due to the longer shut-in time for these wells having an impact on the correlation. Correlation
between flowback water chemistry and the number of stages as well as the HF fluid volume per stage (d) are
negative. These results were calculated using the R package "relaimpo" (Grömping, 2006). The total height
139
4.4.3 Important variables influencing flowback water chemistry
Shut-in time was found to be an important variable influencing flowback water chemistry
and although the relative importance is higher early in the flowback period, it continues to be
correlated with the later flowback water chemistry even after 1,000 m 3 of flowback water has
been produced from a well. The elevated TDS and major ion concentrations in the initial
flowback water from wells with longer shut-in periods are interpreted to be related to a longer
time for mixing between the injected hydraulic fracturing fluid and the formation water as well
as for water-rock interactions prior to initiating flowback from the well. Higher concentrations at
the beginning of the flowback period result in a greater volume of flowback water with higher
ion concentrations over the course of the flowback period. Having higher TDS and higher major
ion concentrations in the flowback water is an important consideration for flowback water
management as it may require additional treatment for reuse or disposal (e.g., Fontenelle et al.,
2013; Notte et al., 2016). The correlation between the ion concentrations and the shut-in time in
the later flowback period would be expected to decrease over time as the ion concentrations are
expected to be influenced by other variables throughout the flowback period, including the
Another consideration for flowback water management is the use of blended freshwater
and recycled flowback water for use for hydraulic fracturing fluids. The higher TDS of the
blended fluids influences the initial flowback water chemistry. A positive correlation with the
hydraulic fracturing fluid chemistry was anticipated as the initial flowback water is expected to
be composed of a relatively high proportion of the injected fluid due to less time for fluid mixing
140
and any water-rock interactions that are occurring in the subsurface. The hydraulic fracturing
fluid chemistry was identified as a significant variable (p-value < 0.05) for Cl, Ca, Mg, and Sr
concentrations in the initial flowback water samples collected for the present study. The lack of
a correlation between the Na and K in the hydraulic fracturing fluid and the initial flowback
water is unexpected (R2: 0.08 and 0.04 for Na and K, respectively). Several of the initial
flowback water samples plot close to a 1:1 line between the hydraulic fracturing fluid chemistry
and the flowback water chemistry for these ions, indicating that there may be a correlation at
some sites. The majority of the initial flowback water samples have higher Na and K
concentrations that are not correlated to the chemistry of the injected fluid, as the concentrations
in the initial flowback water are often high when the concentrations in the injected fluid are low.
This relationship may indicate that Na and K concentrations are increasing due to cation
exchange, which would increase the concentrations of these ions in the initial flowback water
due to exchange with the divalent ions on the exchange sites of the clay minerals. The cation
exchange process would be initiated by the injection of the relatively fresh hydraulic fracturing
fluid into the high TDS fluid present in the formation (e.g., Appelo, 1994). The Montney
Formation has low cation exchange capacity (CEC; Table 4.9). There is some variability in CEC
in the available results (range: 9.30 to 20.4 cmol(+)/kg, median: 17.3 cmol(+)/kg), indicating that
the relative importance of the cation exchange process could vary between wells due to
differences in formation mineralogy and fluid chemistry. Overall, the CEC is not correlated to
the percentage of clay in samples from the Montney Formation (R 2 = 0.01); however, when
examined separately both the exchangeable Na and K ions correlate with the percentage of clay
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Table 4.9: Cation exchange capacity (CEC) of samples from the Montney Formation. These samples were
selected for the CEC analysis based on the variable clay content in order to determine if the CEC is
The formation water chemistry TDS, Cl, Ca, and Mg concentrations have significant
correlations with the intermediate-late flowback water chemistry in the multiple regressions
while the other major cations in flowback water do not show significant correlations with the
formation water chemistry (Fig. 4.5). Intuitively, the formation water chemistry is expected to
be one of the main variables impacting the flowback water chemistry since mixing between the
injected fluid and the formation water is anticipated to be a dominant process influencing the
flowback water chemistry (e.g., Haluszczak et al., 2013; Olsson et al., 2013; Engle and Rowan,
2014; Vengosh et al., 2017), particularly in the later flowback period when the proportion of
formation water is higher. The lack of a correlation between the flowback water chemistry and
the formation water chemistry for Na, K, and Sr could be related to a greater importance of other
142
parameters, such as shut-in time, or other processes not considered in the present study,
including cation exchange or a stronger dependence on lateral variability between sites. The low
variability in the formation water chemistry between sites and the uncertainty in the estimated
values for the formation water chemistry used in the analysis may also contribute to the low
correlation between the formation water and the flowback water for TDS and the major ion
concentrations.
The chemistry of the last flowback water sample collected at each of the wells is used in
a secondary analysis as a proxy for formation water, in as much as this sample has the highest
percentage of formation water for each of the wells. The correlation between the formation
water proxy and the flowback water chemistry is higher relative to the correlation between the
formation water chemistry estimated from the produced water results and the flowback water
chemistry for both the initial and intermediate-late data sets (see Tables 4.6 and 4.8). For the
secondary analysis looking at the initial sample chemistry, a multiple regression was completed
with the shut-in time, the hydraulic fracturing fluid chemistry, and the last sample chemistry as
the variables. The shut-in time remains the variable with the highest relative importance (> 40%;
Fig. 4.6a). The relative importance of the injected fluid and the last sample chemistry is lower
(< 25%).
The intermediate to late flowback water chemistry, approximated by the 1,000 m 3 sample
for each well, shows a higher relative importance for the last sample chemistry (30% to 58%;
Fig. 4.6b). There is a significant increase in the relative importance of this variable from the
initial sample chemistry, supporting the increasing importance of formation water chemistry on
the flowback water chemistry as the flowback period progresses. However, there is some
complication added to the analysis due to using samples from the same site as both an
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independent variable (the 1,000 m3 sample chemistry) and as one of the dependent variables (the
last sample chemistry). An earlier and a later sample from the same site would be expected to
have some correlation since the processes affecting the early sample would also have some effect
on the late sample. The shut-in time remains an important variable for this analysis (18 to 35%
relative importance). In order to investigate the importance of the formation water chemistry in
the absence of the influence of the shut-in time, the initial sample major ion concentrations were
subtracted from the intermediate-late (1,000 m 3) flowback water major ion concentrations.
However, the correlation with formation water was not significantly increased for the modified
data.
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a. b.
Figure 4.6: Relative importance of parameters, including the last sample chemistry as a proxy for the
formation water chemistry for a) the initial flowback water samples; and b) the intermediate-late flowback
water samples. The low correlation seen for Na concentrations (adjusted R2: 0.42) in (a) is due to low
correlations between the initial sample flowback water Na concentrations and both the hydraulic fracturing
fluid (R2: 0.08) and Na concentrations in the last samples from each of the wells (R2: 0.03), which is due to
several samples with relatively low initial Na concentrations and high Na concentrations in the last sample.
For some of the other major ions, these samples also have low concentrations in the initial sample and high
concentrations in the last sample, although they do not have as great of an effect on the overall correlation.
The breakdown pressure was only found to have a significant correlation with Ca
concentrations in intermediate to late flowback water when dataset IV is used (Fig. 4.5d). A
higher breakdown pressure may create a more extensive and more complex fracture network due
to higher pressure conditions. The more extensive fracture system would allow for increased
mixing and a higher surface area exposed for more potential reactions with the injected hydraulic
fracturing fluid (e.g., Bearinger, 2013; Zolfaghari et al., 2015a). A higher breakdown pressure
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would also relate to higher stress in the formation so that during the flowback period more
microfractures would close and decrease the water to rock ratio. When considered alone, there is
a positive correlation between the breakdown pressure and both the initial and intermediate-late
flowback water chemistry (Tables 4.6 and 4.8). This correlation may be due in part to the
moderate correlation between breakdown pressure and shut-in time (R 2: initial: 0.56;
intermediate-late: 0.62), rather than a significant correlation with the flowback water chemistry
since this variable was not significant in the majority of the multiple regressions.
The correlations between the Ca and Mg concentrations with the number of hydraulic
fracturing stages and the hydraulic fracturing fluid volume per stage are negative in cases where
these variables are significant (p-value < 0.05) (Fig. 4.4, 4.5). When considered individually,
these parameters show a weak positive correlation or no correlation with the flowback water
chemistry for the initial samples or 1,000 m3 of flowback water samples (see Tables 4.6 and 4.8).
The low correlation indicates that it is not a relevant parameter and that the change in sign of the
correlation with the number of hydraulic fracturing stages and the hydraulic fracturing fluid
volume per stage in the multiple regression may be due to instability in the model due to the
weak correlation or due to minor correlation with other variables. For example, both the shut-in
time with the number of stages and the breakdown pressure with the hydraulic fracturing fluid
The relationship between the Montney Formation mineralogy and the flowback water
chemistry is discussed separately due to the added complexity of using closed compositional data
formation mineralogy and the flowback water chemistry, both the concentrations of the major
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ions and the ratios of the major cations to Cl were considered. The monovalent ion (Na, K)
concentrations have a negative correlation with median percent (by weight) clay (Fig. 4.7a);
while the Na/Cl and K/Cl ratios have a positive correlation with median percent clay (Fig. 4.7c).
The correlation with median percent carbonate has the opposite sign for both the concentrations
and the ratios. The divalent ions (Ca, Mg, and Sr) have a negative correlation with median
percent clay for both the concentration of the ion and the ratio with Cl (Fig. 4.7b, d). The
The increasing monovalent cation to Cl ratios indicate that the monovalent cation
concentrations are increasing more rapidly than the Cl concentrations as the clay content
increases whereas the divalent cation concentrations are increasing at a slower rate than the Cl
concentrations. These relationships indicate the occurrence of cation exchange. When the
relatively low salinity hydraulic fracturing fluid is injected into the formation containing the
saline formation water, the relatively mobile Na ions would be displaced from the cation
exchange sites for Ca ions (e.g., Appelo, 1994) producing an increase in Na concentrations and a
percentage of clay is supported by the cation exchange results for the Montney Formation
(Table 4.9). The relationship between the ion ratios and the carbonate content could be due to
the inverse relationship between clay content and carbonate content rather than a result of a
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a. b.
c. d.
Figure 4.7: Correlations between (a) Na concentrations; (b) Ca concentrations; (c) Na/Cl; and (d) Ca/Cl with
median clay. The Na, Ca, and Cl concentrations are from the initial sample data. The 1000 m3 data shows
similar results. The ion ratios are molar ratios. Median clay was calculated based on existing data from
nearby wells completed near the same stratigraphic interval of the Montney Formation.
The multiple regressions do not fully characterize the flowback water system (adjusted R 2
values < 0.85) indicating that there are other variables that are not considered in the analysis
and/or the relative importance of studied variables varies by well. Several additional variables
were not evaluated in the present study but are likely important (see Table 4.1) including the
extent and complexity of both the natural and induced fracture systems, the imbibition rate, and
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the reservoir porosity, permeability, and fabric. Percent recovered could act as a proxy for the
amount of imbibition, as a higher percent recovered would correlate with a lower imbibition rate
in the flowback period. A lower imbibition rate would be expected to produce less formation
water through countercurrent imbibition and result in flowback water with a lower salinity. The
current dataset was examined at different times throughout the flowback period and shows only a
weak negative correlation between percent recovered and TDS for the flowback water samples
(e.g., correlation for the day 3 dataset [R2 = 0.09] and for the day 7 dataset [R2 = 0.10]). These
results indicate that the amount of imbibition may not have an important influence on the
flowback water chemistry or its importance may be obscured within the data for percent
recovered by additional factors, including the length of the shut-in period and the flowrate.
A potential source of uncertainty in the study is that particular variables may only be
important at certain sites or certain wells. For example, the number of stages may be important
at one site but not all sites. If this is the case, there would be no correlation for the full dataset
and the variable would not be identified in this type of analysis. The potential for inconsistency
in the variables influencing the flowback water chemistry illustrates the complexity of the
controls on the system. More in-depth studies may identify additional variables that should be
considered and would provide a more complete understanding of the influences on flowback
water chemistry.
4.5 Conclusions
The analysis of the flowback water from multiple wells from the same formation allows
for an investigation into the variables that impact the flowback water chemistry. The influence
of these variables complicates the interpretation of flowback water chemistry data although
working towards a more complete understanding of the controls on flowback water chemistry
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will permit further interpretations to be made on the processes that are occurring in the formation
during and following hydraulic fracturing. The main conclusions from the multiple regression
analysis are:
Of the variables considered in the current study, those identified as important to the
flowback water chemistry were the shut-in time, the hydraulic fracturing fluid chemistry
(Cl, Ca, Mg, Sr – for the initial flowback), and the formation water chemistry (TDS, Cl,
Ca, Mg – for the intermediate to late flowback). Using the last sample flowback water
chemistry to approximate the formation water chemistry shows that the shut-in time
decreases in importance over the flowback period, while the relative importance of the
last sample flowback water chemistry, as a proxy for formation water, increases.
water and the percentage of carbonates in the formation is not interpreted to be due to
carbonate dissolution as the other major ions (e.g., Na) are also positively correlated with
percent carbonate.
