Shales Leaching Modelling For Prediction of Flowback Fluid Composition - Energies-12-01404 PDF

energies
Article
Shales Leaching Modelling for Prediction of
Flowback Fluid Composition
Andrzej Rogala * , Karolina Kucharska and Jan Hupka
Department of Process Engineering and Chemical Technology, Faculty of Chemistry, Gdansk University of
Technology, Narutowicza 11/12, 80-233 Gdansk, Poland; karolina.kucharska@pg.edu.pl (K.K.);
jhupka@pg.edu.pl (J.H.)
* Correspondence: andrzej.rogala@pg.edu.pl; Tel.: +48-58-347-2866

Received: 11 February 2019; Accepted: 8 April 2019; Published: 11 April 2019
Abstract: The object of the paper is the prediction of flowback fluid composition at a laboratory
scale, for which a new approach is described. The authors define leaching as a flowback fluid
generation related to the shale processing. In the first step shale rock was characterized using X-ray
fluorescence spectroscopy, X-ray diffractometry and laboratory analysis. It was proven that shale rock
samples taken from the selected sections of horizontal well are heterogeneous. Therefore, the need to
carry a wide range of investigations for highly diversified samples occurred. A series of leaching
tests have been conducted. The extracts were analyzed after leaching to determine Total Organic
Carbon and selected elements. For the results analysis significant parameters were chosen, and
regression equations describing the influence of rocks and fracturing fluid parameters on the flowback
fluid composition were proposed. Obtained models are described by high values of determination
coefficients with confidence coefficients above 0.99 and a relatively low standard deviation. It was
proven that the proposed approach regarding shale leaching can be properly described using shale
models at a laboratory scale, however scaling up requires further investigations.
Keywords: fracturing fluid; flowback fluid; leaching; solid-liquid extraction
1. Introduction
Shales are fine-grained, fissile and the most common sedimentary rocks found in the Earth’s
crust, composed of clay and other minerals, especially quartz and calcite, as well as organic matter [1].
Shales with proper mature organic matter have gas potential and represent unconventional gas
reservoirs. The division into conventional and unconventional reservoirs is associated primarily
with the permeability of the reservoir. Conventional reservoirs have a permeability above 0.1 mD,
while unconventional reservoirs are below 0.1 mD, and for gas-bearing shales, even below 0.001 mD [2].
The differences in the construction of the reservoir (containing gas in the interstitial space) of a
conventional and unconventional shale type are presented in Figure 1. The yellow area represents the
gas field space whereas grey/white areas represent rock.
High heterogeneity regarding mineralogical structure, elemental composition and reservoir
parameters are typical for shale formations. Individual properties may differ substantially even within
individual formations [3–5]. Clear differences in the properties of the deposit occur on a scale of several
hundreds to even a few meters [6,7]. The high heterogeneity of the deposit makes all of the well
operations diverse and dependent on the given formation. Therefore, a number of deposit stimulation
technologies have been developed [8,9].
Energies 2019, 12, 1404; doi:10.3390/en12071404 www.mdpi.com/journal/energies

Energies 2019, 12, 1404 2 of 21
Energies 2018, 11 FOR PEER REVIEW 2
Figure 1. Schematic structure of conventional (left) and unconventional (right) gas reservoir.
Figure 1. Schematic structure of conventional (left) and unconventional (right) gas reservoir.
In the shale rock gas-filled spaces are not interconnected, and the permeability is very low.
In
To ensurethe shale
gas flow, rockit gas-filled
is necessary spaces are not
to create interconnected,
a grid of fractures. and the permeability
For this is very low.
purpose, stimulation of theTo
ensure gas is
reservoir flow, it is necessary
needed, wherein the to create
hydraulica grid of fractures.
fracturing is theFor thistechnology
main purpose, stimulation of the reservoir
currently applied [10,11].
isHydraulic
needed, whereinfracturing consists of using a fracturing fluid pumped under pressure in the Hydraulic
the hydraulic fracturing is the main technology currently applied [10,11]. range of
fracturing
700–1200consists
bar for gas of using
or/and a fracturing
oil-bearingfluid pumped The
formations. under pressure
amount in the needed
of water range offor 700–1200
fracturingbar isfor
gas or/and oil-bearing formations. The amount of water needed for
usually between 10–25 thousand cubic meters and depends on the length of the horizontal part of the fracturing is usually between 10–25
thousand
borehole.cubicThe meters
fracturing andpressure
dependsmust on the belength
higherofthan the horizontal
the tensile part of the
strength ofborehole.
the rock, Thebut itfracturing
cannot
pressure must be higher than the tensile strength of the rock, but
exceed the strength parameters of the piping, as it is limited by the power of the pumps. The purpose it cannot exceed the strength
parameters
of the fracturing fluid is primarily to create as much contact surface of the deposit with the wellfluid
of the piping, as it is limited by the power of the pumps. The purpose of the fracturing by
iscreating
primarily to create as much contact surface of the deposit with the well
a network of gaps, and to prevent the fractures from closing after fracturing [12]. Fracturing by creating a network of gaps,
and to prevent
fluids usuallythe fractures
consist of atfrom
leastclosing
90% water after fracturing
containing[12]. Fracturing
a proppant asfluids
well as usually
otherconsist
additives of at[13].
least
90% water containing a proppant as well as other additives [13]. Proppant
Proppant is a small grain material added to the fracturing fluid in order to prevent the fractures from is a small grain material added
toclosing
the fracturing fluid inreduction
after pressure order to prevent
resulting thefrom
fractures
hydraulicfrom crushing
closing after pressure
of rocks [14].reduction resulting
Other additives,
from
which are typically introduced at a level of about 0.5% (v/v), are used to modify the propertiesofofabout
hydraulic crushing of rocks [14]. Other additives, which are typically introduced at a level the
0.5%
fluid(v/v), are used
to enable better to penetration
modify the properties
of the formationof the and fluidprovide
to enable better penetration
compatibility between ofthethefluid
formation
and
and provide
reservoir compatibility between the fluid and reservoir [12,15].
[12,15].
After the
After the fracturing
fracturing is completed,
is completed, 10–50%
10–50% of the fluid
of the returns
fluid automatically
returns automatically or byorstimulation
by stimulation to the
surface. The returning stream is called flowback fluid. In extreme
to the surface. The returning stream is called flowback fluid. In extreme cases, the flowback fluid cases, the flowback fluid does not
return
does to notthe surface
return at all,
to the or returns
surface at all,inorlarger
returns quantities.
in largerThe rest of theThe
quantities. fluid remains
rest of the in theremains
fluid reservoir
[16]. Flowback fluid differs significantly from the fracturing fluid, as
in the reservoir [16]. Flowback fluid differs significantly from the fracturing fluid, as it containsit contains suspended fine rocks as
a suspended
result of the fineleaching
rocks asprocess,
a result of reservoir
the leachingwater, drilling
process, muds, and
reservoir water,also various
drilling chemical
muds, and also substances,
various
such as dissolved solids (e.g. chlorides, sulfates, etc., measured as total
chemical substances, such as dissolved solids (e.g., chlorides, sulfates, etc., measured as total dissolved dissolved solids or TDS),
suspended solid particles (TSS), bacteria, metals (e.g. calcium, magnesium,
solids or TDS), suspended solid particles (TSS), bacteria, metals (e.g., calcium, magnesium, barium, barium, strontium), iron
compounds,
strontium), aromatic
iron compounds,hydrocarbons,aromatic carbon dioxide, hydrogen
hydrocarbons, sulphidehydrogen
carbon dioxide, and othersulphide
components and [17].
other
Average
components [17]. results of fracturing and post-treatment fluid analysis from the Marcellus Shale basin in
the United States
Average are presented
results of fracturing in Table 1. The results of
and post-treatment the analysis
fluid concentrations
from the of Marcellus
the ingredients
Shale maybasinvary
in
bythea factor
United ofStates
several aredozen with the
presented concentrations
in Table 1. The results of theoffracturing fluid [18].of the ingredients may
the concentrations
varyAlthough
by a factor theoffracturing
several dozen fluidwithis environmentally
the concentrations friendly,
of theflowback
fracturingfluid fluidshould
[18]. be treated as an
environmental
Althoughthreat due to itsfluid
the fracturing composition. It can havefriendly,
is environmentally adverseflowback
effects on the should
fluid environment,
be treated andas hence
an
requires
environmental threat due to its composition. It can have adverse effects on the environment, and henceto
purifying and/or disposal. Flowback fluid, treated as a mining waste, can be transported
another
requires drilling
purifying plant, and also
and/or be transferred
disposal. Flowbacktofluid, companies
treateddealing with waste,
as a mining the disposal
can beoftransported
mining waste. to
However usually it is transferred to a sewage treatment plant or another
another drilling plant, and also be transferred to companies dealing with the disposal of mining waste. installation that neutralizes
waste
However[19,20]. Due it
usually toisthe high variability
transferred to a sewageof the flowbackplant
treatment fluidorand the difficulties
another installationofthat its neutralizes
composition
estimation, models and tools that help in its prediction are desirable.
waste [19,20]. Due to the high variability of the flowback fluid and the difficulties of its composition
estimation, models and tools that help in its prediction are desirable.
Energies 2019, 12, 1404 3 of 21
Table 1. Comparison of concentrations of the most important components in fracturing fluid and
flowback fluid from the Marcellus Shale [18].
Fracturing Fluid Flowback Fluid