The ratios of the monovalent and divalent cations to Cl show opposing trends with the
percentage of clay. The monovalent cation ratio shows a positive correlation while the
divalent ratio shows a negative correlation. This result indicates that cation exchange is
impacting the flowback water chemistry. Further work should focus on identifying and
quantifying additional variables that may influence the flowback water chemistry in order
to develop more complex models. In addition, some parameters may only be affecting
the flowback water chemistry at certain wells and would therefore not show a correlation
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when the full dataset is examined. More in-depth studies at an individual well level or
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Chapter 5: Key minor elements in Montney Formation flowback water:
5.1 Introduction
Following hydraulic fracturing of unconventional oil and gas wells, fluid returns to the
surface. The initial liquid is referred to as flowback water 8 and has elevated total dissolved
solids (TDS) due to the high concentrations of the major ions, including chloride (Cl), sodium
(Na), calcium (Ca), potassium (K), magnesium (Mg), and strontium (Sr) (e.g., Haluszczak et al.,
2013; Rowan et al., 2015; Ziemkiewicz and He, 2015). If the well is hydraulically fractured with
a freshwater based fluid, the ion concentrations normally increase from the beginning of the
flowback period due to mixing between the injected hydraulic fracturing fluid and the formation
water, possibly with some influence from mineral precipitation and dissolution (Wilke et al.,
2015; Dieterich et al., 2016; Harrison et al., 2017; Marcon et al., 2017) and ion exchange
(Renock et al., 2016; Zolfaghari et al., 2016). The majority of the discussion surrounding the
inorganic chemistry of flowback water has focused on the major ions (e.g., Haluszczak et al.,
2013; Rowan et al., 2015; Rosenblum et al., 2017). However, additional ions are commonly
included as part of the geochemical analysis and can be used to gain further information from the
flowback water. Barium (Ba), for example, is often high in flowback water (> 100 mg/L) and
shows more variability between wells in a particular formation relative to the major cations (e.g.,
Chapman et al., 2012; Barbot et al., 2013). Other ions, including boron (B) and lithium (Li),
8
Flowback water is defined in our study as the water that returns to surface after hydraulically fracturing a well and
prior to the production phase of the well.
152
may be useful in distinguishing the fluid from hydraulically fractured wells from surface water or
from water produced from conventional oil and gas wells, which can be accomplished by
examining the B/Cl and Li/Cl ratios and the B and Li isotopic values of the fluids (Warner et al.,
2014; Vengosh et al., 2015). Additional studies characterize the naturally occurring radioactive
materials (NORM) (e.g., Nelson et al., 2015, 2016) and trace elements in flowback water (e.g.,
Phan et al., 2015), both of which may be important to consider for the storage of flowback water
The present study focusses on Ba, B, and Li concentrations in flowback water from the
Lower Triassic Montney Formation in northeast British Columbia (BC) and northwest Alberta.
These three minor ions were selected for further investigation as these ions are often elevated
(> 10 mg/L) in the Montney Formation flowback water sampled in our study and may show
more variability between different regions or between different members of the Montney
Formation compared to the major ions. High concentrations of these elements are not unique to
Montney Formation flowback water as they are commonly elevated in flowback water from
other hydraulically fractured formations (e.g., Haluszczak et al., 2013; Rowan et al., 2015; Phan
et al., 2016).
(Zonneveld et al., 2011; Zonneveld and Moslow, 2014), deposited along the northwestern coast
of Pangea in a marine inner to distal shelf environment (Davies, 1997; Chalmers and Bustin,
2012). The most recent stratigraphic study on the Montney Formation divides the formation into
lower, middle, and upper informal members, each representing a Third-Order sequence (Davies
and Hume, 2016; Fig. 5.1). The division into these three informal members is used in the present
study. Flowback water samples for this study were obtained from two lower Montney member
153
wells, eleven middle Montney member wells, and eighteen upper Montney member wells. The
wells are located on nine well pads across the formation with one to eight wells sampled per pad
(Fig. 5.2). The current study includes a discussion of Ba, B, and Li concentrations in Montney
Formation flowback water in support of the analysis of the major ion chemistry of the flowback
Figure 5.1: Schematic cross-section of the Montney Formation in BC and Alberta. The formation is divided
into the lower, middle, and upper Montney Formation informal members based on three Third-Order
sequences, determined by lithostratigraphy and biostratigraphy. As defined by Davies and Hume (2016), the
upper Montney member includes the lower Doig siltstone and underlies the Doig Phosphate Zone. This
member thins to the east and is absent in eastern locations in Alberta. Overall, the formation becomes
coarser grained moving from west to east, towards the paleo-shoreline. Modified from Davies and Hume
(2016).
154
Figure 5.2: Location of the study sites in northeastern BC and northwestern Alberta. Fluid samples were
collected from 9 sites in the Montney Formation. Sites with upper Montney member wells include site A (8
wells), site B (2 wells), site C (5 wells), site D (2 wells), and site H (1 well). The sites with middle Montney
member wells include site C (2 wells), site D (2 wells), site E (4 wells), site F (2 wells), and site G (1 well). The
lower Montney member wells include the two wells at site I. The outline of the Montney Formation is
5.2 Methods
5.2.1 Hydraulic fracturing fluid, flowback water, and produced water chemistry
Hydraulic fracturing fluids, comprised of the base fluid with additives, were collected
from all sites, except for site C. For sites A, B, D, E, G, and H a separate sample of the fluid
used in each of the stages of the fracturing program was collected (14 to 26 samples per well).
Samples from consecutive stages with similar electrical conductivity readings were combined in
equal proportions to make composite samples. Combining samples with similar electrical
conductivity reduces the number of analyses required while still allowing for an assessment of
155
the variability in chemistry between the fluids used in different stages of the hydraulic fracturing
process. The Ba, B, and Li concentrations for each well were determined by calculating the
volumetric proportion represented by the stages in the composite samples and using this to
determine the overall concentration. For example, if three composite samples were analyzed and
each represents an equal volume of hydraulic fracturing fluid, the geochemical results from each
of these samples is given equal weight in calculating the overall value. Only one hydraulic
fracturing fluid sample was obtained for the site F wells and each of the site I wells.
Flowback water samples were collected from all sites over the flowback period, which varies
between the wells from one day up to 33 days. A higher sampling frequency of two to three
samples per day was utilized early in the flowback period in order to capture the variation in
fluid chemistry during this time. After the first week of the flowback period one sample per day
was collected. Produced water samples, from after the well has begun producing oil or gas, were
collected from the site A wells, the site B wells, and a well approximately 20 km away from site
I. No produced water samples were collected from the wells at the remaining sites. Publically
available produced water results9 were compiled for wells completed in the Montney Formation
within approximately 20 km of the study wells in order to provide an estimate of the produced
water chemistry in these regions. However, these results are generally limited to the major
cations and only occasionally included Ba concentrations. The B and Li concentrations were not
9
The data was compiled by the BC Oil and Gas Commission and accessed using geoSCOUT ®.
156
All samples were stored at 4°C prior to analysis. As filtering and sample preservation
was not conducted at the time of sampling, the flowback and produced water samples were
heated in Teflon® containers in a hot water bath back to reservoir temperature (75-80°C) prior to
the analysis. This step was conducted to approximate reservoir temperatures and re-dissolve any
precipitate that had formed during sample transportation and storage. The hydraulic fracturing
fluids were not heated. All samples were filtered and subsampled for the separate analyses: 1)
anions; 2) pH, electrical conductivity, and alkalinity; and 3) dissolved metals. The anion
samples were analyzed by ion chromatography at an external laboratory in Victoria, BC. The
remaining analyses were conducted at The University of British Columbia (UBC) in Vancouver,
BC. The pH was measured using an OMEGA ® PHB21 portable pH meter, the electrical
conductivity was measured using a HACH® CDC401 conductivity probe, and the alkalinity was
determined by titrating the sample with sulfuric acid (H2SO4) using a HACH® Model 16900
digital titrator. The dissolved metal samples were preserved with trace metal grade nitric acid
(HNO3) to pH < 2. The preserved samples were acid digested with HNO3 and hydrochloric acid
the analysis. The major cation, Ba, B, and Li concentrations were determined by inductively
Formation flowback water, the Montney Formation mineralogy was investigated. The study
wells were not cored therefore mineralogy is not available directly from these wells. To obtain
an approximation of the mineralogy of the fractured zones of the study wells, publically
available X-Ray Diffraction (XRD) data was compiled for nearby wells completed in the same
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stratigraphic interval of the Montney Formation. Gaps in the available data were identified near
site A and for the upper Montney member at site C and site D. Additional samples from wells
nearby these sites were obtained from the BC Oil and Gas Commission core research facility in
Fort St. John, BC. These samples included both core and drill cutting samples. The additional
samples were prepared following the modified smear mount method (Munson et al., 2016) and
analyzed at UBC using a Bruker D8 Focus X-ray powder diffractometer. The results were
processed using the Rietveld method (Rietveld, 1967, 1969). Identification of trace minerals
observed in the core samples from a well near site A was completed on core fragments with
approximate dimensions of 1cm x 1cm x 0.5cm using a Philips XL30 scanning electron
The potential for barite precipitation or dissolution was investigated by examining the
barite saturation indices (SI) of the flowback water samples. No minerals containing B or Li
ions were close to saturation in the flowback water. A negative SI indicates that the mineral is
undersaturated and will dissolve in the solution, while a positive SI suggests that the mineral is
oversaturated and will precipitate. Values close to zero show that the mineral is in equilibrium
with the solution. All SI values were calculated using the flowback water chemistry in
PHREEQC, version 3.2.0 (Parkhurst and Appelo, 2013) at a reservoir temperature of 75°C.
A brief overview of the major ion chemistry of the Montney Formation flowback water
from the study wells is provided in this paper, while a more in-depth discussion of these results
has been presented in Chapters 2, 3, and 4 of this thesis. The dominant ions in Montney
Formation flowback water are Cl, Na, Ca, K, Mg, and Sr (Table 5.1). Wells completed at the
same site and within the same member of the Montney Formation generally have similar major
158
ion chemistry; however, the many different variables, such as fracture complexity and amount of
imbibition, that can impact the flowback water chemistry and result in differences even between
wells at the same site with similar completion parameters (see Chapter 3; Chapter 4). Overall, the
major ion concentrations are slightly higher in the upper Montney member flowback water,
although this division is not distinct between all of the study wells. Sr concentrations in the
upper Montney member flowback water range from high concentrations in the northwestern
region to low concentrations in the southeastern region of the study area, although sampling
additional wells in the northwestern and the southeastern regions is required to verify the trend.
The other major ions do not show geographic trends across the study area.
The concentrations of the major ions increase over the flowback period for all of the
study wells, which is mainly due to mixing between the injected hydraulic fracturing fluid and
the formation water (see Chapter 2). Mixing has previously been suggested as the source of
increasing TDS and ion concentrations in flowback water by others (e.g., Haluszczak et al.,
2013; Engle and Rowan, 2014; Kondash et al., 2017). The injected hydraulic fracturing fluids
for the wells in our study were composed of a freshwater-based fluid for well A-3, the site C
wells, wells D-1 through D-3, well H-1, and the site I wells and a blend of freshwater with
recycled flowback water for the remaining site A wells, the site B wells, well D-4, and the sites
E, F, and G wells. The TDS10 of the initial flowback water is either close to or higher than the
injected hydraulic fracturing fluid TDS for all wells. The chemistry of the injected fluid was
found to have some influence on the initial flowback water chemistry, with higher injected fluid
major ion concentrations resulting in higher initial flowback water concentrations for Cl, Ca, Mg,
10
The ion concentrations are added together to calculate the TDS.
159
and Sr (see Chapter 4). The length of the shut-in period was determined to be the dominant
influence on the flowback chemistry with longer shut-in periods correlating to higher initial TDS
and major ion concentrations, likely due to a longer time for mixing in the fractures (see Chapter
4). The increasing contribution from formation water over the flowback period was calculated
for the study wells using Cl and the stable water isotopes (δ18O and δ2H) as conservative tracers
(see Chapter 2). In general, the proportion of formation water for the study wells increases to
approximately 60% by the end of the flowback period, based on the 75 th percentile calculated
using the proportions from the last sample for each well (see Chapter 2). Although mixing
between the hydraulic fracturing fluid and the formation water is interpreted to be the dominant
influence on Montney Formation flowback water chemistry, the divalent ions (Ca, Mg, and Sr)
are also influenced by ion exchange (see Chapter 2). This interpretation is based on the lower
concentrations of these ions in the early time flowback water due to exchange with Na ions,
In contrast to the Cl and major cation concentrations, sulfate (SO 4) concentrations are not
elevated in all wells (Table 5.1). In addition, the SO 4 concentrations do not show the constant
rate of increase that was observed for other ions. For the study wells, the SO 4 concentrations
suggested by others (Engle and Rowan, 2014; Wilke et al., 2015; Harrison et al., 2017). SO 4
Table 5.1 (following page): Summary of the general chemistry and the major ion, Ba, B, and Li
concentrations for the study wells. The results for wells located on the same site and within the same member
of the Montney Formation are grouped together. In general, the charge balance error falls within ±15% for
the flowback water samples from the study wells. The higher charge balance errors are interpreted to be due
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5.4 Key Minor Elements in Flowback Water
Similarly to the major ions, the concentrations of Ba, B, and Li are likely significantly
influenced by mixing between the injected hydraulic fracturing fluid and the formation water and
possibly by water-rock interactions (e.g., Phan et al., 2016; Renock et al., 2016). The minor ion
concentrations are not directly related to the injected hydraulic fracturing fluid chemistry as the
concentrations of these ions are generally low (< 10 mg/L) in this fluid and for sites where
freshwater is used as the base fluid, the Ba, B, and Li concentrations are < 3 mg/L (Table 5.2).
The variability between sites and the potential sources of Ba, B, and Li in flowback water are
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Table 5.2: Summary of the hydraulic fracturing fluid Ba, B, and Li concentrations for each of the study wells.