Component Range of Median Concentration Range of Median Concentration
Concentrations (ppm) (ppm) Concentrations (ppm) (ppm)
Na+ 25.70–6190 67.8 10700–65100 18000
Ca2+ 6.70–2990 32.9 1440–23500 4950
Mg2+ 1.20–235 6.7 135–1550 559
Fe2+ 0.00–14.3 1.2 10.8–180 39
Ba2+ 0.06–87.1 0.4 21.4–13900 686
Cl− 4.10–3000 42.3 26400–148000 41850
HCO3 − <1.00–188 49.9 29.8–162 74.4
NH4 + 0.58–441 5.9 15–242 82.4
Flowback fluid analysis is being widely used in shale gas recovery modelling. There are many
models describing propagation of shale fracture to assess possible production of shale gas [21–26]. Some
attempts to describe flowback fluid production mechanisms are reported [27–30] and several methods
to develop volume control are described [31,32]. Unfortunately, there are not many investigations
dedicated to the prediction of the composition of fracturing flowback fluid and hardly any tools to
limit the migration of chosen chemical compounds from the reservoir to the fluid. Methods focused on
computer programs, supported by precipitation tests [33], statistics of reservoir data [34] or statistics
of fracturing wells in chosen basin of gas bearing shales can be specified. However evaluation is not
possible because the proposed tools are often unavailable and not described enough to test them due to
the unnormalized character of the data [35]. Nevertheless very useful information can be found on the
basis of Total Organic Carbon (TOC) regarding salt migration into flowback fluid streams [33]. Also
ionic strength and the influence of ion interactions exhibit a crucial role [35]. Due to the unnormalized
character of the data presented in the literature, the models are often non-comparable. The most
interesting modeling approaches are presented below.
A promising model was presented by Gdanski et al. [35]. The model allows one to predict the
amount and composition of the flowback fluid. A two-dimensional numerical modelling was used,
taking into account the physics of fracturing fluid flow and flowback fluid and chemical interactions
in the borehole. Leaching of sodium, potassium, chlorides, sulphates, carbonates and boron were
considered in the model. The model provides separate data for post-treatment fluids and reservoir
waters. Based on the adjustment of the fluid production rate, it is also possible to estimate certain
properties of the reservoir, such as relative permeability and capillary pressure. However, it should be
noted that the author based his model on a commercial simulator [36], that is unfortunately commonly
unavailable and therefore, impossible to evaluate. In addition, the conducted considerations concerned
on small-scale fracturing in a vertical hole with accurate characteristics. Such a large amount of
data cannot be obtained for full-scale horizontal wells with diversified fluids, therefore, the model is
unapplicable for the conditions presented by other types of wells.
Another model was developed by the Barbot team [33,34]. It concerned the fracturing of wells in
the Devonian shale in the north-eastern United States. An analysis of 160 flowback fluids was used to
build a model for the prediction of the quantity and composition of the flowback fluids in the American
Marcellus basin. Models for the concentration prediction of sodium, calcium, magnesium, barium,
strontium, bromides and chlorides were developed. The performed tests may be applicable during the
management of the flowback fluid on this deposit. Despite the authors’ conclusions, analysis of only
160 flowback fluid samples cannot give enough data for modelling with no proper relation to shale
rock properties. This type of model can be built at the advanced stage of shale gas extraction only for
very specific areas and it is impossible to extend it for other reservoirs.
A much more advanced model was presented by Balashov [37] In addition to analyzing a larger
amount of data, Balashov et. al. included considerations regarding the diffusion model based on
shale rock. A numerical model was created and calibrated using field data from a specific area. In the
Energies
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rock. A numerical model was created and calibrated using field data from a specific area. In the
conclusions, the author claimed that well-fitting numerical models were obtained, unfortunately we
conclusions, the author claimed that well-fitting numerical models were obtained, unfortunately we
cannot verify this, as the model itself has not been sufficiently presented.
cannot verify this, as the model itself has not been sufficiently presented.
Unfortunately, the approaches presented in the literature are completely different and there is a
Unfortunately, the approaches presented in the literature are completely different and there is a
lack of available data to evaluate and compare them. Therefore, an idea to create a new type of model
lack of available data to evaluate and compare them. Therefore, an idea to create a new type of model
for flowback fluid composition prediction was proposed and presented in this paper. The authors will
for flowback fluid composition prediction was proposed and presented in this paper. The authors will
make an attempt to contribute to the understanding of leaching method development.
make an attempt to contribute to the understanding of leaching method development.
A new approach to modeling flowback fluid composition prediction has been proposed. Research
A new approach to modeling flowback fluid composition prediction has been proposed. Research
was carried out to describe the mechanism of flowback fluid production and composition generated
was carried out to describe the mechanism of flowback fluid production and composition generated
during leaching of shale rock by fracturing fluid. The process was considered in a state of equilibrium
during leaching of shale rock by fracturing fluid. The process was considered in a state of equilibrium
due to the long residence time of fracturing fluid in the reservoir. Leaching course depends mainly
due to the long residence time of fracturing fluid in the reservoir. Leaching course depends mainly on
on physical parameters like the heterogeneity of solids, size of particles, porosity, permeability and
physical parameters like the heterogeneity of solids, size of particles, porosity, permeability and
temperature of the process as well as pH, conductivity, total organic carbon (abr. TOC), time complexed
temperature of the process as well as pH, conductivity, total organic carbon (abr. TOC), time complexed
reactions, redox potential and biological activity [38]. For shale leaching applying complexed fracturing
reactions, redox potential and biological activity [38]. For shale leaching applying complexed fracturing
fluids, a model complexity limiting approach needs to be applied. It was proposed to find a model based
fluids, a model complexity limiting approach needs to be applied. It was proposed to find a model based
on rock properties which cannot be modified. Statistically significant parameters for leaching were
on rock properties which cannot be modified. Statistically significant parameters for leaching were
identified as follows: pH, temperature, TOC and ionic strength [39–41], and the mentioned paramaters
identified as follows: pH, temperature, TOC and ionic strength [39–41], and the mentioned paramaters
can be modified by changing the fracturing fluid composition. To make the model applicable, shale
can be modified by changing the fracturing fluid composition. To make the model applicable, shale rock
rock particles from drilling mud logging were prepared and used. Application of drill cuttings from
particles from drilling mud logging were prepared and used. Application of drill cuttings from mud
mud logging can cause problems with sample preparation [42]. Nevertheless, at the same time,
logging can cause problems with sample preparation [42]. Nevertheless, at the same time, cross-sectional
cross-sectional material from the fracturing process with no need for much expensive coring may come
material from the fracturing process with no need for much expensive coring may come in handy. The
in handy. The proposed approach will allow other scientific groups and laboratories to evaluate the
proposed approach will allow other scientific groups and laboratories to evaluate the presented data
presented data and extend the presented considerations using samples from other different shale gas
and extend the presented considerations using samples from other different shale gas reservoirs. An
reservoirs. An overall conceptualization of data generation and processing is presented in Figure 2.
overall conceptualization of data generation and processing is presented in Figure 2.
Figure 2.
Figure Overall conceptualization
2. Overall conceptualization of
of data
data generation
generation and
and processing.
processing.
2. Materials and Methods

2. Materials and Methods
2.1. Shale Sample Acquisition
2.1. Shale Sample Acquisition
Samples of drill cuttings for further research were obtained from bentonite drilling mud.
TheSamples
samplesof drillfrom
come cuttings for further
the Baltic research
basin, in were obtained
the Pomeranian from bentonite
area (Pomeranian drilling mud.
voivodeship, The
Poland),
samples come from
from a depth the 4.250
of about Balticmeters,
basin, in the Pomeranian
taken arealength
along the entire (Pomeranian voivodeship,
of the horizontal Poland),
section from a
(120 meters
depth of
each). about 4.250 meters, taken along the entire length of the horizontal section (120 meters each).
2.2. Shale
2.2. Sample
Shale Preparation
Sample Preparation
InInorder
ordertotoremove
removethe themud
mudfrom
from the
the surface
surface of the cuttings,
of the cuttings, cleaning
cleaning ofofthe
thetested
testedmaterial
materialwas
was
carried
carriedout. ForFor
out. thisthis
purpose,
purpose,thethe
shale sample
shale waswas
sample sprinkled withwith
sprinkled a stream of water,
a stream next different
of water, sieves
next different
were used
sieves (sieve
were usedsizes: 2.362,
(sieve 0.18,
sizes: 0.0880.18,
2.362, mm). Samples
0.088 mm). were separated
Samples until the mud
were separated untilwas
the completely
mud was
removed. According
completely removed. to According
Carugo et al.’s [43] recommendations,
to Carugo a 2.362–0.18 amm
et al.’s [43] recommendations, size fraction
2.362–0.18 wasfraction
mm size selected
for further investigations. The higher fraction represents cuttings that could move from other parts of
the well, or come from a damaged well walls, smaller drill cuttings were too small to perform further
Energies 2019, 12, 1404 5 of 21
was selected for further investigations. The higher fraction represents cuttings that could move from
other parts of the well, or come from a damaged well walls, smaller drill cuttings were too small to
perform further research due to their properties. After cleaning and sieving, the samples were dried at
40 ◦ C for 24 h. The dried samples were ground in a vibratory ball mill to achieve a grain size below
0.088 mm, and then reduced by a flattened pile.
2.3. Shale Samples Analysis