These values are derived from the composite fluid samples and are estimates of the overall fluid chemistry
based on the volumetric proportion of fluid that was used in each of the hydraulic fracturing stages. Only
one hydraulic fracturing fluid sample was collected for the site F wells and for each of the site I wells. No
5.4.1 Barium
Within the sampled flowback waters, the Ba concentrations span from below the
detection limit (< 1 mg/L) up to 467 mg/L (Table 5.1). There is generally an increase in Ba in
flowback water over the flowback period for each of the study wells with considerable variability
between different sites (Fig. 5.3). The shut-in time has some effect on the Ba concentrations,
with a longer shut-in period correlating to a higher Ba concentration in the initial flowback water
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samples (R2 = 0.37). The length of the shut-in period for the study wells would influence the
chemistry by controlling the amount of time for mixing and geochemical reactions prior to the
initiation of flowback from the well. The overall geographic trend for Ba concentrations across
the study area is a decrease from the northwestern region of the study area near sites A and I to
the southeastern region near site H. The site C wells in the central region of the study area are an
exception to the trend with higher Ba concentrations (12 to 311 mg/L) relative to wells at nearby
sites, which have concentrations that remain < 10 mg/L. The higher Ba concentrations in
flowback water from site C are likely related, at least in part, to the length of the shut-in period
for these wells. Regional variability in Ba concentrations in flowback water has previously been
observed in samples from the Marcellus Shale in Pennsylvania, although in the Marcellus
Formation flowback water the Ba concentrations often reach concentrations > 1,000 mg/L after
one week of flowback (Chapman et al., 2012; Barbot et al., 2013) which is considerably higher
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a. b.
c. d.
e. f.
Figure 5.3: Ba concentrations over the flowback period plotted as cumulative flowback volume for a) Site A
wells; b) Site B wells; c) Site C wells; d) Site D wells; e) Site E-H wells; and f) Site I wells. The Ba
concentrations increase over the flowback period for the majority of wells. The upper Montney member
wells include the site A wells, the site B wells, wells C-1 through C-5, well D-1, well D-2, and well H-1; the
middle Montney member wells include well C-6, well C-7, well D-3, well D-4, the site E and site F wells, and
well G-1; the lower Montney member wells include the site I wells. Note the variability in the scales.
165
There is some indication of differences in Ba concentrations in flowback water from the
upper and middle members of the Montney Formation when comparing wells completed at the
same site. At site C, the upper Montney member flowback water generally has lower Ba
concentrations compared to the middle Montney member flowback water; however, well C-5
which was completed in the upper Montney member is an exception with similar Ba
concentrations to the two middle Montney member wells (Fig. 5.3c). The site D wells show the
opposite trend with the upper Montney member flowback water having higher Ba concentrations
relative to the middle Montney member flowback water, although there is some overlap over the
flowback period for these wells (Fig. 5.3d). The upper Montney member wells at site D also
have longer shut-in periods which likely contribute to the higher concentrations. The only two
wells completed in the lower Montney member are located at site I. Both of these wells had high
Ba concentrations (> 100 mg/L) near the end of the flowback period; however as there are no
other wells in this region with comparable cumulative flowback volumes an evaluation of the Ba
concentration in flowback water from the lower Montney member relative to another member of
the formation in the same region was not possible with the current data.
The regional variability in the flowback water Ba concentrations may be related to spatial
variability in Ba concentrations in formation water. The formation water chemistry in this study
is approximated by the produced water results (Table 5.3), as the produced water concentrations
are expected to approach those in formation water. Ba concentrations are high in the publically
available produced water results from wells completed within the Montney Formation near site
C, as well as in the produced water sample near site I that was analyzed as part of our study
(Fig. 5.4), corresponding to the locations of the two sites where the highest flowback water Ba
concentrations were measured. The Ba concentrations in the hydraulic fracturing fluid are low
166
(< 5 mg/L) for the majority of wells and would not have a large impact on the flowback water
chemistry. There are some elevated Ba values (up to 32 mg/L) in the fluids used at site A
(Table 5.2). These higher Ba concentrations could result in higher concentrations in the initial
flowback water, although, the later stage flowback water is expected to be influenced mainly by
Figure 5.4: Ba concentrations in produced water samples from wells completed in the Montney Formation
and located up to 20 km from the study sites. Results for sites A, B, and I are for samples collected in the
present study, results for sites D-H were compiled from publically available produced water results. The box
portion of the boxplot shows the 25th percentile, the median, and the 75th percentile. The whiskers show the
interquartile range (IQR). Site H and site I appear as a line as only one sample which included Ba results was
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Table 5.3: Summary of produced water Ba, B, and Li concentrations compiled as part of the study. The
results for site A and site B are from produced water samples collected from the study wells. The results for
sites C-H are from publically available results, which did not include B and Li concentrations. The
concentrations for site I were from a produced water sample obtained from a nearby well. Where multiple
The Ba concentrations in both the formation water and the flowback water may be
the study wells are negatively correlated with SO4 concentrations (Fig. 5.5). A negative
correlation has also been observed in previous studies with Marcellus Shale flowback water and
creating a more favorable, lower salinity environment for the bacteria as a result of the injection
of the hydraulic fracturing fluid into the formation (Engle and Rowan, 2014). The presence and
abundance of SO4 reducing bacteria in different regions would vary the amount of SO 4 reduction
occurring in the formation. If the bacteria are present the onset of SO 4 reduction is rapid
168
(Machel, 2001).The removal of SO4 would increase the barite solubility in the formation, thereby
increasing the Ba concentrations. Barite dissolution has previously been suggested as a source of
correlated to the amount of barite in the formation (Renock et al., 2016; Zolfaghari et al., 2016).
Barite is not found in the Montney Formation at a high enough percentage to be detected by an
XRD analysis; however, small (< 0.5 cm) crystals were observed in the core examined from the
region near site A and identified as barite using SEM (Fig. 5.6). A Ba precipitate has also been
observed along natural fractures in other formations (e.g., the Lower Keg River formation;
Zolfaghari et al., 2016). Additional factors contributing to higher barite solubility in the
formation in comparison to the solubility in freshwater at surface include the high ionic strength
of the water involved in the water-rock interactions during hydraulic fracturing combined with
the reducing conditions in the formation (Renock et al., 2016), the elevated temperatures and
pressures in the formation (Blount, 1977), and the presence of organic matter (He et al., 2014),
which may also act to inhibit barite precipitation (Marcon et al., 2017).
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Figure 5.5: The relationship between Ba and SO4 concentrations for the sampled wells. Results for individual
wells are grouped by site. These parameters are negatively correlated, which is related to SO 4 reduction and
barite solubility. Note the logarithmic scale is used due to the large variability in concentrations between
wells. ▲- upper Montney member wells; ● – upper and middle Montney member; - middle Montney
Barite
100 µm
Figure 5.6: Barite in a core sample from a well located near site A.
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The results of our study do not directly support barite dissolution as a dominant
geochemical process impacting the Ba concentrations given that the Ba and SO 4 concentrations
in flowback water do not increase together as would be expected if only barite dissolution was
occurring. The Ba and SO4 concentrations at each of the sites were investigated in more detail.
The SI for barite in the flowback water remains close to equilibrium or slightly over/under-
saturated for site A, site B, and site D with SI values generally remaining between -0.4 and 0.4.
The flowback water from the wells at sites A and D typically have increasing Ba concentrations
and stable SO4 concentrations over time. The increase in Ba may be due primarily to mixing
with formation water as the SI values do not show an increasing trend which would indicate
barite dissolution. Site B is notable in that it has relatively stable (well B-1) or decreasing (well
B-2) Ba concentrations over the flowback period, differing from the increasing Ba
concentrations that are observed in the flowback water from the majority of the other wells. The
flowback water from the site B wells also show stable or decreasing SO 4 concentrations and
negative SI values for barite. Well B-1 has barite SI values that generally remain between -0.4
and -0.1 indicating that the flowback water from this well is close to equilibrium with barite.
The decreasing Ba and SO4 concentrations at well B-2, along with the decreasing barite SI values
which decrease from -0.1 to -1.0, support barite precipitation in this well.
The site C wells have high Ba in flowback water, reaching concentrations > 20 mg/L by
the middle of the flowback period, and low (< 30 mg/L) SO4 concentrations. As these wells
were shut-in for 21 to 30 days prior to beginning flowback, bacterial SO 4 reduction along with
barite dissolution may have taken place in the reservoir during the shut-in time. These two
processes would in combination explain the low SO 4 and high Ba in the flowback water from
these wells. Mixing with formation water also likely contributes to the Ba concentrations. The
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SI for barite in several of these wells is negative (site C, wells 1 through 5) and often below -1.
If SO4 reduction was occurring at a faster rate than barite dissolution, the flowback water could
still remain undersaturated with respect to barite in this scenario. Flowback water from well C-6
and well C-7 is oversaturated in barite, although the SI is stable over time, which may indicate
Flowback water from well E-1, well E-2, and well E-4 have barite SI values that are
slightly oversaturated early in the flowback period (SI = 0.6-0.7) and remain positive but show a
decreasing trend towards equilibrium. The decreasing SI indicates barite precipitation. The
decreasing SO4 concentrations in the flowback water from these wells may be due to Ba
precipitation rather than SO4 reduction, while the increasing Ba concentrations may be due to
mixing with formation water with higher Ba concentrations and not Ba dissolution. Well E-3 has
barite SI values that increase over the flowback period from 0.2 to 0.4 and also shows a more
rapid increase in Ba concentrations relative to the other site E well (see Fig. 5.3e). The
increasing SI, along with the increase in Ba and SO4 concentrations supports barite dissolution in
this well. SO4 reduction may be occurring but at a slower rate relative to SO4 production by
barite dissolution.
The site F wells have increasing SO4 and decreasing Ba over the flowback period. The
barite SI for both wells decreases over the flowback period from slightly oversaturated (SI = 0.3
to 0.5) to either equilibrium (-0.04; well F-2) or until undersaturated (-0.4; well F-1). The
decreasing trend for SI indicates barite precipitation and is supported by the decreasing Ba
concentrations over the flowback period. The site F flowback waters show increasing SO 4
concentrations; however, this is likely a result of the chemical reaction that occurs due to the
addition of sodium hypochlorite (NaOCl) to treat hydrogen sulfide (H 2S) in the flowback water
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at surface. SO4 concentrations would continue to increase as it is continually produced by the
The site G and site H wells have high sulfate (> 600 mg/L) and among the lowest Ba in
the study with Ba concentrations that remain below 1.5 mg/L and often below the detection limit
(< 1 mg/L). The elevated SO4 is likely related to pyrite oxidation which has been suggested as a
source of SO4 in both formation water (Dresel, 1985) and in flowback water, as pyrite oxidation
may increase during the hydraulic fracturing process due to the injection of oxic hydraulic
fracturing fluid into the formation (Wilke et al., 2015; Harrison et al., 2017). There is no
indication that SO4 reduction is a dominant process in these wells as the SO 4 concentrations
remain high and relatively stable. The stable SO4 concentrations may indicate that SO4 reducing
bacteria are not present or are inactive in the site G and site H wells. The decreasing SI of barite
over the flowback period at well G-1 (SI = 0.8 to 0.1) and well H-1 (SI = 0.6 to 0.2) indicates
that the flowback water is moving towards equilibrium as any barite introduced through mixing
The flowback water from the two site I wells attain among the highest Ba concentrations
of the wells in our study with maximum values of 215 mg/L and 467 mg/L for well I-1 and well
I-2, respectively. The initial Ba concentrations in the flowback water from these wells however
are low (< 10 mg/L) and the highest SO4 concentrations are measured during this period of
flowback (Fig. 5.7a). The elevated SO4 may be due to pyrite oxidation caused by the injection of
the hydraulic fracturing fluid (Wilke et al., 2015; Harrison et al., 2017). In the early flowback
water, the SI for barite is near equilibrium (-0.1 < SI < 0.1). Later in the flowback period for
both wells, the SO4 concentrations decrease, which may be related to barite precipitation and SO 4
reduction. The barite SI initially increases due to the increase in Ba from from formation water
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(up to 0.6 and 0.8, for well I-1 and well I-2, respectively) then decreases (to 0.2 and -0.4, for well
I-1 and well I-2, respectively), showing that the system is moving back towards equilibrium (Fig.
5.7b). The decreasing SI values suggest barite precipitation; however, the continually increasing
Ba concentrations do not support precipitation and may indicate that the source of the high Ba in
these wells is from mixing with formation water with high Ba concentrations. The variable
behavior of Ba and SO4 concentrations in the study wells shows that these ions are influenced by
both barite precipitation and dissolution, as well as SO 4 reduction and mixing with formation
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a.
b.
Figure 5.7: a) Ba and SO4 concentrations for well I-1 and well I-2. Ba concentrations are initially low in the
flowback water from both wells. As the Ba concentrations begin to increase, the SO 4 concentrations decrease.
b) The saturation indices (SI) for barite for well I-1 and well I-2. The flowback water is initially close to
equilibrium with barite. The increasing SI is due to increasing Ba from formation water, while the
decreasing SI supports barite precipitation. Both barite dissolution and mixing with high Ba formation water
are interpreted to contribute to the Ba concentrations, while bacterial SO 4 reduction and barite precipitation
water in previous studies is cation exchange with clay (Renock et al., 2016). In sequential
extraction experiments on Marcellus Shale samples, the majority of the Ba ions were found in
the exchangeable fraction (Phan et al., 2015; Stewart et al., 2015; Renock et al., 2016) providing
support for the release of Ba ions through cation exchange. The cation exchange capacity (CEC)
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for the Montney Formation is low (< 25 cmol(+)/kg) and does not correlate with the percentage
of clay in the rock (R2 < 0.05) (see Chapter 2; Chapter 4). Consequently cation exchange may
not be as important in the Montney Formation compared to other formations where hydraulic
fracturing is occurring. Additionally, geochemical modelling with the major ions in our study
indicated that ion exchange would produce a decrease in the concentrations of the divalent ions
rather than an increase, due to these ions displacing Na ions on the exchange sites when the
relatively low TDS hydraulic fracturing fluid is injected into the formation (see Chapter 2).