Mineralogical characterization was realized using X-ray Diffraction (XRD) using a Miniflex 600
X-ray diffractometer (Rigaku, Neu-Isenburg, Germany). The semi-quantitative mineral composition
was calculated using Rietveld method, dedicated to rocks with high concentration of clay minerals.
Elemental analysis was performed using an X-Ray fluorescence (XRF) spectrometer (S8 TIGER
Wavelength Dispersive X-ray Fluorescence WDXRF, Bruker, Billerica, MA., USA). Total organic carbon
was analyzed using a CHNS elemental analyzer (Flash, 2000; Thermo, Waltham, UK).
2.4. Preparation of Model Fracturing Fluids

In order to prepare model fracturing fluids, acetate (pH = 5), dihydrogen phosphate (pH = 7) and
ammonium (pH = 9) buffers with appropriate acid-base ratios were used. The prepared fluid was
buffered at 0.002 M. It results from the analysis of the components of fracturing fluids used in Polish
deposits. Also, ionic strength and total organic carbon range is a result of calculations based on the
compositions of these fracturing fluids. The ionic strength was controlled by the addition of potassium
chloride and the organic carbon content added as propylene glycol.
2.5. Leaching Tests

Leaching tests were carried out according to OECD 106: Adsorption - Desorption method [42]
using 10 g of a shale sample per 100 mL of “model fracturing fluid” (MFF) which is a laboratory
composed model fluid to conduct leaching tests. Liquid/solid phase separation was preformed via
centrifugation at 4000 rpm, vacuum filtration and final separation with 0.45 µm pore size polypropylene
membranes. Leaching tests were conducted according to parameters presented in Table 2 which
contains a summarized plan listing the following variables: temperature, pH, ionic strength and TOC.
Table 2. Parameters of “model fracturing fluids” (MFF) for leaching tests of shale samples.
t (◦ C) pH IS (mol/L) TOC (g/L)

No. MFF
X1 X2 X3 X4
1 P1 60 9 0.51 0.06
2 P2 60 9 0.03 4.06
3 P3 60 5 0.51 4.06
4 P4 60 5 0.03 0.06
5 P5 80 9 0.51 4060
6 P6 80 9 0.03 0.06
7 P7 80 5 0.51 0.06
8 P8 80 5 0.03 4.06
9 P9 80 7 0.51 4.06
10 P10 60 7 0.03 0.06
11 P11 80 9 0.51 2.06
12 P12 60 5 0.03 2.06
13 P13 70 7 0.27 2.06
14 P13 70 7 0.27 2.06
15 P13 70 7 0.27 2.06
t—temperature of the experiment equal to assumed wellbore conditions, pH—pH of the MFF, IS—ionic strength of
the MFF, TOC—total organic carbon of MFF.
Energies 2019, 12, 1404 6 of 21
For each of 10 rock samples 15 tests were performed—13 different fluids and two repetitions for
fluid P13 (for the statistical approach) which is the average value of the range of the analyzed variables.
The range of temperatures chosen for leaching tests is based on field data from service companies in
Poland (i.e. BNK Petroleum, Camarillo, CA, USA) and corresponds with real temperatures in the depth
of fractured horizontal sections of the well from Polish reservoirs with the highest gas production
potential. Unfortunately, the tests presented are destructive to the core samples. Therefore, it is highly
recommended to use shale cuttings which are cheaper and more available in comparison with core
samples. Leachate compositions was analyzed by ICP-OES using an iCAP 6500 Duo spectrometer
(Thermo, Waltham, UK). Data analysis and other calculations were performed using the RStudio
Desktop (v. 1.0.143) software. Laboratory data obtained during analyses of liquids after leaching were
grouped and entered into the program as descriptive variables. Temperature, ionic strength, pH, TOC
and possible interactions between them as well as the results of rock analysis were variables. Then
RStudio Desktop tools were used to compare different possible models, allowing the selection of the
best one. A multistep linear regression was used to obtain the presented models. Only the models
for which the coefficient of determination (abr. R2 ) was above 0.85 were taken into consideration,
the probability value for all describing variables was below 0.05 (variable values are not random),
so the confidence level was always above 0.95 (note: R2 coefficients are calculated for obtained model
equations not for the residual analysis diagrams). In the next step only those equations for which all
separate levels of confidence for every separate parameter were above 0.95 were considered. Then the
model with the highest determination coefficient was chosen for further analysis. For chosen model
the standard deviation was always the lowest taking into account considered models and its value
justifies the correctness of application of R2 as a crucial parameter to choose the most adequate model.
The residual analysis showed a sufficient number of describing variables (small inclination angle to the
abscissa) and there was no correlation between residuals and described variables (Pearson between −0.5
and 0.5). The Pearson coefficients were calculated for the correlation between elements concentrations
in leachates and the residuals of the model. The residuals were calculated as the difference between
laboratory and model data values. The model was selected basing on the comparison of the standard
model error, the determination coefficient, the level of significance and the number of parameters
relevant to the correct description of the model. Other parameters presented in the next section were
calculated using statistical and mathematical methods implemented in RStudio software [43].
3. Results and Discussion

Results of elemental and mineralogical analysis are presented in Tables 3 and 4. In Table 3, only
elements which provided data for creating models are presented.
Table 3. Results of elemental analysis of shale samples (A1 ÷ A10) using the XRF method.
No. of Element Concentration in the Shale Sample (CS) (ppm) Aw TOCS

Sample (m2 /g) (%)
B Ba Li Mg Mo Rb Si Sr Ca
A1 4050 821 139 18240 10 3372 247285 401 116287 15.17 2.11
A2 3988 593 149 14820 95 3570 278445 175 35020 16.15 0.84
A3 3325 708 97 19570 82 2542 229900 605 179117 12.77 2.41
A4 3637 967 112 15960 9 3469 241965 179 131634 10.24 2.43
A5 3467 1208 110 17670 97 2578 262200 178 114948 10.67 2.72
A6 3694 774 115 23560 97 3369 262105 262 100013 14.05 1.40
A7 3361 1119 88 26695 82 3280 248045 212 123188 14.61 1.61
A8 3918 1455 122 20805 106 3068 273505 178 68804 9.72 4.40
A9 3425 1395 120 19665 100 2777 277400 154 58916 13.29 1.81
A10 3513 842 119 18335 105 3358 282150 140 59019 12.62 1.77
Aw—internal area of shale sample, TOCS —Total organic carbon in shale sample, B, Ba, Li, etc.—symbols of the
indicated elements, CSX —element X concentration in shale sample.
Energies 2019, 12, 1404 7 of 21
Table 4. Results of mineralogical analysis of shale samples (A1 ÷ A10) using the XRD method.
Group of Minerals (%)