5.4.2 Boron
The B concentrations increase with TDS over the flowback period. Several of the site C
wells (wells 1, 5, 6, and 7) and well D-2 are exceptions and have B concentrations that remain
relatively stable over the course of the flowback period (Fig. 5.8). The B concentrations are
typically similar between wells from the same site and which are completed in the same member
of the Montney Formation (Fig. 5.8). In upper Montney member flowback water, the
concentrations are lower for the site A and site B wells (3.1 to 14 mg/L), moderate for site C and
site D wells (11 to 21 mg/L), and highest at well H-1 (13 to 38 mg/L). The middle Montney
member wells can be divided into sites D-G with lower B (3.1 to 16 mg/L) and site C with higher
B (19 to 24 mg/L). The lower Montney member wells have similar or slightly lower B values
relative to the upper and middle Montney member flowback water with maximum values of
approximately 11 mg/L. The B concentrations in the Montney Formation flowback water are
comparable to or slightly higher than the concentrations in flowback water from other
hydraulically fractured formations, including the Marcellus Shale which typically reaches
al., 2015). The high B concentrations in the flowback water from the study wells are not related
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to the hydraulic fracturing fluid chemistry as B concentrations are low in this fluid (≤5.1 mg/L;
Table 5.2). The initial B concentrations in the study wells show some correlation with the length
Figure 5.8: Boron concentrations over the flowback period, plotted as cumulative flowback volume. a) upper
Montney member wells. The produced water samples from sites A and B are not included; b) middle and
lower Montney member wells. Individual wells are grouped by site. ▲- upper Montney member wells; -
The available B results for Montney Formation produced waters, which are expected to
approach the B concentrations in formation water, were limited to the produced water samples
collected as part of the present study from site A wells, site B wells, and the well nearby to site I.
There is low variability in the B concentrations in the produced water from these wells with
values ranging from 9.3 to 15 mg/L, although this is expected as the flowback waters from these
three sites all had low (< 15 mg/L) and similar B concentrations. Further sampling of produced
waters from the Montney Formation and the inclusion of B concentrations in the analysis is
required to determine the variability in formation water between the different regions in order to
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determine if the variability in the concentrations in flowback water is related to differences in
The B content in kerogen is high and can be released under high temperature conditions
(~150°C) (Williams et al., 2001). The current temperature of the Montney Formation is 75-
80°C; however, the maximum paleo-temperature is estimated at 175°C (Desrocher et al., 2004).
There was a moderate correlation (R2 = 0.58; Fig. 5.9) between the completion depth and the
maximum flowback water B concentration from the study wells. This relationship was
investigated as greater depths correlate with higher formation temperatures; however, as the
formation temperature for the Montney Formation for the study wells remains close to 75°C at
all sites, this trend may be indicative of variation in the paleo-temperature across the formation
rather than the current temperature conditions. There is also an observable regional geographic
variation in B concentrations in flowback water across the study sites related to differences in
depth as the completion depth increases from the northwest to the southeast (Fig. 5.10).
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Figure 5.9: Correlation between the maximum B concentration in flowback water for each of the wells and
the total vertical depth (TVD) of the well. There is some correlation with increasing B concentrations and
increasing depth; however, this relationship could also be impacted by the percentage of illite due to
Figure 5.10: Boron concentrations across the formation plotted as cumulative flowback volume. The highest
concentrations are observed in the well to the southeast, while the lowest concentrations are observed in the
wells to the northwest, although there is some overlap with some of the central wells. The produced water
samples from site A, site B, and nearby to site I are not included in this plot.
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In cases where the temperature of the formation is lower (< 150°C), B can be removed
tetrahedral sites (Williams and Hervig, 2005; Engle and Rowan, 2014). This process applies to
longer timescales for water-rock interactions altering the formation water chemistry rather than
occurring on the timescale of the hydraulic fracturing process. In the portion of the Montney
Formation in BC, there is a decrease in clay content from the northwest to the southeast (BC
OGC, 2012). The mineralogy results compiled in the regions near the study wells indicate that
the clays present include illite, kaolinite, and chlorite, with illite making up the majority of the
clay (Table 5.4). A negative correlation between the percentage of illite and the B
concentrations may indicate that a greater amount of B has been removed from the formation
water by illitization during diagenesis. However, based on the wells included in our study, there
is only a weak negative correlation (R2 = 0.12) between maximum B concentrations and median
weight percent illite due to the large amount of variability in B concentrations in the flowback
water from the study wells. For example, the regions near site A, site C, site D – upper Montney
member wells, and site H all have relatively low clay (< 10%, by weight) although the flowback
water from these wells have B concentrations spanning from low (< 10 mg/L) to high
(> 30 mg/L). There may also be further substitution and leaching of the B from the clay over
time which would minimize the correlation between illite and B in the water. Additional
mineralogical analyses focusing specifically on the hydraulically fractured zones are necessary to
further investigate the trend between B concentrations in flowback water and illite.
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Table 5.4: Summary of the compiled mineralogy for the study sites. The values provided are medians.
Results are divided based on the member of the Montney Formation where the study wells were completed.
The data are from a combination of publically available results and analyses completed for the present study
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In addition to the impact of the formation water B concentrations on the flowback water
chemistry through mixing, there is also the potential for ion exchange during the hydraulic
fracturing process as B that had been adsorbed onto the clay surface could be released due to the
injection of the relatively low salinity hydraulic fracturing fluid (Williams and Hervig, 2002;
Warner et al., 2014). As previously discussed in relation to Ba concentrations, the CEC of the
Montney Formation is low and therefore cation exchange is likely not the main source of B ions
in flowback water.
5.4.3 Lithium
Lithium concentrations increase slightly over the flowback period with some variability
between wells sampled across the formation. The majority of the flowback water samples from
upper and middle Montney member wells have Li concentrations < 20 mg/L; with the site B
wells and wells C-5, C-6, and C-7 reaching slightly higher concentrations (> 30 mg/L;
Table 5.1). Li concentrations in lower Montney member flowback water remain low for well I-1
with a maximum concentration of 15 mg/L and moderate for well I-2 with a maximum of 22
mg/L. Both maximum values for the site I wells were measured at the end of the flowback
period. The Montney Formation flowback water Li concentrations are lower relative to the
concentrations in flowback water from other formations, such as the Marcellus Shale where the
concentrations are often > 50 mg/L within the first week and > 90 mg/L within the first 30 days
of the flowback period (Rowan et al., 2015; Phan et al., 2016). The produced water samples
collected from Montney Formation wells as part of the present study remain lower with Li
concentrations between 27 and 41 mg/L for the site A and site B wells and 61 mg/L for the well
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The dominant control on the increasing Li concentrations in flowback water is likely
mixing between the injected fluid and the formation water (Phan et al., 2016). Mixing is
supported by the increasing Li concentrations observed over the flowback period in our study.
The hydraulic fracturing fluids used in the study wells have low Li concentrations (≤ 11 mg/L);
therefore, the injected fluid does not produce the elevated concentrations measured in flowback
water. The Li concentrations in the initial flowback water samples are impacted by the length of
the shut-in period and have a moderate positive correlation (R 2 = 0.43). In sequential extraction
experiments on shale samples conducted by Phan et al. (2016), the greatest proportion of Li in
the rock was found in the silicate mineral fraction, most of which is likely in clays, although the
oxidizable fraction, including organic matter, could account for up to 20% of the total Li. The
organic matter is a potential source of Li in formation water, as Li can be released from organic
matter under high temperatures (Clauer et al., 2014). Variation in formation temperature has
been used to explain the regional variation in Li concentrations in other regions since a trend
between formation water Li concentrations and depth has been observed (Macpherson et al.,
2014; Macpherson, 2015; Phan et al., 2016). In these studies, the maximum depth of burial was
positively correlated with the maximum formation temperature. The results of the current study
show no correlation (R2 < 0.01) between the maximum Li concentration in flowback water and
the completion depth; however, this may be due to differences in the current depth and the
maximum depth of burial at the study sites, as well as due to the varying lengths of the flowback
diagenesis (Macpherson et al., 2014; Macpherson, 2015; Phan et al., 2016). During diagenesis,
Li ions can substitute for the cations in the octahedral layers of the clay (Williams and Hervig,
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2005; Clauer et al., 2014). The incorporation of Li into illite during diagenesis would be
water, which would be observable in the late stage flowback water chemistry. The results from
the present study only show a weak negative correlation (R 2 = 0.14) between the maximum Li
concentration and the median percent illite for the study wells. The low correlation may be due
to the release of Li ions during diagenesis as Li can also substitute for the interlayer cation in
hydraulic fracturing, through the same process as B ions (Warner et al., 2014). However, a
sequential extraction study conducted on shale samples found only a minor amount of Li (< 2%)
on the exchangeable sites (Phan et al., 2016). The ion exchange capacity of the Montney
Formation is likely less than the shale used in the Phan et al. (2016) study due to the low clay
content of the Montney Formation (Zonneveld and Moslow, 2014), relative to the average clay
content of the Marcellus Shale (30%) used in the investigation by Phan et al. (2016).
both Li and B concentrations, the relationship between the two ions is examined in more detail.
The correlation between these ions is consistent between wells from the same site and overall
there are three general regions in which the B-Li flowback water values plot for our study
(Fig. 5.11). The first region has relatively high Li and relatively low B values. The flowback
water samples from sites A and B plot in this region, with later samples from site I approaching
this region. The second region can be divided into two sub-regions. The first of these sub-
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regions has moderate Li and moderate B values and includes sites C through G and early samples
from site I. The second sub-region includes wells C-5, C-6, and C-7, which have high Li and
moderate B values. These wells are included as a sub-region as they plot in a distinct area but
still follow the general trend of other wells from site C. The third region is relatively low Li and
relatively high B values. Only the samples from site H fall within this region. There is an
indication of a geographic trend with region 1 being comprised of wells from the northwestern
region with the site B wells, region 2 being the remaining wells located in the central region, and
region 3 being the well in the southeastern region of the study area (Fig. 5.11). Site B is the
northern most well in the central region; however, it is much closer to the other central region
wells relative to the northwestern region wells (sites A and I, see Fig. 5.2). The similarity
between site A and site B may be due to the factors which are impacting the formation water
chemistry in these two regions. These two sites may have similarities in the B and Li content of
the organic matter and the amount of substitution of these ions in illite. Differences in the
correlation between these ions may also be related to differences in paleo-temperature across the
formation, as B and Li are released from organic matter at different temperatures (Clauer et al.,
2014). A more detailed study focusing on the local mineralogy and organic matter content
within the fractured units is necessary to provide further conclusions on the impact of these
variables on the flowback water chemistry and the correlations seen between B and Li ions.
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Figure 5.11: Li-B plot showing the three regions where the sampled wells plot. Wells from the same site
consistently fall within the same region. ▲- upper (u) Montney member wells; - middle (m) Montney
5.5 Conclusions
The selected key minor ions in flowback water – Ba, B, and Li – show greater variability
compared to the major ions across the study area. More variation in the concentrations of the
minor ions in formation water between regions is likely a contributing factor to the differences in
the concentrations of Ba, B, and Li in flowback water as mixing between the hydraulic fracturing
fluid and the formation water is an important geochemical process influencing the flowback
water chemistry. In addition to mixing, these three ions show some indication of the impact of
The Ba concentrations in flowback water generally show a decreasing trend over the
study area from the northwestern sites (sites A and I) to the southeastern site (site H), although
high Ba concentrations were also measured in the flowback water from site C in the central
region. The negative correlation observed between Ba and SO 4 concentrations for the flowback
water from the study wells supports the influence of SO 4 reduction on the concentrations of these
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ions, as suggested for flowback waters from the Marcellus Formation by Engle and Rowan
(2014). SO4 reduction would in turn increase the barite solubility due to the removal of SO 4 ions
from solution. If only barite dissolution were occurring a positive correlation would be expected
between Ba and SO4 concentrations for all wells. A detailed examination of the data for each of
the wells indicates that both barite dissolution and/or precipitation may be occurring in different
wells. Barite precipitation has been observed in laboratory experiments by others where a rock
sample was exposed to synthetic hydraulic fracturing fluid under formation temperatures and
pressures (Dieterich et al., 2016; Paukert Vankeuren et al., 2017). The observation of barite
precipitation indicates that the kinetics of the reaction are rapid enough to occur during hydraulic
fracturing. The increasing Ba concentrations in flowback water may be impacted by both barite
precipitation/dissolution and mixing with formation water, while the SO 4 concentrations are
precipitation/dissolution.
The B concentrations in the studied flowback water show an increasing trend across the
study area from the northwestern sites to the southeastern site, with site B in the central region
Formation flowback water show less variability between wells relative to both Ba and B
concentrations and remain < 20 mg/L for most sites. Higher Li concentrations > 30 mg/L were
measured in the flowback water from the site B wells and wells C-5, C-6, and C-7. No B or Li
containing minerals are close to saturation in the flowback water. The controls on the formation
water chemistry are expected to have an increasing influence on the flowback water chemistry
over the flowback period due to a greater fraction of formation water contributing to flowback
water over time. Both B and Li ions are present in organic matter and can be released from the
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organic matter into the formation water under high temperatures (Williams et al., 2001; Clauer et
al., 2014). As higher temperatures are associated with greater depths, a correlation between the
maximum B and Li concentrations in flowback water and completion depth was expected.
However, only B concentrations showed a correlation (R2 = 0.58). The lack of correlation for Li
concentrations (R2 < 0.01) may be due to differences between the current depth and the paleo-
depth of burial or due to a greater importance of other processes on the concentration of this ion.
Substitution of B and Li ions in smectite-illite diagenesis and ion exchange during hydraulic
fracturing were not clearly supported by the results of the flowback water chemistry from the
The relationship between B and Li was consistent for wells from the same site. Overall,
there is a trend from the northwestern region (high Li, low B) to the southeastern region (low Li,
high B), except for site B in the central region which has B/Li ratios closer to those in the
flowback water from the northwestern region wells. These differences may be due to the release
of B and Li ions from organic matter at different temperatures, variation in the B and Li content
of the organic matter, and/or variation in the amount of substitution in illite during diagenesis.