No. of Sample
G1 G2 G3 G4 G5
A1 21.50 11.95 9.13 15.24 42.19
A2 25.25 3.66 0.08 10.74 60.28
A3 18.10 37.19 0.12 20.83 23.75
A4 28.14 25.49 0.25 18.47 27.64
A5 25.94 27.60 0.12 23.84 22.50
A6 29.33 43.72 1.85 6.16 18.94
A7 19.61 46.83 0.24 8.82 24.50
A8 32.52 24.94 0.12 5.98 36.44
A9 46.16 20.36 0.88 9.31 23.29
A10 25.56 21.96 0.12 9.22 43.15
G1—sum of quartz, plagioclase (albite) and potassium feldspar (microcline, orthoclase), G2—sum of calcite and
dolomite content, G3—sum of barite and pyrite content, G4—sum of chlorite, illite, montmorillonite and kaolinite
content, G5—sum content of muscovite, biotite, paragonite and glauconite.
A detailed mineralogical analysis is attached in the Appendix A (Table A1). The shale samples
were tested for organic carbon content. When analyzing the results in Table 4, it can be assumed that the
section of the well from which the A8 sample was taken is the most promising in terms of hydrocarbon
production. Also, the TOC content for samples A1, A3, A4 and A5, which is above 2%, theoretically
indicates that the hydrocarbon content in the test rock is sufficient for gas operation. However, this fact
cannot be unambiguously conducted because no thermal maturity studies of organic matter have been
carried out.
The analysis of the results of the mineralogical composition proves that the mineral structure of
the rocks forming the gas-bearing slate form shows high heterogeneity in the single well’s circle. The
distance between successive sections was only 120 meters, and the composition of the rocks from each of
them is completely different, even for neighboring sections. During hydraulic fracturing, the operator
should pay attention to the need to use different fracturing fluid compositions and parameters to
obtain an effective gas flow. The big advantage of such a heterogeneity of the deposit in relation to the
proposed model is the wide scope of the model’s application. The disadvantage is the poor estimation
of impurities in the flowback fluid.
The content of minerals from the smectites group (montmorillonite) for samples A3 and A5 and
A7 (Table A1 in the Appendix A) is respectively 10.73%, 0.12% and 0.24%, while for the remainder it is
equal to 0%. This result means that the formation is heterogeneous on the scale of a single well. Most
sections should be slightly susceptible to water. The content of carbonate minerals (which include
calcite and dolomite) for the tested samples is in the range of 3.7–46.8%. Such a large variation indicates
that the tested samples differ significantly in reactivity, which will certainly have an impact on the
conducted leaching tests. The amount of quartz from the analyzed cuttings ranges from 13.6% to
35%. It can be deduced that in individual sections of the borehole, the formation will exhibit varied
mechanical properties (diversification of brittleness). The content of other minerals is also very diverse,
so the leaching process may proceed with different leaching efficiency for different rocks using the
same model fracturing (leaching) fluids.
Differences in specific surface (which is actually the open surface as a result of grinding samples
in vibratory mills) probably occur mainly due to differences in hardness and cleavage of the rock
and random factors. The reference to the open area is necessary for the quantitative mathematical
description of the model to be reliable. In selected cases, the surface may be negligible when the
content of the component available through the open surface exceeds the solubility of this component
in the fracturing fluid of a given composition and temperature.
The results of elemental analysis of leaching fluids and derived, as equations, models that describe
correlation between concentrations of chosen elements (cB , cBa , etc.) and variables. Residual analysis
(difference between measured and calculated values) and maximum and minimum values calculated
Energies 2019, 12, 1404 8 of 21
for the part of the model that can be influenced by controllable parameters of the fracturing fluid
(c’min (60), c’min (80), c’max (60), c’max (80)) are presented in Tables 5–13. Composition of shales and
temperature in the borehole are parameters of a particular well, therefore, we can change: IS, TOC and
pH (by changing
Energies 2018,the fracturing
11 FOR PEER REVIEW fluid composition) so c’B , is a part of the whole c equation which 8 can be
manipulated Energies
and is 2018,
used 11 FOR
to PEER REVIEW
calculate the possible range of changeability of the model by fracturing 8 fluid
(60), c’min (80), c’max (60), c’max (80)) are presented in Tables 5–13. Composition of shales and temperature
(60),
in thec’min (80), c’max
borehole are(60), c’max (80))ofare
parameters presented in
a particular Tables
well, 5–13. Composition
therefore, we can change: of shales
IS, TOCand and
temperature
pH (by
parameter manipulations.
(60), c’min (80), The values
c’parameters
max (60), c’maxof
of
(80)) c’ min
are and
presented c’max were5–13.
intherefore,
Tables calculated
Composition for two extreme
of shales and pH temperature
temperature
in the borehole are a particular well,
changing the fracturing fluid composition) so c’B, is a part of the whole c equation which we can change: IS, TOC and can (by be
values. Itchanging
was in calculated
thethe borehole
fracturingthat the minimum
are fluid
parameters
composition) and
of a particular
so c’maximum
B, iswell, values
therefore,
the we
a changeability
part of wholefor
canall models
change:
cmodel
equation are equal
IS,which
TOC and
can beto(by
pH 60 or
◦ manipulated and is used to calculate the possible range of of the by fracturing fluid
80 C (minimum changing
manipulated and the
andmaximumfracturing
is used toThe fluid composition)
temperature).
calculate theofpossible The so
range c’ , is a
differences
ofwere
B part
changeability of the
between whole
offor
thetwo c
these
model equation
byvalues which
fracturing arefluid can be
presented
parameter manipulations. values c’min and c’max calculated extreme temperature
manipulated
parameter and is used
manipulations. The tovalues
calculateof the
minpossible
c’and and range
c’max were of calculated
changeability of theextreme
forelement
two model by fracturing fluid
temperature
in Table 14. These
values. It was results
calculatedindicate
that thehow much
minimum the concentration
maximum values forofallthemodels are equalin the
to 60flowback
or 80°C fluid
values.parameter
It was manipulations.
calculated that theThe values and
minimum of c’maximum
min and c’max werefor
values calculated forare
two extreme temperature
can be reduced
(minimum by proper
and maximum control of the
temperature). parameters
The differences of the theseall
fracturing
between models
fluid
values equal
according
are presented toin60Table
to
or
the
80°C
developed
14.
values.and
(minimum It was calculated
maximum that the minimum
temperature). and maximum
The differences values for all models are equal to 60 14.or 80°C
These
models. Due results
to the indicate
statistical how much of
nature thethe
concentration
model, in thebetween
ofsome element
cases
these
in thevalues
lowering flowbackare presented
the fluid can be
concentration
in Table
reduced could
These (minimum
results and
indicate maximum
how temperature).
much theof The
concentration differences
of fluid between
the element in thethese values
flowback are presented
fluid models.
can be reducedin Table 14.give
by proper control of the parameters the fracturing according to the developed Due to
a negativeby value.
TheseThis
proper results
control should
indicate
of the be taken
how
parametersmuchinto
ofthe
theaccount
fracturing when
concentration fluidof using
the and
element
according to possibly
in thedeveloped
the
the statistical nature of the model, in some cases lowering the concentration could give a negative value.
implementing
flowback fluid
models. canDue the
be reduced
to model
by proper
the statistical control of the parameters of theare
fracturing fluid according to the
14.developed models. Due to
using a computer
This shouldtool. benatureModel
taken of the
into model,
fracturing
account in some
when cases
fluids
using lowering
and the
characterized
possibly concentration
implementingin Table could
the giveusing
model a negative value.
a computer
the statistical
This Model
should nature
be taken into of the model,
account wheninusing
someand
cases lowering
possibly the concentration could give a negative value.
tool. fracturing fluids are characterized in Table 14. implementing the model using a computer
tool. This
Model should be taken
fracturing into
fluids areaccount when using
characterized and14.
in Table possibly implementing the model using a computer
Table 5. Results of leaching samples A1 to A10 rocks using fluids P1 to P13 for Boron (B).
tool. Model fracturing fluids are characterized in Table 14.
B concentration in samples after leaching of A1 to A10 rocks using fluids P1 to P13
Model
cB = −5155 + 35.6t − 549.7TOC − 74.7(TOC)2 − 341.7pH Model× IS + 25.5pH × TOC + 21.5t × IS + 9.3t × TOC − 211.6G1
cB = −5155 + 35.6t − 549.7TOC − 74.7(TOC) 2 − 341.7pH × ISModel
− 115.4G2 − 60.2G4 − 183.9G5 + 2.4CS+B −25.5pH
81CSMo×+TOC 0.06CS+ 21.5t × IS + 9.3t × TOC − 211.6G1
Si ± [286.4]
cB = c−5155B = −5155 + 35.6t −
+ 35.6t −549.7TOC
549.7TOC
− 115.4G2 −− 74.7(TOC)
− 60.2G474.7(TOC)
− 183.9G5 2 2
−− + 341.7pH
341.7pH
2.4CSB×− IS ×+IS
81CS ++25.5pH
25.5pH
Mo × TOC
0.06CS Si×±+ 21.5t+× 21.5t
TOC
[286.4] × IS
IS + 9.3t + 9.3t− ×
× TOC 211.6G1
TOC − 211.6G1− 115.4G2 − 115.4G2 − −60.2G4
60.2G4 183.9G5++2.4CS
−− 183.9G5 2.4CS − 81CS
B −B81CS Mo + 0.06CS
Mo + 0.06CS Si ± [286.4]
Si ± [286.4]
c’B = −35.6t − 549.7TOC − 74.7 (TOC) − 341.7pH × IS + 25.5pH × TOC + 21.5t × IS + 9.3t × TOC
2
c’B = −35.6t − 549.7TOC − 74.7 (TOC)2 − 341.7pH × IS + 25.5pH × TOC + 21.5t × IS + 9.3t × TOC
R2 c’ = −35.6t −0.90 549.7TOC − 74.7 (TOC) 2Residual
− 341.7pH analysis
× IS + 25.5pH × TOC + 21.5t × IS + 9.3t × TOC
R2 B = −35.6t − 549.7TOC
c’B0.90 − 74.7 Residual
(TOC) 2 − 341.7pH
analysis × IS + 25.5pH × TOC + 21.5t × IS + 9.3t × TOC
p 22 <0.000001
p R R 0.90
<0.000001 0.90 Residual analysis
a 0.0888
a pp <0.000001
0.0888<0.000001
α = arctan (a) 5.1°
aa
α = arctan
Pearson
(a) 5.1° 0.0888
0.30 0.0888
Pearson α = arctan (a) 0.30 5.1° ◦
α ==60arctan
cmin (t °C) (a) 1238 ppb 5.1
cmin (tPearson
= 60 °C) 0.30
1238 ppb Residual analysis
Pearson
cmax (t = 60 °C) 1967 ppb 0.30
cmax (tc=min60(t°C)= 60 °C) 1967 ppb 1238 ppb
cmin (t
cmin= 80(t°C) = 60 ◦ C)2181 ppb 1238 ppb
cmin (tc=max80(t°C) = 60 °C)2181 ppb 1967 ppb
cmax (t = 80 °C) 3159 ppb 1967 ppb
==80
◦ C)
cmax c(tmax
c=min80(t
(t°C) 60°C) 2181 ppb
3159 ppb
cB—concentration of boron in leachates; rA-residual in residual analysis; a—directional coefficient; arctan-
cmin
ccmax (t(t == 80
B—concentration
◦ C)
80°C) 3159
of 2181
boronppbinppb
leachates; rA-residual in residual
arcus tangent which is equal to angle between regression line analysis;
in residual a—directional
analysis andcoefficient; arctan-
0x axis; Pearson-
cmaxarcus (t =
Pearson
c 80
tangent
B ◦
—concentration
correlation
of
C)whichcoefficient
is3159
equalboron
ppb
to in leachates;
forangle
rA and between rA-residual inline
cB; c’minregression
residual analysis;
(t = 60 °C); c’min(tin=residual
a—directional
80 °C); c’analysis
coefficient;
and 0x axis; Pearson-
max(t = 60 °C); c’max(t = 80 °C)—
arctan-
Pearson
cB —concentration arcus tangent
correlation which is
coefficient equal
for r to angle
and c ; between
c’ (t = 60regression
°C); c’ (tline
= 80 in residual
°C); c’ (t =analysis
60 °C); and
c’ 0x
(t = axis;
80 Pearson-
°C)—
explained of boron
before in leachates;
Table 5; CSB, CSMor,ACS A -residual
Si- B, Mo,in
B min
Si residual
concentrationsanalysis;
min a—directional
in shale max
sample. coefficient; arctan-arcus
max
tangent which explainedisPearson