The addition of these three minor elements to the flowback water geochemical analysis provides
additional information on the variability in flowback water chemistry in the Montney Formation
that was not evident from the analysis of the major ions alone. Further detailed studies focusing
on the variability in formation water chemistry and the mineralogy of the fractured zones,
specifically the abundance of barite and the clay mineralogy, will improve the understanding of
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Chapter 6: Conclusions and Recommendations
6.1 Conclusions
The inorganic geochemistry of flowback water can provide important insights into the
processes that are occurring in the reservoir during hydraulic fracturing. Prior to being of use for
more in-depth studies on reservoir processes, the flowback water chemistry must be
characterized for a formation and the variability between wells within that formation examined.
Following the initial characterization, the controls on the flowback water chemistry need to be
determined. The series of studies presented in this thesis focused on the inorganic geochemistry
of flowback water from the Montney Formation. An examination on how the chemistry varied
between wells in the study area was completed and an analysis of some of the potential variables
The results of the study provide support for mixing as the most likely geochemical
process that is impacting the flowback water chemistry. Through the use of Cl concentrations,
δ18O isotopes, and δ2H isotopes as conservative tracers, it was possible to calculate the mixing
proportions of hydraulic fracturing fluid and formation water in the flowback water samples.
The results show that the proportion of formation water increased over the flowback period and
in some cases attained Cl concentrations and isotopic values similar to those that were estimated
for formation water. However, for the majority of the study wells the contribution of formation
water by the end of the flowback period remained below 60%. The mixing ratios calculated with
the conservative tracers were then used to compare the concentrations of the other major ions
with geochemical models to investigate potential processes impacting the chemistry. The
simplest model included only mixing between the hydraulic fracturing fluid and the formation
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water. This model was found to provide a reasonable approximation for the Na and K
concentrations in flowback water. The addition of ion exchange to the mixing model was
required to improve the fit of the model for Ca, Mg, and Sr concentrations. The analytical results
for the divalent ions displayed lower concentrations in the flowback water than those predicted
by mixing alone, which is supported by ion exchange since the divalent ions would replace the
Na ions on the exchange sites due to the relative mobility of the ions. As such, ion exchange
would also impact the Na concentrations; however, the relative increase in Na concentrations is
Although mixing is the dominant process influencing the Montney Formation flowback
water chemistry, the rate of increase in the proportion of formation water in flowback water was
observed to vary between wells. The consequence of the variability between wells is that the
major ions increase at different rates and higher concentrations can be attained earlier in the
flowback period after less time has elapsed or at a lower cumulative flowback volume for some
wells relative to others. In general wells completed at the same site and within the same informal
member of the Montney Formation had similar flowback water chemistry; however, there were
examples of wells from the same site with similar completion depths with different rates of
increase for the major ions over the flowback period. This variability is due to the influence of
additional variables on the flowback water chemistry, including the length of the shut-in period
and the fracture complexity. A challenge in comparing flowback water between wells is that the
length of the flowback period varies between wells; therefore, it is not possible to simply
compare the median or maximum ion concentrations. A trend analysis using linear regression
and linear mixed effects models was presented as a method to compare the flowback water
chemistry between wells. This method allowed the sites to be grouped together using the slope
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coefficients from the regression of major ion concentration as a function of time. It was found
that nearby sites often have similar slope coefficients, likely due to similarities in the formation
water chemistry and the properties of the formation. The linear regression analysis completed
for the volume of flowback water produced as a function of time did not show any obvious
An additional complication with evaluating the flowback water chemistry from different
wells is that there are a plethora of variables that can impact the chemistry. Several of these
variables were considered in a multiple regression analysis. This analysis identified shut-in time
as a dominant variable. Longer shut-in times were consistently correlated to higher major ion
concentrations in both the early flowback water and the flowback water after 1,000 m 3 of fluid
had been produced from a well. However, the relative importance of the shut-in time decreases
later in the flowback period. The initial high ion concentrations associated with longer shut-in
times are likely related to a prolonged time for mixing within the reservoir between the hydraulic
fracturing fluid and the formation water accessed in the fracture network prior to the initiation of
flowback from a well. In addition, a lengthier shut-in period would allow for a greater
and/or osmosis (Balashov et al., 2015; Zolfaghari et al., 2016; Wang et al., 2016; 2017). The
impact of the length of the shut-in period on flowback water chemistry would have implications
for water treatment and re-use, as longer shut-in periods would produce flowback water with
higher TDS.
Other notable variables identified in the multiple regression analysis are the hydraulic
fracturing fluid chemistry and the formation water chemistry, although the influence of these
variables was not consistent between the different ions. In the early flowback water, the
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hydraulic fracturing fluid chemistry was found to be important for Cl, Ca, Mg, and Sr
concentrations, while in the flowback water for samples collected later in the flowback after
1,000m3 of flowback water had been produced, the formation water chemistry is an important
variable for TDS, Cl, Ca, and Mg concentrations. These variables were anticipated to be
identified as dominant variables impacting the flowback water chemistry. The complexity of the
system and the interrelationships between many variables may obscure the importance of these
variables in the multiple regression analysis. Furthermore, the relative importance of the
formation water chemistry may be impacted by the low variability in this parameter between
sites as well as the uncertainty in the data since this water was not directly sampled.
The minor ions considered in the study are Ba, B, and Li. The concentrations of these
ions exhibited more variability in the flowback water across the study area relative to the major
ions. The Ba concentrations as well as the B/Li ratio generally had a decreasing trend from the
northwest sites to the southeast site. Mixing between the hydraulic fracturing fluid and the
formation water is likely the dominant geochemical process impacting the B and Li
dissolution and precipitation, in addition to mixing between the injected fluid and formation
water. The relative importance of these geochemical processes on Ba concentrations was found
to vary between the different wells. The SO4 concentrations are another control on Ba in
flowback water. As proposed by others, the SO4 concentrations in flowback water are impacted
by pyrite oxidation (Wilke et al., 2015; Harrison et al., 2017) and bacterial SO 4 reduction (Engle
and Rowan, 2014), which can impact the saturation index of barite and determine if this mineral
will dissolve or precipitate in the well. The examination of these additional ions shows that there
is variability in the Montney Formation flowback water which may have implications for both
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water treatment and for determining the processes occurring in the formation at the different
sites.
The summary of the flowback water chemistry from multiple wells completed in the
Montney Formation provides a basis for future flowback water research. The use of multiple
wells in the study illustrates the complexity of the system and demonstrates that there are
numerous interacting variables influencing the flowback water chemistry. These factors must be
considered when conducting research in this field of study. By improving on the understanding
of the variability and controls on flowback water chemistry, it will be possible to use the
changing chemistry to further investigate reservoir processes and to develop predictions for the
flowback water chemistry to assist with water management at future hydraulic fracturing
operations.
6.2 Recommendations
Based on this thesis, additional areas of study that can provide further insight into the Montney
Further sampling of flowback water from wells completed in the Montney Formation in
the northwest and southeast regions of the study area. Potential regional trends in Sr
and Ba concentrations and the B/Li ratios were identified in our studies; however, only
two wells in the northwest region and one well in the southeast region were sampled for
the present series of studies. Additional sampling in these regions may provide support
for the observed trends which will provide information on the variability in the
formation water chemistry and the geochemical processes taking place in the formation.
Further investigation into the variables that are impacting the flowback water chemistry
at different sites. Potential variables were listed in Table 3.1 (Chapter 3). Identification
193
and quantification of other relevant variables should be completed through more
detailed investigations at well sites. For example, rock sampling along the horizontal
portion of the well to better understand the controls of mineralogy on flowback water
chemistry, continued sampling of the produced water from the well until the chemistry
analysis to determine the fracture complexity at the site. Laboratory studies could be
conducted in support of field investigations and include studies on the fluid chemistry of
Completing laboratory and field studies on rock and fluid samples from the same site
would help with validating the laboratory experiments and provide a more complete
A more detailed study on the mineralogy and organic matter in the horizontal portion of
concentrations are impacted by the amount of illite and the organic matter present in the
formation. The site-specific mineralogy may help with the interpretation of other ions
Additional geochemical studies should be completed to look at trace elements (e.g., As,
Cu, and Zn), minor elements (e.g., Fe, Mn, and Si), and organic compounds in the
Montney Formation flowback water. Understanding the occurrence and the variability
of these additional elements and compounds is important as they may impact water
treatment and recycling and have the potential to provide a more complete
understanding of the processes taking place in the reservoir during hydraulic fracturing.
194
References
Abualfaraj, N., Gurian, P.L. and Olson, M.S. 2014. Characterization of Marcellus Shale
Flowback Water: Environmental Engineering Science, v. 31(9), p. 514-524, doi:
10.1089/ees.2014.0001.
Aitchison, J. 1982. The Statistical Analysis of Compositional Data: Journal of the Royal
Statistical Society. Series B (Methodological), v. 44(2), p. 139-177.
Akob, D.M., Cozzarelli, I.M., Dunlap, D.S., Rowan, E.L. and Lorah, M.M. 2015. Organic and
inorganic composition and microbiology of produced waters from Pennsylvania shale gas
wells: Applied Chemistry, v. 60, p. 116-125, doi: 10.1016/j.apgeochem.2015.04.011.
Alessi, D.S., Zolfaghari, A., Kletke, S., Gehman, J., Allen, D.M. and Goss, G.G. 2017.
Comparative analysis of hydraulic fracturing wastewater practices in unconventional shale
development: Water sourcing, treatment and disposal practices: Canadian Water
Resources Journal/Revue canadienne des ressources hydriques, v. 42(2), p. 105-121, doi:
10.1080/07011784.2016.1238782
Anderson, T.F. and Chai, B.H. 1974. Oxygen isotope exchange between calcite and water under
hydrothermal conditions, in A.W. Hofmann, B.J. Giletti, H.S. Yoder, Jr. and R.A. Yund,
eds., Geochemical Transport and Kinetics, Carnegie Institution of Washington, p. 219-
227.
Appelo, C.A.J. 1994. Cation and proton exchange, pH variations, and carbonate reactions in a
freshening aquifer: Water Resources Research, v. 30 (10), p. 2793-2805, doi:
10.1029/94wr01048.
Bagheri, R., Nadri, A., Raeisi, E., Eggenkamp, H.G.M., Kazemi, G.A. and Montaseri, A. 2014.
Hydrochemical and isotopic (δ18O, δ2H, 87Sr/86Sr, δ37Cl and δ81Br) evidence for the origin
of saline formation water in a gas reservoir: Chemical Geology, v. 384, p. 62-75, doi:
10.1016/j.chemgeo.2014.06.017.
Balashov, V.N., Engelder, T., Gu, X., Fantle, M.S. and Brantley, S.L. 2015. A model describing
flowback chemistry changes with time after Marcellus Shale hydraulic fracturing: AAPG
Bulletin, v. 99(1), p. 143-154, doi: 10.1306/06041413119.
Barbot E., Vidic N.S., Gregory K.B. and Vidic R.D. 2013. Spatial and Temporal Correlation of
Water Quality Parameters of Produced Waters from Devonian-Age Shale following
Hydraulic Fracturing: Environmental Science & Technology, v. 47, p. 2562-2569, doi:
10.1021/es304638h.
Bates, D.M. 2010. lme4: Mixed-effects modeling with R. Madison, WI, USA: Springer.
195
Bates, D., Maechler, M., Bolker, B. and Walker, S. 2015. Fitting Linear Mixed-Effects Models
Using lme4: Journal of Statistical Software, v. 67(1), p. 1-48, doi: 10.18637/jss.v067.i01.
BC Oil and Gas Commission (BC OGC). 2012. Montney Formation Play Atlas NEBC. Retrieved
from https://www.bcogc.ca/montney-formation-play-atlas-nebc.
Bird, T.D., Barclay, J.E., Campbell, R.I. and Lee, P.J. 1994. Part I: Geological Play Analysis and
Resource Assessment In Triassic Gas Resources of the Western Canada Sedimentary
Basin, Interior Plains: Geological Survey of Canada Bulletin 483, p. 1-66, doi:
10.4095/194156.
Blauch M.E., Myers R.R., Moore T.R., Lipinski B.A. and Houston N.A. 2009. Marcellus Shale
Post-Frac Flowback Waters – Where is All the Salt Coming From and What are the
Implications?: SPE 125740, Prepared for presentation at the 2009 SPE Eastern Regional
Meeting, September 23-25, 2009, Charleston, West Virginia, USA, doi: 10.2118/125740-
ms.
Blount, C.W. 1977. Barite solubilities and thermodynamic quantities up to 300°C and 1400 bars:
American Mineralogist, v. 62, p. 942-957.
Capo, R.C., Stewart, B.W., Rowan, E.L., Kolesar Kohl, C.A., Wall, A.J., Chapman, E.C.,
Hammack, R.W. and Schroeder, K.T. 2014. The strontium isotopic evolution of Marcellus
Formation produced waters, southwestern Pennsylvania: International Journal of Coal
Geology, v. 126, p. 57-63, doi: 10.1016/j.coal.2013.12.010.
Carpenter, A.B. 1978. Origin and chemical evolution of brines in sedimentary basins: SPE 7504,
Prepared for presentation at the 53rd Annual Fall Technical Conference and Exhibition of
the Society of Petroleum Engineers, October 1-3, 1978, Houston, Texas, USA, doi:
10.2523/7504-ms.
Chan, L.-H., Starinsky, A. and Katz, A. 2002. The behavior of lithium and its isotopes in oilfield
brines: Evidence from the Heletz–Kokhav field, Israel: Geochimica et Cosmochimica
Acta, v. 66(4), p. 615-623, doi: 10.1016/s0016-7037(01)00800-6.