equal correlation
before
to 5; coefficient
Tablebetween
angle Mo, for
CSB, CSregression rAB,
CSSi- and Mo,
linecB;Si
c’min
in (t = 60 °C);
concentrations
residual c’min
analysisin(tshale
= 80 °C);
and c’max(t
sample.
0x axis; = 60 °C); c’max(t = 80
Pearson-Pearson °C)—
correlation
min (t = 60 ◦5; , CS(tMo=, CS
80Si-◦ C); = 60 ◦ C); c’max = 80sample.
coefficient for rAexplained and cB ; c’before Table C);CSc’Bmin B, Mo,
c’maxSi(tconcentrations in(tshale ◦ C)—explained before Table 5;
CSB , CSMo , CSSi- B, Mo, Si concentrations in shale sample.

Energies 2019, 12, 1404 9 of 21

Table 6. Results of leaching samples A1 to A10 rocks using fluids P1 to P13 for Barium (Ba).
Energies 2018, 11 FOR
Table PEER REVIEW
6. Results of leaching samples A1 to A10 rocks using fluids P1 to P13 for Barium (Ba). 9
Table 6. Results of leaching samples A1 to A10 rocks using fluids P1 to P13 for Barium (Ba).
Ba concentrations in in
Ba concentrations samples
samplesafter
afterleaching
leaching of A1
of A1totoA10
A10 rocks using fluids P1P13
to P13
Table 6. Results of leaching samples A1 to A10 rocks usingrocks
fluidsusing
P1 tofluids P1Barium
P13 for to (Ba).
Ba concentrations in samples after leaching of A1 to A10 rocks using fluids P1 to P13
Ba concentrations in samples after leaching of A1 to A10 rocks using fluids P1 to P13
Model
cBa = 1664 – 1792pH + 122pH2 + 43.8TOC2 + 157.7pH × IS − 3.14t × TOC − 48.73G2 − 118.41G3 − 271Aw − 0.44CSBa+
cBa = 1664 – 1792pH + 122pH2 + 43.8TOC 2 + 157.7pH ×Model
34.44CSLi + 0.276CSIS − 3.14t × TOC − 48.73G2 − 118.41G3 − 271Aw − 0.44CSBa+
Model
Mg + 0.00071CSCa ± [168]
c
cBaBa = 1664 – 1792pH + 122pH
2 2 + 43.8TOC
34.44CS2 Li + 2 + 157.7pH
= 1664 – 1792pH + 122pH + 43.8TOC + 157.7pH × IS+−0.00071CS
0.276CS Mg × ×ISTOC
3.14t ±−[168]
−Ca3.14t × TOC− −
48.73G2 − 118.41G3
48.73G2− 271Aw
118.41G3 − Ba+
− 0.44CS
c’Ba =−−1792pH
271Aw 0.44CSBa++ 34.44CS
34.44CS Li + Mg
Li + 20.276CS
122pH 0.276CS
+ 43.8TOC Mg +Ca
+2 0.00071CS
+ 157.7pH 0.00071CS
× ±IS[168]
− 3.14t Ca ± [168]
× TOC
c’Ba = −1792pH + 122pH2 + 43.8TOC2 + 157.7pH × IS − 3.14t × TOC
R2 0.90 Residual2analysis
R2 0.90c’Ba = −1792pH
c’Ba = −1792pH + 122pH
+ 122pH+2 +43.8TOC
2
Residual 2+
43.8TOCanalysis 157.7pH× ×
+ 157.7pH ISIS − 3.14t
− 3.14t × TOC× TOC
p <0.000001
pR2 R2 <0.000001
0.90 0.90 Residual analysis
a 0.061
ap p
α = arctan (a) <0.000001 <0.000001
0.061
3.5°
αa= arctan
a (a) 3.5°
0.061 0.061
Pearson 0.28
Pearson (a) 0.28
c'α = (tarctan
min α = arctan (a)
= 60°C) 3.5°
−6741 3.5◦
c'Pearson
min (t = 60°C) −6741
0.28
c'maxPearson
(t = 60°C) −5524 0.28 Residual analysis
c'c'
max
min(t(t= =60°C)
60°C) −5524−6741
c'min (t = 80°C) −6898
c'c' c’
(t min (t = 60 −6898
= 80°C)
◦ C) −6741
(t(t= =80°C)
60°C) −5524
min
max
c'max −5527
c'c' c’
(t
min (t
max =
max (t
80°C)
= 80°C)= 60 ◦ C)
−5527
−6898 −5524
cBa—concentration◦ of barium in leachates; rA—residual; a—directional coefficient, arctan-arcus tangent; Pearson-
c’min
c'max
cPearson (t = 80 C)
(t = 80°C)
Ba—concentration barium−6898
−5527
ofcoefficient
infor
leachates;
correlation rA and crBA; —residual;
c’min(t = 60 °C); a—directional coefficient,
c’min(t = 80 °C); c’max(t =arctan-arcus
60 °C); c’max(ttangent;
= 80 °C)—Pearson-
c’
Pearson (t = 80
maxcorrelation
◦ C) −5527
coefficient
cBa—concentration
explained before Table 5; CSBa, for
of barium in rA and cB; rc’
CSleachates;
Li, CSMg, CS
min(t = 60 °C);
—residual;
ACa -Ba, Li, Mg, c’minconcentrations
(t = 80 °C);
a—directional
Ca c’maxin(t shale
coefficient, = 60 °C); c’max(t =tangent;
arctan-arcus
sample 80 °C)—Pearson-
explained
cPearson before Table
Ba —concentration
correlation CSBa, CS
of5;barium
coefficient Li, rCS
in
for A Mg, CS
and cB;Cac’-Ba,
leachates; Li, Mg,
rA(t—residual;
min = 60 Cac’concentrations
°C); (t = 80 °C); c’in
a—directional
min max shale
(t = 60sample
coefficient, arctan-arcus
°C); c’ max(t = 80 °C)— tangent;
Pearson-Pearson correlation coefficient for r A and c B ; c’min (t = 60 ◦ C); c’
explained before Table 5; CSBa, CSLi, CSMg, CSCa-Ba, Li, Mg, Ca concentrations in shale sample min (t = 80 ◦ C); c’
max (t = 60 ◦ C); c’
max (t =
80 ◦ C)—explained before Table 5; CSBa , CSLi , CSMg , CSCa -Ba, Li, Mg, Ca concentrations in shale sample.
Energies 2019, 12, 1404 10 of 21

Table 7. Results of leaching samples A1 to A10 rocks using fluids P1 to P13 for Strontium (Sr).
Energies 2018, 11 FOR
Table PEER REVIEW
7. Results of leaching samples A1 to A10 rocks using fluids P1 to P13 for Strontium (Sr). 10
SrTable 7. Results of
concentration inleaching
samplessamples A1 to A10
after leaching of rocks
A1 tousing
A10 fluids
rocks P1 to P13
using for Strontium
fluids P1 to P13(Sr).
TableSr7.concentration in samples
Results of leaching afterA1
samples leaching
to A10 of A1 to
rocks A10fluids
using rocks P1
using fluids
to P13 for P1 to P13 (Sr).
Strontium
Sr concentration in samples after leaching of A1 to A10 rocks using fluids P1 to P13
Sr concentration in samples after leaching of A1 to A10 rocks using fluids P1 to P13
cSr = 11995 − 4001pH + 273.6pH2 + 12.1TOC2 + 2.2pHModel × Model

t − 4.8pH × TOC − 7t × IS − 72.4IS × TOC + 40.2G2 + 25.6G5 +
cSr = 11995 − 4001pH + 273.6pH 2 + 12.1TOC2 + 2.2pH ×Model
129.1Aw + 1.11CSBa − 0.1CSt Mg − 4.8pH × TOC
− 0.005CS − 7t × SrIS±−[134.6]
Si + 1.5CS 72.4IS × TOC + 40.2G2 + 25.6G5 +
Sr==11995 + 273.6pH 2 + 12.1TOC +×2.2pH + +
cSr 11995 − 4001pH
− 4001pH 129.1Aw
+ 273.6pH + 1.11CS
2 + 12.1TOC 2 + Ba − 20.1CS
2.2pH t Mg × t ×−TOC
− 0.005CS
− 4.8pH 4.8pH
Si + − 7t××TOC
1.5CS − 7t ×× TOC
IS±−[134.6]
Sr 72.4IS IS − 72.4IS × +TOC
+ 40.2G2 25.6G5
40.2G2 + 25.6G5 + 129.1Aw
129.1Aw + + 1.11CS
1.11CS Ba − 0.1CS
2 Ba −Mg0.1CS
− 0.005CS
Mg −
Si 0.005CS
+ 1.5CS Sr ±
Si
c’Sr = −4001pH + 273.6pH + 12.1TOC + 2.2pH × t − 4.8pH × TOC − 7t × IS − 72.4IS × TOC
2 + 1.5CS
[134.6] Sr ± [134.6]
R2 c’Sr =0.95
−4001pH + 273.6pH2 + 12.1TOCResidual 2 + 2.2pH × t − 4.8pH × TOC − 7t × IS − 72.4IS × TOC
= −4001pH + 2 + 12.1TOC2 + 2.2pH ×analysis

Rp 2 c’ Sr c’Sr =0.95 273.6pH
−4001pH + 273.6pH + 12.1TOC Residual
<0.000001
2 2 ×tt −
+ 2.2pH analysis 4.8pH××TOC
− 4.8pH TOC − ×7tIS×−IS
− 7t − 72.4IS
72.4IS × TOC× TOC
R 2 0.95
Rp a
2 0.95
<0.000001
0.046 Residual analysis
paα
p = arctan (a) 0.046
2.6° <0.000001
<0.000001
aα
a = arctan (a)
Pearson 0.046
2.6°
0.24 0.046
α = arctan
(t = 60(a)
Pearson 2.6°
0.24
α = arctan (a)
c'min °C) −13910 ppb◦
2.6
Pearson
c'
c' min (t = 60 °C)
max (t = 60 °C)
0.24
−13910
−12700 ppb
ppb
Pearson 0.24 Residual analysis
c'
c'min (t = 80 °C)◦ −13670 ppb
c' max (t
min (t == 60
60 °C)
°C) −13910
−12700 ppb
ppb
c’min
c'
c'maxmin(t (t
= 60= 60 C)−13670 ppb
80 °C) −12700
−13910
ppb
c'max (t = 80 °C) −12310 ppb ppb
c'min (t = 80 °C) −13670 ppb
cc'
Sr
max (t = 80 °C)◦
max (t = 60 C)
c’—concentration
−12310 ppb in leachates; rA—residual; a-directional coefficient; arctan-arcus tangent; Pearson-
of strontium
−12700
c'Srmax
cPearson (t = correlation
80 °C) −12310
—concentration ppb forinrAleachates;
ofcoefficient
strontium and cB; c’minrA—residual;
(t = 60 °C); c’a-directional
min(t = 80 °C);coefficient;
c’max (t = 60 arctan-arcus tangent;
°C); c’max(t = 80 Pearson-
°C)—explained
ppb
cPearson correlation
—concentration
before ofcoefficient
strontium for
inr and c
leachates;
A B ; c’ r
min (t = 60
—residual;°C); c’ (t = 80
a-directional
min °C); c’ (t =
coefficient;
max 60 °C); c’ (t
arctan-arcus
max = 80 °C)—explained
tangent; Pearson-
c’min Table C)Ba, CSLi, CS
5; ◦CS Mg, CSCa—Ba, Li, Mg, Ca concentrations in shale sample
Sr A
(t = 80 −13670
before
Pearson Table 5; CSBa,coefficient
correlation CSLi, CSMgfor
, CSrCa
A —Ba,
and cBLi,
; c’Mg,
min(t Ca= 60concentrations
°C); c’min(t = 80in°C);
shale sample
c’max (t = 60 °C); c’max(t = 80 °C)—explained
ppb
before Table 5; CSBa, CSLi, CSMg, CSCa—Ba, Li, Mg, Ca concentrations in shale sample
c’max (t = 80 ◦ C) −12310
ppb
cSr —concentration of strontium in leachates; rA —residual; a-directional coefficient; arctan-arcus tangent;
Pearson-Pearson correlation coefficient for rA and cB ; c’min (t = 60 ◦ C); c’min (t = 80 ◦ C); c’max (t = 60 ◦ C); c’max (t = 80
◦ C)—explained before Table 5; CS , CS , CS
Ba Li Mg , CSCa —Ba, Li, Mg, Ca concentrations in shale sample.
Energies 2019, 12, 1404 11 of 21

Table 8. Results of leaching samples A1 to A10 rocks using fluids P1 to P13 for Molybdenum (Mo).
EnergiesTable 8. FOR
2018, 11 Results
PEERof REVIEW
leaching samples A1 to A10 rocks using fluids P1 to P13 for Molybdenum (Mo). 11
Table 8. Results of leaching
Mo concentrations samples
in samples A1 to
after A10 rocks
leaching of using
A1 tofluids P1 to P13
A10 rocks forfluids
using Molybdenum (Mo).
P1 to P13
Mo concentrations in samples after leaching of A1 to A10 rocks using fluids P1 to P13
Table
Mo8.concentrations
Results of leaching samples
in samples A1leaching
after to A10 rocks
of A1using fluids
to A10 P1using
rocks to P13 for Molybdenum
fluids P1 to P13 (Mo).
Mo concentrations in samples after leaching of A1 to A10 rocks using fluids P1 to P13
cMo = −1002.7 + 37.82t − 15576IS + 207.9TOC + 17.68pHModel 2Model

− 4.05pH × t + 145.83pH × IS − 3.59t × TOC + 166.94IS × TOC
cMo = −1002.7 + 37.82t − 15576IS + 207.9TOC
+ 3.82G4 + 17.68pH
+ 2.41G5 − 0.38CS−BModel
2
+4.05pH
10.19CS × tMo+ −145.83pH
0.22CSSr ±× [32.7]
IS − 3.59t × TOC + 166.94IS × TOC
cMo = −1002.7 + 37.82t+ − 15576IS
3.82G4 + 207.9TOC
+ 2.41G5 − 0.38CS+ B2 +17.68pH
2
10.19CSMo−− 4.05pH
0.22CSSr × t + 145.83pH × IS − 3.59t ×
± [32.7]
cMo = −1002.7 + 37.82t − 15576IS + 207.9TOC + 17.68pH − 4.05pH × t + 145.83pH × IS − 3.59t × TOC + 166.94IS × TOC
TOC + 166.94IS × TOC + 3.82G4 + 2.41G5 − 0.38CS B + 10.19CS Mo − 0.22CSSr ± [32.7]
c’Mo = 37.82t − 15576IS + 207.9TOC 17.68pH−20.38CS
+ 3.82G4 + 2.41G5 − 4.05pH × t + 145.83pH
B + 10.19CS × IS Sr− ±3.59t
Mo − 0.22CS × TOC + 166.94IS × TOC
[32.7]
R2 c’ Mo = 37.82t − 15576IS
0.91 + 207.9TOC + 17.68pH 2 − 4.05pH × t + 145.83pH × IS − 3.59t × TOC + 166.94IS × TOC
Residual analysis
Rp2
c’Mo = 37.82t − 15576IS + 207.9TOC + 17.68pH 2 4.05pH × t + 145.83pH × IS − 3.59t × TOC +
−analysis
c’Mo = 37.82t0.91
<0.000001
− 15576IS + 207.9TOC + 17.68pH Residual
2 − 4.05pH
166.94IS × t + 145.83pH × IS − 3.59t × TOC + 166.94IS × TOC
× TOC
p
aR2 <0.000001
0.069
2
R 0.91
aα p= arctan (a) 0.069
4.0°
<0.000001
α = p
arctan (a) 4.0° <0.000001
Pearson
a 0.29
0.069
α =a(tarctan
Pearson
c'min = 60 °C) (a) 0.29
1069
4.0° 0.069
c'
c'min (t
α
(t
Pearson
max =
= = 6060 °C)
arctan
°C) 1069
(a)
1695
0.29 4.0◦
c'
c'max (t(t== =80
(t
Pearson
c'min
min
6060°C)
°C)
°C) 1695
1342
1069 0.29 Residual analysis
c'
c'min (t == 80 °C)
°C) 1342
c’min (t = 60 C)
(t (t
c'max
max =8060
°C) 1431
◦ 1695 1069
c'max
c'min(t(t= =8080°C) 1431
c’max (t °C)
= 60 ◦ C)1342 1695
cMoc'-concentration of
max (t = 80 °C) ◦ 1431 molybdenum in leachates; rA—residual; a-directional coefficient; arctan-arcus tangent; Pearson-
cPearsonc’min
Mo-concentration(t =
correlation coefficient1342
80 of C)molybdenum for rin leachates; rA—residual; a-directional coefficient; arctan-arcus tangent; Pearson-
A and cB; c’min(t = 60 °C); c’min(t = 80 °C); c’max(t = 60 °C); c’max(t =80 °C)—explained
Pearson
before c’Table
max (t5;
cMo-concentration =CS
correlation ◦ coefficient
80B, of
C)molybdenum
CS for r
1431 Mo,
Mo, CSSr—Ba,
A andSrcBconcentrations
; c’min(t = 60 °C);
in leachates; in c’
rA—residual;
min(t = 80 °C); c’max(t = 60 °C); c’max(t =80 °C)—explained
shale sample coefficient; arctan-arcus tangent; Pearson-
a-directional
before Table 5;
cMo -concentration CS B, CS Mo, CS Sr—Ba, Mo, Sr concentrations in shale sample
Pearson correlation of molybdenum
coefficient for rA in
andleachates;
cB; c’min(t r=A60
—residual;
°C); c’min(ta-directional
= 80 °C); c’maxcoefficient;
(t = 60 °C); arctan-arcus tangent;
c’max(t =80 °C)—explained
Pearson-Pearson correlation coefficient for rA and cB ; c’min (t = 60 ◦ C); c’min (t = 80 ◦ C); c’max (t = 60 ◦ C);
before Table ◦5; CSB, CSMo, CSSr—Ba, Mo, Sr concentrations in shale sample
c’max (t = 80 C)—explained before Table 5; CSB , CSMo , CSSr —Ba, Mo, Sr concentrations in shale sample.
Energies 2019, 12, 1404 12 of 21