196
Chapman, E.C., Capo, R.C., Stewart, B.W., Kirby, C.S., Hammack, R.W., Schroeder, K.T. and
Edenborn, H.M. 2012. Geochemical and strontium isotope characterization of produced
water from Marcellus Shale natural gas extraction: Environmental Science & Technology,
v. 46, p. 3545-3553, doi: 10.1021/es204005g.
Chaudhuri, S. and Clauer, N. 1993. Strontium isotopic compositions and potassium and rubidium
contents of formation waters in sedimentary basins: Clues to the origin of the solutes:
Geochimica et Cosmochimica Acta, v. 57(2), p. 429-437, doi: 10.1016/0016-
7037(93)90441-x.
Clarkson, C.R. 2013. Production data analysis of unconventional gas wells: Review of theory
and best practices: International Journal of Coal Geology, v. 109-110, p. 101-146, doi:
10.1016/j.coal.2013.01.002.
Clauer, N., Williams, L.B. and Fallick, A.E. 2014. Genesis of nanometric illite crystals
elucidated by light-element (hydrogen, lithium, boron and oxygen) isotope tracing, and K–
Ar and Rb–Sr dating: Chemical Geology, v. 383, p. 26-50, doi:
10.1016/j.chemgeo.2014.05.025.
Connolly, C.A., Walter, L.M., Baadsgaard, H. and Longstaffe, F.J. 1990. Origin and evolution of
formation waters, Alberta Basin, Western Canada Sedimentary Basin. 1. Chemistry:
Applied Geochemistry, v. 5, p. 375-395, doi: 10.1016/0883-2927(90)90016-X.
Connor, J.A., Molofsky, L.J., Richardson, S.D. and Bianchi-Mosquera, G.C. 2015.
Environmental issues and answers related to shale gas development: SPE-174164-MS,
Prepared for presentation at the SPE Latin American and Caribbean Health, Safety,
Environment and Sustainability Conference, July 7-8, 2015, Bogotá, Columbia, doi:
10.2118/174164-ms.
Cooley, H. and Donnelly, K. 2012. Hydraulic Fracturing and Water Resources: Separating the
Frack from the Fiction. Oakland, California: Pacific Institute. Retrieved from
http://pacinst.org/publication/
Davies, G.R., Moslow, T.F. and Sherwin, M.D. 1997. The Lower Triassic Montney Formation,
west-central Alberta: Bulletin of Canadian Petroleum Geology, v. 45 (4), p. 474-505.
Davies, G.R. and Hume, D. 2016. Lowstand/slope onlap wedges in the Montney: Stratigraphic
and sequence framework, reservoir significance: Canadian Society of Petroleum
Geologists, GeoConvention 2016: Optimizing Resources, March 7-11, 2016, Calgary,
Alberta, Canada, Abstract.
197
Dehghanpour, H., Lan, Q., Saeed, Y., Fei, H. and Qi, Z. 2013. Spontaneous Imbibition of Brine
and Oil in Gas Shales: Effect of Water Adsorption and Resulting Microfractures: Energy
Fuels, v. 27, p. 3039-3049, doi: 10.1021/ef4002814.
Desrocher, S., Hutcheon, I., Kirste, D. and Henderson, C.M. 2004. Constraints on the generation
of H2S and CO2 in the subsurface Triassic, Alberta Basin, Canada: Chemical Geology, v.
204, p. 237-254, doi: 10.1016/j.chemgeo.2003.11.012.
Dieterich, M., Kutchko, B. and Goodman, A. 2016. Characterization of Marcellus Shale and
Huntersville Chert before and after exposure to hydraulic fracturing fluid via feature
relocation using field-emission scanning electron microscopy: Fuel, v. 182, p. 227-235,
doi: 10.1016/j.fuel.2016.05.061.
Dixon J. 2000. Regional lithostratigraphic units in the Triassic Montney Formation of western
Canada: Bulletin of Canadian Petroleum Geology, v. 48 (1), p. 80-83, doi:
10.2113/48.1.80.
Dresel, P.E. 1985. The Geochemistry of Oilfield Brines from Western Pennsylvania.
Pennsylvania State University, M.Sc. Thesis.
Dresel, P.E. and Rose, A.W. 2010. Chemistry and Origin of Oil and Gas Well Brines in Western
Pennsylvania: Pennsylvania Geological Survey, 4th ser., Open-File Report OFOG 10-01.0,
48 p., doi: 10.3996/052013-JFWM-033.S11.
Droge, S. and Goss, K.-U. 2012. Effect of Sodium and Calcium Cations on the Ion-Exchange
Affinity of Organic Cations for Soil Organic Matter: Environmental Science &
Technology, v. 46, p. 5894-5901, doi: 10.1021/es204449r.
Edwards D.E., Barclay J.E., Gibson D.W., Kvill G.E. and Halton E. 1994. Triassic Strata of
Western Canada Sedimentary Basin In Geological Atlas of the Western Canada
Sedimentary Basin, G.D. Mossop and I. Shetsen (comp.), Canadian Society of Petroleum
Geologists and Alberta Research Council. Retrieved from
http://www.ags.gov.ab.ca/publications/wcsb_atlas/atlas.html.
Engelder, T., Cathles, L.M. and Bryndzia, L.T. 2014. The fate of residual treatment water in gas
shale: Journal of Unconventional Oil and Gas Resources, v. 7, p. 33-48, doi:
10.1016/j.juogr.2014.03.002.
Engle, M.A., Reyes, F.R., Varonka, M.S., Orem, W.H., Ma, L., Ianno, A.J., Schell, T.M., Xu, P.
and Carroll, K.C. 2016. Geochemistry of formation waters from the Wolfcamp and
“Cline” shales: Insights into brine origin, reservoir connectivity, and fluid flow in the
Permian Basin, USA: Chemical Geology, v. 425, p. 76-92, doi:
10.1016/j.chemgeo.2016.01.025.
198
Engle, M. and Rowan, E.L. 2014. Geochemical evolution of produced waters from hydraulic
fracturing of the Marcellus Shale, northern Appalachian Basin: A multivariate
compositional data analysis approach: International Journal of Coal Geology, v. 126, p.
45-56, doi: 10.1016/j.coal.2013.11.010.
Esmaeilirad, N., White, S., Terry, C., Prior, A. and Carlson, K. 2016. Influence of inorganic ions
in recycled produced water on gel-based hydraulic fracturing fluid viscosity: Journal of
Petroleum Science and Engineering, v. 139, p. 104-111, doi:
10.1016/j.petrol.2015.12.021.
Fontenelle, L., Weston, M., Lord, P. and Haggstrom, J. 2013. Recycling water: Case studies in
designing fracturing fluids using flowback, produced, and nontraditional water sources:
SPE 165641, Prepared for presentation at SPE Latin American and Caribbean Health,
Safety, Environment and Sustainability Conference, June 26-27, 2013, Lima, Peru, doi:
10.2118/165641-ms.
FracFocus. 2016. What Chemicals Are Used: FracFocus Chemical Disclosure Registry (Canada).
Web. Date of access 15 February 2017. Retrieved from http://fracfocus.ca/chemical-
use/what-chemicals-are-used.
Freeman, J.T. 2007. The use of bromide and chloride mass ratios to differentiate salt-dissolution
and formation brines in shallow groundwaters of the Western Canadian Sedimentary
Basin: Hydrogeology Journal, v. 15, p. 1377-1385, doi: 10.1007/s10040-007-0201-1.
Ghanbari, E., Abbasi, M.A., Dehghanpour, H. and Bearinger, D. 2013. Flowback volumetric and
chemical analysis for evaluating load recovery and its impact on early-time production:
SPE 167165-MS, Prepared for presentation at the SPE Unconventional Resources
Conference – Canada, November 5-7, 2013, Calgary, Alberta, Canada, doi:
10.2118/167165-ms.
Goss, G., Alessi, D., Allen, D., Gehman, J. Brisbois, J., Kletke, S., Zolfaghari Sharak, A., Notte,
C., Thompson, D.Y., Hong, K., Covalski Junes, V.R., Guedes de Araujo Neto, W.B. and
Prosser, C. 2015. Unconventional Wastewater Management: A Comparative Review and
Analysis of Hydraulic Fracturing Wastewater Management Practices Across Four North
American Basins. Canadian Water Network. Retrieved from http://www.cwn-
rce.ca/reports/
Gregory, K.B., Vidic, R.D. and Dzombak, D.A. 2011. Water Management Challenges
Associated with the Production of Shale Gas by Hydraulic Fracturing: Elements, v.7, p.
181-186, doi: 10.2113/gselements.7.3.181.
Grömping, U. 2006. Relative Importance for Linear Regression in R: The Package relaimpo:
Journal of Statistical Software, v. 17(1), p. 1-27. Version 2.2-2, doi:
10.18637/jss.v017.i01.
199
Gupta, I., Wilson, A.M. and Rostron, B.J. 2012. Cl/Br compositions as indicators of the origin of
brines: Hydrogeologic simulations of the Alberta Basin, Canada: GSA Bulletin, v. 124
(1&2), p. 200-212, doi: 10.1130/B30252.1.
Haluszczak L.O., Rose A.W. and Kump L.R. 2013. Geochemical evaluation of flowback brine
from Marcellus gas wells in Pennsylvania, USA: Applied Geochemistry, v. 28, p. 55-61,
doi: 10.1016/j.apgeochem.2012.10.002.
Harrison A.L., Jew, A.D., Dustin, M.K., Thomas, D.L., Joe-Wong, C.M., Bargar, J.R., Johnson,
N., Brown Jr., G.E. and Maher, K. 2017. Element release and reaction-induced porosity
alteration during shale-hydraulic fracturing fluid interactions: Applied Geochemistry, v.
82, p. 47-62, doi: 10.1016/j.apgeochem.2017.05.001.
He, C., Li., M., Liu, W., Barbot, E. and Vidic, R.D. Kinetics and Equilibrium of Barium and
Strontium Sulfate Formation in Marcellus Shale Flowback Water: Journal of
Environmental Engineering, v. 140(5), p. B4014001-1-9, doi: 10.1061/(ASCE)EE.1943-
7870.0000807.
Johnson, J.D., Graney, J.R., Capo, R.C. and Stewart, B.W. 2015. Identification and
quantification of regional brine and road salt sources in watersheds along the New
York/Pennsylvania border, USA: Applied Geochemistry, v. 60, p. 37-50, doi:
10.1016/j.apgeochem.2014.08.002.
Kanfar, M.S. and Clarkson, C.R. 2016. Reconciling flowback and production data: A novel
history matching approach for liquid rich shale wells: Journal of Natural Gas Science and
Engineering, v. 33, p. 1134-1148, doi: 10.1016/j.jngse.2016.04.042.
Kirste, D., Desrocher, S., Spence, B., Hoyne, B., Tsang, B. and Hutcheon, I. 1997. Fluid flow,
water chemistry, gas chemistry and diagenesis in the subsurface Triassic in Alberta and
British Columbia: Bulletin of Canadian Petroleum Geology, v. 45 (4), p. 742-764.
Kolesar Kohl C.A., Capo R.C., Stewart B.W., Wall A.J., Schroeder K.T., Hammack R.W. and
Guthrie G.D. 2014. Strontium Isotopes Test Long-Term Zonal Isolation of Injected and
Marcellus Formation Water after Hydraulic Fracturing: Environmental Science &
Technology, v. 48, p. 9867-9873, doi: 10.1021/es501099k.
Kondash A.J., Albright, E. and Vengosh, A. 2017. Quantity of flowback and produced water
from unconventional oil and gas exploration: Science of the Total Environment, v. 574, p.
314-321, doi: 10.1016/j.scitotenv.2016.09.069.
Lan, Q., Ghanbari, E., Dehghanpour, H. and Hawkes, R. 2014. Water loss versus soaking time:
Spontaneous imbibition in tight rocks: Energy Technology, v. 2, p. 1033-1039, doi:
10.1002/ente.201402039.
200
Lester, Y., Ferrer, I., Thurman, E.M., Sitterley, K.A., Korak, J.A., Aiken, G. and Linden, K.G.
2015. Characterization of hydraulic fracturing flowback water in Colorado: Implications
for water treatment: Science of the Total Environment, v. 512-513, p. 637-644, doi:
10.1016/j.scitotenv.2015.01.043.
Lindeman, R.H., Merenda, P.F. and Gold, R.Z. 1980. Introduction to Bivariate and Multivariate
Analysis. Glenview, Illinois: Scott, Foresman.
Lu, J., Mickler, P.J., Nicot, J.-P., Choi, W., Esch, W.L. and Darvari, R. 2017. Geochemical
interactions of shale and brine in autoclave experiments – Understanding mineral reactions
during hydraulic fracturing of Marcellus and Eagle Ford Shales: AAPG Bulletin, v.
101(10), p. 1567-1597, doi: 10.1306/11101616026.
Machel, H.G. 2001. Bacterial and thermochemical sulfate reduction in diagentic settings – old
and new insights: Sedimentary Geology, v. 140, p. 143-175, doi: 10.1016/s0037-
0738(00)00176-7.
Macpherson, G.L., Capo, R.C., Stewart, B.W., Phan, T.T., Schroeder, K. and Hammack, R.W.
2014. Temperature-dependent Li isotope ratios in Appalachian Plateau and Gulf Coast
Sedimentary Basin saline water: Geofluids, v. 14, p. 419-429, doi: 10.1111/gfl.12084.
Macpherson, G.L. 2015. Lithium in fluids from Paleozoic-aged reservoirs, Appalachian Plateau
region, USA: Applied Geochemistry, v. 60, p. 72-77, doi:
10.1016/j.apgeochem.2015.04.013.
Makhanov, K., Habibi, A., Dehghanpour, H. and Kuru, E. 2014. Liquid uptake of gas shales: A
workflow to estimate water loss during shut-in periods after fracturing operations: Journal
of Unconventional Oil and Gas Resources, v. 7, p. 22-32, doi:
10.1016/j.juogr.2014.04.001.
Marcon, V., Joseph, C., Carter, K.E., Hedges, S.W., Lopano, C.L., Guthrie, G.D. and Hakala,
J.A. 2017. Experimental insights into geochemical changes in hydraulically fractured
Marcellus Shale: Applied Geochemistry, v. 76, p. 36-50, doi:
10.1016/j.apgeochem.2016.11.005.
McCaffrey, M.A., Lazar, B. and Holland, H.D. 1987. The evaporation path of seawater and the
coprecipitation of Br- and K+ with halite: Journal of Sedimentary Petrology, v. 57(5), p.
928-937, doi: 10.1306/212f8cab-2b24-11d7-8648000102c1865d.
McLaughlin, M.C., Borch, T. and Blotevogel, J. 2016. Spills of Hydraulic Fracturing Chemicals
on Agricultural Topsoil: Biodegradation, Sorption, and Co-contaminant Interactions:
Environmental Science & Technology, v. 50, p. 6071-6078, doi: 10.1021/acs.est.6b00240.
201
Michael, K., Machel, H.G. and Bachu, S. 2003. New insights into the origin and migration of
brines in deep Devonian aquifers, Alberta, Canada: Journal of Geochemical Exploration,
v. 80, p. 193-219, doi: 10.1016/S0375-6742(03)00191-2.
Munson, E.O., Chalmers, G.R.L., Bustin, R.M. and Li, K. 2016. Utilizing smear mounts for X-
ray diffraction as a fully quantitative approach in rapidly characterizing the mineralogy of
shale gas reservoirs: Journal of Unconventional Oil and Gas Resources, v. 14, p. 22-31,
doi: 10.1016/j.juogr.2016.01.001.
Nelson, A.W., May, D., Knight, A.W., Eitrheim, E.S., Mehrhoff, M., Shannon, R., Litman, R.
and Schultz, M.K. 2014. Matrix Complications in the Determination of Radium Levels in
Hydraulic Fracturing Flowback Water from Marcellus Shale: Environmental Science &
Technology – Letters, v. 1, p. 204-208, doi: 10.1021/ez5000379.
Nelson, A.W., Eitrheim, E.S., Knight, A.W., May, D., Mehrhoff, M.A., Shannon, R., Litman, R.,
Burnett, W.C., Forbes, T.Z. and Schultz, M.W. 2015. Understanding the Radioactive
Ingrowth and Decay of Naturally Occurring Radioactive Materials in the Environment: An
Analysis of Produced Fluids from the Marcellus Shale: Environmental Health
Perspectives, doi: 10.1289/ehp.1408855.
Nelson, A.W., Johns, A.J., Eitrheim, E.S., Knight, A.W., Basile, M., Bettis III, E.A., Schultz,
M.K. and Forbes, T.Z. 2016. Partitioning of naturally-occurring radionuclides (NORM) in
Marcellus Shale produced fluids influenced by chemical matrix: The Royal Society of
Chemistry – Environmental Science: Processes & Impacts, v. 18, p. 456-463, doi:
10.1039/C5EM00540J.
Notte, C., Allen, D.M., Gehman, J., Alessi, D.S. and Goss, G.G. 2016. Comparative analysis of
hydraulic fracturing wastewater practices in unconventional shale developments:
Regulatory regimes: Canadian Water Resources Journal/Revue canadienne des
ressources hydriques, doi: 10.1080/07011784.2016.1218795.
Olsson, O., Weichgrebe, D. and Rosenwinkel, K.-H. 2013. Hydraulic fracturing wastewater in
Germany: composition, treatment, concerns: Environmental Earth Sciences, v. 70, p.
3895-3906, doi: 10.1007/s12665-013-2535-4.
O'Neil, J.R. and Kharaka, Y.K. 1976. Hydrogen and oxygen isotope exchange reactions between
clay minerals and water: Geochimica et Cosmochimica Acta, v. 40, p. 241-246, doi:
10.1016/0016-7037(76)90181-2.
Parkhurst, D.L. and Appelo, C.A.J. 2013. Description of input and examples for PHREEQC
version 3 – A computer program for speciation, batch-reaction, one-dimensional transport,
and inverse geochemical calculations: U.S. Geological Survey Techniques and Methods,
book 6, chap. A43, 497 p., available at https://pubs.usgs.gov/tm/06/a43/.
202
Paukert Vankeuren, A.N., Hakala, J.A., Jarvis, K. and Moore, J.E. 2017. Mineral Reactions in
Shale Gas Reservoirs: Barite Scale Formation from Reusing Produced Water as Hydraulic
Fracturing Fluid: Environmental Science & Technology, v. 51, p. 9391-9402, doi:
10.1021/acs.est.7b01979.
Pawlowsky-Glahn, V. and Egozcue, J.J. 2006. Compositional data and their analysis: an
introduction. In Buccianti, A., Mateu-Figueras, G. and Pawlowsky-Glahn, V. (Eds.):
Compositional Data Analysis in the Geosciences: From Theory to Practice. Geological
Society, London, Special Publications, v. 264, p. 1-10. Retrieved from
http://sp.lyellcollection.org/
Phan, T.T., Capo, R.C., Stewart, B.W., Graney, J.R., Johnson, J.D., Sharma, S. and Toro, J.
2015. Trace metal distribution and mobility in drill cuttings and produced waters from
Marcellus Shale gas extraction: Uranium, arsenic, barium: Applied Geochemistry, v. 60, p.
89-103, doi: 10.1016/j.apgeochem.2015.01.013.
Phan, T.T., Capo, R.C., Stewart, B.W., Macpherson, G.L., Rowan, E.L. and Hammack, R.W.
2016. Factors controlling Li concentration and isotopic composition in formation waters
and host rocks of Marcellus Shale, Appalachian Basin: Chemical Geology, v. 420, p. 162-
179, doi: 10.1016/j.chemgeo.2015.11.003.
R Core Team. 2017. R: A language and environment for statistical computing. R Foundation for
Statistical Computing, Vienna, Austria. https://www.R-project.org/.
Reible, D.D., Honarparvar, S., Chen, C.-C., Illangasekare, T.H. and MacDonell, M. 2016.
Chapter 6 – Environmental Impacts of Hydraulic Fracturing. In S. Orszulik (Ed.),
Environmental Technology in the Oil Industry, p. 199-219, Switzerland: Springer
International Publishing, doi: 978-3-319-24334-4_6.
Renock, D., Landis, J.D. and Sharma, M. 2016. Reductive weathering of black shale and release
of barium during hydraulic fracturing: Applied Geochemistry, v. 65, p. 73-86, doi:
10.1016/j.apgeochem.2015.11.001.
Rietveld, H.M. 1967. Line profiles of neutron powder-diffraction peaks for structure refinement.
Acta Crystallographica, v. 22(1), p. 151-152, doi: 10.1107/S0365110X67000234.
Rietveld, H.M. 1969. A profile refinement method for nuclear and magnetic structures. Journal
of Applied Crystallography, v. 2(2), p. 65-71, doi: 10.1107/s0021889869006558.
Rivard, C., Lavoie, D., Lefebvre, R., Séjourné, S., Lamontagne, C. and Duchesne, M. 2014. An
overview of Canadian shale gas production and environmental concerns: International
Journal of Coal Geology, v. 126, p. 64-76, doi: 10.1016/j.coal.2013.12.004.
203
Rokhforouz, M.R. and Amiri, H.A.A. 2017. Phase-field simulation of counter-current
spontaneous imbibition in a fractured heterogeneous porous medium: Physics of Fluids, v.
29, p. 062104-1-9, doi: 10.1063/1.4985290.
Rosenblum, J., Nelson, A.W., Ruyle, B., Schultz, M.K., Ryan, J.N. and Linden, K.G. 2017.
Temporal characterization of flowback and produced water quality from a hydraulically
fractured oil and gas well: Science of the Total Environment, v. 596-597, p. 369-377, doi:
10.1016/j.scitotenv.2017.03.294.
Rostron, B. and Arkadakskiy, S. 2014. Fingerprinting "stray" formation fluids associated with
hydrocarbon exploration and production: Elements, v. 10, p. 285-290, doi:
10.2113/gselements.10.4.285.
Rostron, B.J. and Holmden, C. 2000. Fingerprinting formation-waters using stable isotopes,
Midale Area, Williston Basin, Canada: Journal of Geochemical Exploration, v. 69-70, p.
219-223, doi: 10.1016/s0375-6742(00)00024-8.
Rowan, E.L., Engle, M.A., Kraemer, T.F., Schroeder, K.T., Hammack, R.W. and Doughten,
M.W. 2015. Geochemical and isotopic evolution of water produced from Middle
Devonian Marcellus shale gas wells, Appalachian basin, Pennsylvania: AAPG Bulletin, v.
99 (2), p. 181-206, doi: 10.1306/07071413146.
Seales, M.B., Dilmore, R., Ertekin, T. and Wang, J.Y. 2016. Numerical analysis of the source of
excessive Na+ and Cl- species in flowback water from hydraulically fractured shale
formations, SPE 180911: 2016 SPE Journal, p. 1-14, doi: 10.2118/180911-pa.
Shipman, S., McConnell, D., McCutchan M.P., and Seth, K. 2013. Maximizing Flowback Reuse
and Reducing Freshwater Demand: Case Studies from the Challenging Marcellus Shale:
SPE-165693-MS, Prepared for presentation at the SPE Eastern Regional Meeting, August
20-22, 2013, Pittsburgh, Pennsylvania, USA.
Sharma, S., Mulder, M.L., Sack, A., Schroeder, K. and Hammack, R. 2014. Isotope approach to
assess hydrologic connections during Marcellus Shale drilling: Groundwater, v. 52 (3), p.
424-433, doi: 10.1111/gwat.12083.
204
Stewart, B.W., Chapman, E.C., Capo, R.C., Johnson, J.D., Graney, J.R., Kirby, C.S. and
Schroeder, K.T. 2015. Origin of brines, salts and carbonate from shales of the Marcellus
Formation: Evidence from geochemical and Sr isotope study of sequentially extracted
fluids: Applied Geochemistry, v. 60, p. 78-88, doi: 10.1016/j.apgeochem.2015.01.004.
Strong, L.C., Gould, T., Kasinkas, L., Sadowsky, M.J., Aksan, A. and Wackett, L.P. 2014.
Biodegradation in waters from hydraulic fracturing: Chemistry, Microbiology, and
Engineering: Journal of Environmental Engineering, v. 140, p. 1-8, doi:
10.1061/(ASCE)EE.1943-7870.0000792.
Stueber, A.M and Walter, L.M. 1991. Origin and chemical evolution of formation waters from
Silurian-Devonian strata in the Illinois basin, USA: Geochimica et Cosmochimica Acta, v.
55, p. 309-325, doi: 10.1016/0016-7037(91)90420-A.
Sullivan, R., Woodroof, R., Steinberger-Glaser, A., Fielder, R. and Asadi, M. 2004. Optimizing
fracturing fluid cleanup in the Bossier sand using chemical frac tracers and aggressive gel
breaker deployment: SPE 90030, Prepared for presentation at the SPE Annual Technical
Conference and Exhibition, September 26-29, 2004, Houston, Texas, USA, doi:
10.2523/90030-ms.
Vengosh, A., Warner, N., Jackson, R. and Darrah, T. 2013. The effects of shale gas exploration
and hydraulic fracturing on the quality of water resources in the United States: Procedia
Earth and Planetary Science, v. 7, p. 863-866, doi: 10.1016/j.proeps.2013.03.213.
Vengosh, A., Warner, N.R., Kondash, A., Harkness, J.S., Lauer, N., Millot, R., Kloppman, W.
and Darrah, T.H. 2015. Isotopic fingerprints for delineating the environmental effects of
hydraulic fracturing fluids: Procedia Earth and Planetary Science, v. 13, p. 244-247, doi:
10.1016/j.proeps.2015.07.057.
Vengosh, A., Kondash, A., Harkness, J., Lauer, N., Warner, N. and Darrah, T.H. 2017. The
geochemistry of hydraulic fracturing fluids: Procedia Earth and Planetary Science, v. 17,
p. 21-24, doi: 10.1016/j.proeps.2016.12.011.
Vidic R.D., Brantley S.L., Vandenbossche J.M., Yoxtheimer D. and Abad J.D. 2013. Impact of
Shale Gas Development on Regional Water Quality: Science, v. 340, p. 826-835, doi:
10.1126/science.1235009.
Wang, F., Pan, Z. and Zhang, S. 2016. Modeling fracturing-fluid flowback behavior in
hydraulically fractured shale gas under chemical potential dominated conditions: Applied
Geochemistry, v. 74, p. 194-202, doi: 10.1016/j.apgeochem.2016.10.008.
Wang, F., Pan, Z. and Zhang, S. 2017. Impact of chemical osmosis on water leakoff and
flowback behavior from hydraulically fractured gas shale: Journal of Petroleum Science
and Engineering, v. 151, p. 264-274, doi: 10.1016/j.petrol.2017.01.018.
205
Ward, H., Eykelbosh, A. and Nicol, A.-M. 2016. Addressing uncertainty in public health risks
due to hydraulic fracturing: Environmental Health Review, v. 59(2), p. 57-61, doi:
10.5864/d2016-013.
Warner, N.R., Darrah, T.H., Jackson, R.B., Millot, R., Kloppmann, W. and Vengosh, A. 2014.
New Tracers Identify Hydraulic Fracturing Fluids and Accidental Releases from Oil and
Gas Operations: Environmental Science & Technology, v. 48, p. 12552-12560, doi:
10.1021/es5032135.