Table 9. Results of leaching samples A1 to A10 rocks using fluids P1 to P13 for Rubidium (Rb).
Table
Energies 2018, 9. Results
11 FOR of leaching samples A1 to A10 rocks using fluids P1 to P13 for Rubidium (Rb).
PEER REVIEW
Rb concentrations in in
samples
12
Rb concentrations samplesafter
afterleaching of A1
leaching of A1totoA10
A10rocks
rocks using
using fluids
fluids P1P13
P1 to to P13
Rb concentrations in samples after leaching of A1 to A10 rocks using fluids P1 to P13
Rb concentrations in samples after leaching of A1 to A10 rocks using fluids P1 to P13
cRb = −77.42 + 1.05t + 462.79 IS + 27.92 pH × IS − 6.49t

Model× IS − 21.88IS × TOC − 0.42G2 + 0.024CSRb ± [18.71]
Model
cRb = −77.42 + 1.05t + 462.79 IS + 27.92 pH × IS − 6.49t × IS − 21.88IS × TOC − 0.42G2 + 0.024CSRb ± [18.71]
cRb = −77.42 + 1.05t + 462.79
c’Rb = 1.05t IS + 27.92
+ 462.79IS pH ×× IS
Model
+ 27.92pH IS − 6.49t××ISIS
− 6.49t − 21.88IS
− 21.88IS × TOC − 0.42G2 +
× TOC
R2 cRb = −77.42 + 0.86
1.05t + c’
462.79 IS ++27.92
Rb = 1.05t pH 0.024CS
462.79IS ×+ IS Rb ××±IS
− 6.49t
Residual
27.92pH IS[18.71]
−−analysis
21.88IS
6.49t × IS× −TOC − 0.42G2
21.88IS × TOC+ 0.024CSRb ± [18.71]
Rp2 <0.000001
=Rb1.05t
c’Rb c’ + 462.79IS
= 1.05t + 462.79IS++27.92pH
27.92pH ××ISIS− − 6.49t
6.49t ×−IS21.88IS
× IS − 21.88IS × TOC
× TOC
a
p 0.102
<0.000001
R2 (a)
Raα2 = arctan 0.86
5.8°
0.102 0.86 Residual analysis
pα p
Pearson
= arctan (a) <0.000001
0.31
5.8° <0.000001
aPearson
c'min a(t = 60 °C) 0.102
125.9
0.31 0.102
αc'=minarctan
(t = (a) 5.8°
maxα = 60 °C)
arctan (a) 227.5
125.9 5.8◦
Pearson
min (t = 80
c'max 60 °C) 0.31
80.6
227.5
c'c'min (t = 60 °C)
max (t = 80 °C)
min
125.9
182.2
80.6
c'c'max c’
(t(tmin
==60 (t = 60 C)◦ 125.9
cmax 80°C)
°C)
Rb-concentration
227.5
182.2
c’ (t = 60 ◦of
C)
rubidium in leachates; rA—residual; a-directional coefficient; arctan-arcus tangent; Pearson-
227.5
c'min (t max = 80 °C) 80.6
cPearson correlation
Rb-concentration ofcoefficient
rubidium forin rleachates;
A and cB; c’ rmin (t = 60 °C); a-directional
A—residual; c’min(t = 80 °C);coefficient;
c’max(t = 60arctan-arcus
°C); c’max(t = 80 °C)—explained
tangent; Pearson-
max c’
c'before (t min 80(t°C)
= Table =5;80CSRb
◦ C)
182.2
,–Rb 80.6
concentrations
Pearson correlation coefficient for rA andincBshale sample
; c’min(t = 60 °C); c’min(t = 80 °C); c’max(t = 60 °C); c’max(t = 80 °C)—explained
cbeforec’max Table(t =5;80
Rb-concentration
◦ C)
CSof rubidium
Rb,–Rb 182.2
in leachates;
concentrations in shalerA—residual;
sample a-directional coefficient; arctan-arcus tangent; Pearson-
Pearson
cRb -concentration of rubidium in leachates; r=A60
correlation coefficient for r A and c B; c’min (t °C); c’min(t a-directional
—residual; = 80 °C); c’max(tcoefficient;
= 60 °C); c’max(t = 80 °C)—explained
arctan-arcus tangent;
Pearson-Pearson
before Table 5; CSRbcorrelation coefficient
,–Rb concentrations in for
shale and cB ; c’min (t = 60 ◦ C); c’min (t = 80 ◦ C); c’max (t = 60 ◦ C);
rAsample
c’max (t = 80 ◦ C)—explained before Table 5; CSRb ,–Rb concentrations in shale sample.
Energies 2019, 12, 1404 13 of 21

Table 10. Results of leaching samples A1 to A10 rocks using fluids P1 to P13 for Lithium (Li).
Energies 2018, Table
11 FOR10.
PEER REVIEW
Results of leaching samples A1 to A10 rocks using fluids P1 to P13 for Lithium (Li). 13
LiTable 10. Results in

concentrations of samples
leaching samples
after A1 to A10
leaching rocks
of A1 to using
A10 fluids using
rocks P1 to P13 for Lithium
fluids P1 (Li).
to P13
TableLi10.
concentrations in samples
Results of leaching afterA1
samples leaching
to A10 of A1 to
rocks A10fluids
using rocksP1using fluids
to P13 for P1 to P13(Li).
Lithium
Li concentrations in samples after leaching of A1 to A10 rocks using fluids P1 to P13
Li concentrations in samples after leaching of A1 to A10 rocks using fluids P1 to P13
cLi = 500.56 + 78.85pH + 150.00IS − 7.51pH2 + 0.38pH Model