Wei, W., Clinch, S., Shafer, J.L. and Lasswell, P. 2010. Improving connate water salinity
analysis on preserved clay rich cores: SCA2010-29, Prepared for presentation at the
International Symposium of the Society of Core Analysts, October 4-7, 2010, Halifax,
Nova Scotia, Canada.
Wilke, F.D.H., Vieth-Hillebrand, A., Naumann, R., Erzinger, J. and Horsfield, B. 2015. Induced
mobility of inorganic and organic solutes from black shales using water extraction:
Implications for shale gas exploitation: Applied Geochemistry, v. 63, p. 158-168, doi:
10.1016/j.apgeochem.2015.07.008.
Williams, L.B., Hervig, R.L., Wieser, M.E. and Hutcheon, I. 2001. The influence of organic
matter on the boron isotope geochemistry of the gulf coast sedimentary basin, USA:
Chemical Geology, v. 174, p. 445-461, doi: 10.1016/s0009-2541(00)00289-8.
Williams, L.B. and Hervig, R.L. 2002. Exploring intra-crystalline B-isotope variations in mixed-
layer illite-smectite: American Mineralogist, v. 87, p. 1564-1570, doi: 10.2138/am-2002-
11-1206.
Williams, L.B. and Hervig, R.L. 2005. Lithium and boron isotopes in illite-smectite: The
importance of crystal size: Geochimica et Cosmochimica Acta, v. 69(24), p. 5705-5716,
doi: 10.1016/j.gca.2005.08.005.
Williams-Kovacs, J.D. and Clarkson, C.R. 2016. A modified approach for modeling two-phase
flowback from multifractured horizontal shale gas wells: Journal of Natural Gas Science
and Engineering, v. 30, p. 127-147, doi: 10.1016/j.jngse.2016.02.003.
Wood, J.M. 2015. Crushed-rock vs. full-diameter core samples for water-saturation
determination in a tight-gas siltstone play: SPE Reservoir Evaluation & Engineering, v. 18
(3), p. 407-416, doi: 10.2118/174548-pa.
Zheng, Z., Zhang, H., Chen, Z., Li, X., Zhu, P. and Cui, X. 2017. Hydrogeochemical and
Isotopic Indicators of Hydraulic Fracturing Flowback Fluids in Shallow Groundwater and
Stream Water, derived from Dameigou Shale Gas Extraction in the Northern Qaidam
Basin: Environmental Science & Technology, v. 51, p. 5889-5898, doi:
10.1021/acs.est.6b04269.
206
Zhou, Q., Dilmore, R., Kleit, A. and Wang, J.Y. 2015. Evaluating fracturing fluid flowback in
Marcellus using data mining technologies: SPE-173364-MS, Prepared for presentation at
the SPE Hydraulic Fracturing Technology Conference, February 3-5, 2015, The
Woodlands, Texas, USA, doi: 10.2118/173364-ms.
Ziemkiewicz, P.F. and He, Y.T. 2015. Evolution of water chemistry during Marcellus Shale gas
development: A case study in West Virginia: Chemosphere, v. 134, p. 224-231, doi:
10.1016/j.chemosphere.2015.04.040.
Zolfaghari, A., Noel, M., Dehghanpour, H. and Bearinger, D. 2014. Understanding the origin of
flowback salts: A laboratory and field study: SPE-171647-MS, Prepared for presentation
at the SPE/CSUR Unconventional Resources Conference – Canada, September 30-
October 2, 2014, Calgary, Alberta, Canada, doi: 10.2118/171647-ms.
Zolfaghari, A., Tang, Y., Holyk, J., Binazadeh, M., Dehghanpour, H., and Bearinger, D. 2015b.
Chemical Analysis of Flowback Water and Downhole Gas Shale Samples: SPE-175925-
MS, Prepared for presentation at the SPE/CSUR Unconventional Resources Conference,
October 20-22, 2015, Calgary, Alberta, Canada, doi: 10.2118/175925-ms.
Zolfaghari, A., Dehghanpour, H., Noel, M. and Bearinger, D. 2016. Laboratory and field analysis
of flowback water from gas shales: Journal of Unconventional Oil and Gas Resources, v.
14, p. 113-127, doi: 10.1016/j.juogr.2016.03.004.
Zonneveld, J.-P., Gingras, M.K. and Beatty, T.W. 2010. Diverse ichnofossil assemblages
following the P-T mass extinction, Lower Triassic, Alberta and British Columbia, Canada:
Evidence for shallow marine refugia on the northwestern coast of Pangaea: Palaios, v. 25,
p. 368-392, doi: 10.2110/palo.2009.p09-135r.
Zonneveld, J.-P., Golding, M., Moslow, T.F., Orchard, M.J., Playter, T. and Wilson, N. 2011.
Depositional framework of the Lower Triassic Montney Formation, west-central Alberta
and Northeastern British Columbia: Recovery - 2011 CSPG CSEG CWLS Convention.
Zonneveld, J.-P. and Moslow, T.F. 2014. Perennial river deltas of the Montney Formation:
Alberta and British Columbia subcrop edge: GeoConvention 2014 – Focus.
207
Appendices
A summary of the sample preparation method for the dissolved metals analysis was
provided in the methods sections of chapters 2, 3, 4, and 5. This section of the appendix
provides a detailed step-by-step breakdown of the method used to prepare the samples for
All glassware was acid washed in a 5% hydrochloric acid (HCl) bath for a minimum of 4
hours and transferred to a 10% nitric acid (HNO3) bath overnight. All acids used are trace metal
grade. The test tubes used in sampling were new and were acid washed in the 10% HNO 3 acid
bath for a minimum of 4 hours. Glassware and test tubes were rinsed with deionized (DI) water
prior to soaking in the acid baths and again when removed from the acid baths. Acid washed
The procedure for the hydraulic fracturing fluids, flowback water, and produced water samples
2) If an oil layer was visible in the sample, the sample was put into a separatory funnel and
the water portion was collected as a sub-sample (flowback water and produced water
only);
3) The water sample was gently mixed by turning the container upside down two to three
times and then poured into an acid-washed 120 mL Teflon ® container. The sample was
heated to reservoir temperature (75-80°C) in a hot water bath for approximately 24 hours.
208
This step was included to return the fluid to reservoir temperature and re-dissolve any
precipitate that had formed during sample shipment and storage (flowback water and
4) The heated sample was filtered with a 0.45 µm filter and divided for 1) pH, conductivity,
metals (40 mL of sample). The dissolved metals sample was preserved to pH < 2 with
HNO3;
5) A 50 mL glass beaker was weighed then 5 mL of sample was added to the beaker and re-
weighed. For the first step of the acid-digestion, 0.5 mL of HCl and 1mL of HNO 3 were
added to the sample in the fumehood. The beaker was placed on a hot plate in the
fumehood and covered with a ribbed watch glass, which minimizes contamination to the
sample in the open beaker while allowing the sample to evaporate. The sample was
heated until almost dry. The second step of the acid-digestion was adding an additional
1 mL of HNO3 and re-evaporating the solution until almost dry. The remaining
15 mL test tube. The test tube was filled to 10 mL (2x dilution) and re-weighed. Further
dilutions were required due to the high concentrations in the samples – 100x and 1000x
dilutions were made for each sample. All dilutions were calculated by weight;
6) The samples were run on the ICP-OES in two batches, the first run analyzed the 1000x
dilutions for Na and Ca. For some samples, (e.g., for the hydraulic fracturing fluids), a
lower dilution was used for the Na and Ca analysis if the concentrations of these elements
were below the detection limit in the 1000x dilution. The second run analyzed the 100x
and 2x dilutions for the remaining cations of interest. An internal standard of 10 ppm
209
indium (In) was used and was added to all samples as the sample was injected into the
ICP-OES.
210
Appendix B Example of code used for PHREEQC geochemical mixing model
model for mixing between the injected hydraulic fracturing fluid and the formation water. The
data used are an example from site I, well 1. The first model includes mixing only; the second
model includes mixing and secondary mineral precipitation; the third model includes mixing,
secondary mineral precipitation, and ion exchange; and the fourth model includes mixing,
211
MIX 1 # All models
1 0
2 1
Calcite 0 0
Dolomite 0 0
Huntite 0 0
Magnesite 0 0
Celestite 0 0
212
Appendix C Percentages of formation water for all analyzed samples using δ 2H isotopes,
Well Sample Based Based Based on Cl Well Sample Based Based Based on Cl
on δ2H on δ18O concentrations on δ2H on δ18O concentrations
213
Percentage of Formation Water (%) Percentage of Formation Water (%)
Well Sample Based Based Based on Cl Well Sample Based Based Based on Cl
on δ2H on δ18O concentrations on δ2H on δ18O concentrations
D-3 8 31.3 36.1 33.6 F-1 8 34.4 17.4 n.a.
D-4 1 -3.3 7.6 -0.3 F-1 9 34.5 12.0 19.0
D-4 2 0.7 0.4 4.4 F-1 10 32.7 19.5 16.2
D-4 3 8.0 12.9 18.0 F-2 1 34.9 33.0 5.4
D-4 4 n.a. n.a. 16.9 F-2 2 34.9 29.3 8.9
D-4 5 9.9 12.4 16.3 F-2 3 49.1 72.4 7.1
D-4 6 n.a. n.a. 18.0 F-2 4 37.9 34.7 n.a.
D-4 7 22.9 37.8 38.4 F-2 5 32.1 23.8 11.6
D-4 8 n.a. n.a. 32.5 F-2 6 41.5 47.8 n.a.
D-4 9 17.3 23.0 28.8 F-2 7 31.3 21.5 n.a.
D-4 10 n.a. n.a. 42.4 F-2 8 32.2 17.1 n.a.
D-4 11 27.3 24.9 44.1 F-2 9 35.2 18.2 22.5
D-4 12 n.a. n.a. 48.0 F-2 10 34.9 20.3 26.6
D-4 13 n.a. n.a. 55.9 G-1 1 1.5 13.8 16.3
D-4 14 29.3 23.3 49.4 G-1 3 n.a. n.a. 32.1
E-1 1 1.9 30.2 3.3 G-1 5 17.1 21.1 32.4
E-1 3 2.2 6.0 4.7 G-1 7 26.8 32.0 46.9
E-1 5 4.3 28.9 7.2 G-1 8 n.a. n.a. 70.9
E-1 7 n.a. n.a. 8.9 G-1 9 43.3 53.1 85.8
E-1 8 19.1 32.6 15.0 G-1 11 n.a. n.a. 95.3
E-1 10 n.a. n.a. 17.6 G-1 13 57.6 63.7 102.5
E-1 12 24.0 27.3 28.2 H-1 1 8.4 8.4 15.8
E-2 1 16.3 31.2 7.3 H-1 2 7.6 9.6 19.3
E-2 3 n.a. n.a. 10.1 H-1 3 20.9 20.4 24.4
E-2 5 18.0 42.2 11.2 H-1 4 n.a. n.a. 19.3
E-2 7 n.a. n.a. 13.6 H-1 5 18.5 23.8 26.9
E-2 9 22.3 44.5 13.6 H-1 6 n.a. n.a. 31.2
E-2 11 n.a. n.a. 20.3 H-1 7 26.2 38.0 45.7
E-2 14 31.2 68.6 23.6 H-1 8 n.a. n.a. 55.7
E-3 1 15.3 27.9 15.7 H-1 9 33.1 14.5 60.6
E-3 3 5.7 -30.3 19.6 H-1 10 n.a. n.a. 65.5
E-3 6 24.0 45.6 20.0 H-1 11 n.a. n.a. 74.3
E-3 10 n.a. n.a. 25.8 H-1 12 31.1 25.0 69.2
E-3 11 38.9 98.0 26.1 H-1 13 n.a. n.a. 77.6
E-4 1 1.1 11.5 3.5 H-1 14 n.a. n.a. 77.5
E-4 3 2.0 8.0 8.2 H-1 15 25.5 51.4 81.8
E-4 5 n.a. n.a. 3.5 H-1 16 n.a. n.a. 79.9
E-4 7 7.9 10.4 12.8 H-1 17 n.a. n.a. 82.9
E-4 9 n.a. n.a. 15.5 H-1 18 30.7 50.8 86.2
E-4 11 4.6 -40.2 21.9 I-1 1 7.5 7.3 1.2
F-1 2 38.8 46.1 n.a. I-1 3 9.9 10.6 3.3
F-1 4 32.1 22.9 14.2 I-1 4 n.a. n.a. 4.2
F-1 5 43.2 49.6 n.a. I-1 7 11.9 13.6 6.5
F-1 6 31.8 16.1 13.1 I-1 9 n.a. n.a. 7.3
F-1 7 33.7 21.3 13.5 I-1 11 16.1 17.1 8.6
214
Percentage of Formation Water (%)
Well Sample Based Based Based on Cl
on δ2H on δ18O concentrations
I-1 13 20.7 17.2 12.3
I-1 16 23.2 18.7 14.0
I-1 18 n.a. n.a. 18.4
I-1 20 28.5 21.2 19.1
I-1 23 n.a. n.a. 23.2
I-1 26 28.8 30.6 29.4
I-1 29 n.a. n.a. 32.2
I-1 32 31.1 32.2 33.0
I-2 1 13.5 15.7 4.6
I-2 3 21.7 21.2 8.8
I-2 5 n.a. n.a. 8.9
I-2 7 23.9 24.0 11.9
I-2 9 n.a. n.a. 15.6
I-2 11 25.9 25.9 20.1
I-2 13 n.a. n.a. 26.6
I-2 14 45.4 43.1 30.8
I-2 18 n.a. n.a. 39.0
I-2 21 51.8 41.5 43.5
I-2 23 n.a. n.a. 46.0
I-2 26 55.2 43.2 50.8
I-2 29 n.a. n.a. 54.4
I-2 32 59.1 39.5 56.9
215