× t − 2.50t × IS − 3.53IS × TOC − 3.03G1 + 1.23G4 − 1.73G5 +
Model
cLi = 500.56 + 78.85pH + 150.00IS − 7.51pH
0.41CS
2 + 0.38pH
Li − 0.0019CS
Model
× t − 2.50t
Si + 0.08CS × IS − 3.53IS
Sr − 0.0018CS Ca ± × TOC − 3.03G1 + 1.23G4 − 1.73G5 +
[10.66]
cLicLi = 500.56
= 500.56 + 78.85pH
+ 78.85pH + 150.00IS
+ 150.00IS − 7.51pH
0.41CS −0.0019CS
Li −
27.51pH
+ 0.38pH
2 + 0.38pH × t − 2.50t × IS − 3.53IS × TOC − 3.03G1 +
Si +×0.08CS
t − 2.50t × 0.0018CS
Sr − IS − 3.53IS Ca ×
± TOC − 3.03G1 + 1.23G4 − 1.73G5 +
[10.66]
1.23G4c’Li− =1.73G5 +
0.41CS0.41CS
Li − 0.0019CS
Li − 0.0019CS
Si + 0.08CS SiSr+
− 0.08CS
0.0018CS Sr −
Ca
78.85pH + 150.00IS − 7.51pH + 0.38pH × t − 2.50t × IS − 3.53IS
2 ±0.0018CS
[10.66] Ca ×±TOC
[10.66]
R 2 c’
0.88 Li = 78.85pH + 150.00IS − 7.51pH2 + 0.38pH × t − 2.50t × IS − 3.53IS × TOC
Residual analysis
Rp2
c’Li =c’78.85pH + 150.00IS − 7.51pH
Li = 78.85pH + 150.00IS − 7.51pH
0.88
2 + 0.38pH
2 + 0.38pH × ×
Residual
− 2.50t
t −t 2.50t
analysis × IS×−IS − 3.53IS
3.53IS × TOC × TOC
<0.000001
2
R2apR 0.88
<0.000001
0.082
pαap= arctan (a) 0.082 <0.000001
<0.000001
4.7
a Pearson
αa = arctan (a) 0.082
4.7 0.082
0.27
α c'
=min
αarctan
Pearson
=(tarctan
= 60(a)°C)
(a) 4.7
0.27 4.7
298.8
Pearson
c'max
c' min (t = 60 °C)
(t = 60 °C) 0.27
298.8
343.6
c'min
c' (t (t
c'min
max = =60
(t = 80
60°C)
°C)
°C) 298.8
343.6
341.6
c’
c'max min
(t(t
(t = 60 ◦ C) 298.8
c'max
c' min
(t= ==6080
80°C)°C) ◦ 343.6
°C) 341.6
371.4
c'minc’max
(t = 80(t
c'max (t = 80 °C)=
°C) 60 C)341.6 371.4 343.6
c’
c'cmax (t = 80
(t = 80 °C) of371.4
Li-concentration
min
◦ C)
lithium341.6 in leachates; rA—residual; a-directional coefficient; arctan-arcus tangent; Pearson-Pearson
ccorrelation
Li-concentration
80 C) lithium
c’max (t =coefficient ◦ of Ain leachates;
and
for r371.4 cB; c’minr(tA—residual;
= 60 °C); c’min a-directional
(t = 80 °C); coefficient;
c’max(t = 60 arctan-arcus
°C); c’max(t = tangent; Pearson-Pearson
80 °C)—explained before
cLiTable
-concentration
correlation
5; CSLi, CSSi,ofCSof
coefficientlithium for in
r
Sr, CSCa
leachates;
and c ; c’ r —residual;
A(t = 60 °C); a-directional
c’ (t = 80 coefficient;
°C); c’ (t = arctan-arcus
60 °C); c’ (t tangent;
= 80 Pearson-Pearson
°C)—explained before
in–Li, Si, Sr, Ca concentrations in shalecoefficient;
sample arctan-arcus tangent; Pearson-Pearson
A B min min max max
cLi -concentration lithium leachates; rA —residual; a-directional
correlation
Table 5; CS
correlation coefficient
, CSSi, CSfor
Licoefficient Sr,for
CS and
rArCa
A
–Li,
and c ;
BSi,
c c’
B
Sr,
;min
c’ (t
Ca
min
=(t60
= °C);
60 c’
concentrations
◦ C);min
c’ (t
min
= 80
in
(t °C);
shale
= 80 c’
sample
◦ C);
max (t
c’ =
max
60
(t °C);
= 60 ◦c’ (t
maxc’
C); =
max
80
(t °C)—explained
= 80 before
◦ C)—explained
Table
before5; CS Li, CS
Table , CS
5;SiCS , ,CS
LiSr CSSiCa –Li,
, CS Sr ,Si,
CSSr,Ca Ca–Li,concentrations in shale sample
Si, Sr, Ca concentrations in shale sample.
Energies 2019, 12, 1404 14 of 21

Energies 2018, 11 FOR PEER REVIEW
Table 11. Results of leaching samples A1 to A10 rocks using fluids P1 to P13 for Calcium (Ca). 14
Energies 2018,Table
11 FOR PEER
11. REVIEW
Results of leaching samples A1 to A10 rocks using fluids P1 to P13 for Calcium (Ca). 14
CaTable 11. Results of

concentrations in leaching
samplessamples A1 to A10
after leaching of rocks
A1 tousing
A10 fluids
rocks P1 to P13
using for Calcium
fluids (Ca).
P1 to P13
TableCa
11.concentrations in samples
Results of leaching after
samples A1leaching of A1 using
to A10 rocks to A10fluids
rocksP1
using fluids
to P13 P1 to P13(Ca).
for Calcium
Ca concentrations in samples after leaching of A1 to A10 rocks using fluids P1 to P13
Ca concentrations in samples after leaching of A1 to A10 rocks using fluids P1 to P13
cCa = 1000(3749.56 − 553.95pH − 52.84t + 799.88IS − Model Model+ 39.86TOC2 + 7.84pH × t − 322.63IS × TOC − 1.12G2 −
83TOC
cCa = 1000(3749.56 − 553.95pH − 52.84t + 799.88IS − Model
83TOC
0.05CSBa − 0.09CSSr + 0.000553CS+ 39.86TOC 2 + 7.84pH × t − 322.63IS × TOC − 1.12G2 −
Ca ± [27.07])
Ca==1000(3749.56
cCa 1000(3749.56 − 553.95pH
− 553.95pH − 52.84t
− 52.84t +0.09CS
+ 799.88IS
0.05CS Ba − 799.88IS
− 83TOC − +83TOC
39.86TOC
Sr + 0.000553CS +Ca 39.86TOC
± [27.07]) × +
2 + 7.84pH 2 322.63IS×× tTOC
t −7.84pH − 322.63IS
− 1.12G2×−
TOC − 1.12G2 − 0.05CS
0.05CS Ba − 0.09CS
Ba − Sr0.09CS
+ + 0.000553CS
0.000553CS
Sr Ca ± [27.07]) Ca ± [27.07])
c’Ca = 1000(−553.95pH − 52.84t + 799.88IS − 83TOC + 39.86TOC + 7.84pH × t − 322.63IS × TOC)
2
R2 c’Ca = 1000(−553.95pH
0.90 − 52.84t + 799.88ISResidual− 83TOCanalysis
+ 39.86TOC2 + 7.84pH × t − 322.63IS × TOC)
c’ = 1000(−553.95pH − 52.84t + 799.88IS
+ 799.88IS−Residual
−83TOC ++39.86TOC
39.86TOC 2 + 7.84pH × t − 322.63IS × TOC)
Rp2 Ca c’Ca = 1000(−553.95pH
0.90
<0.000001
− 52.84t 83TOC analysis 2 + 7.84pH × t − 322.63IS × TOC)
R2pR2 0.90
<0.000001 0.90 Residual analysis
a 0.080
pap
α = arctan (a) 0.080 <0.000001
<0.000001
4.6°
a αa = arctan (a) 0.080 4.6° 0.080
Pearson 0.29
αPearson
= arctan (a) 4.6°
0.29
=(tarctan
c'αmin = 60 °C)(a) −3897280 4.6◦
Pearson
c' min (t = 60 °C) 0.29
−3897280
c'Pearson
max (t = 60 °C) −3527670 0.29 Residual analysis
c'c'
min (t(t= =6060°C)
max °C)◦ −3897280
−3527670
c'min (t = 80 °C) −3836130
c’min
c'c' (t =°C)60 C) −3897280
min(t(t==60 −3527670
(t = 80
80 °C) −3836130
max
c'max °C)◦ −3172780
c’max
c'c'
min (t(t= (t
max =°C)
=8080 60
°C) C)−3836130
−3172780 −3527670
cCa(t
—concentration of calcium in leachates; rA—residual; a-directional coefficient; arctan-arcus tangent; Pearson-
c’
c'max min=(t80=°C) 80 ◦ C)
−3172780 −3836130
cCa—concentration
Pearson correlation of calcium for
coefficient in leachates;
rA and cB; c’rAmin
—residual;
( t= 60 °C); a-directional
c’min(t = 80 °C);coefficient;
c’max(t = 60arctan-arcus tangent;
°C); c’max(t = 80 Pearson-
°C)—explained
cc’
Ca max
Pearson (t =
—concentration80 ◦ C) ofcoefficient
correlation −3172780
calcium inforleachates;
r and c ;rA—residual;
c’ ( t= 60 a-directional
°C); c’ (t = 80 coefficient;
°C); c’ (t = arctan-arcus
60 °C); c’ (t =tangent;
80 Pearson-
°C)—explained
before Table 5; CSBa, CSCa, CSSr-Ba, Ca, Sr concentrations in shale sample
A B min min max max
cCa —concentration
Pearson
before correlation
Table of
, CScalcium
5; CSBacoefficient for
Ca, CSSr in
-Ba, leachates;
rACa,
and ; c’min(rt=
A —residual;
SrcBconcentrations
60 °C);inc’min (ta-directional
shale 80 °C); c’maxcoefficient;
= sample arctan-arcus
(t = 60 °C); c’max tangent;
(t = 80 °C)—explained
Pearson-Pearson
before Table 5; CS correlation coefficient for rA and cB ; c’in
Ba, CSCa, CSSr-Ba, Ca, Sr concentrations
(t = 60
minshale
◦ C); c’
sample min (t = 80 C); c’max (t = 60 C); c’max (t
◦ ◦
= 80 ◦ C)—explained before Table 5; CSBa , CSCa , CSSr -Ba, Ca, Sr concentrations in shale sample.
Energies 2019, 12, 1404 15 of 21

Energies2018,
Energies 2018,1111FOR
FORPEER
PEERREVIEW
REVIEW 1515
Table 12. Results of leaching samples A1 to A10 rocks using fluids P1 to P13 for Magnesium (Mg).
Table 12. Results of leaching samples A1 to A10 rocks using fluids P1 to P13 for Magnesium (Mg).
Table12.
Table 12.Results
Resultsofofleaching
leachingsamples
samplesA1
A1totoA10
A10rocks
rocksusing
usingfluids
fluidsP1
P1totoP13
P13for
forMagnesium
Magnesium(Mg).
(Mg).
Mg concentrations in samples after leaching of A1 to A10 rocks using fluids P1 to P13
Mg concentrations in samples after leaching of A1 to A10 rocks using fluids P1 to P13
Mgconcentrations
Mg concentrationsininsamples
samplesafter
afterleaching
leachingofofA1
A1totoA10
A10rocks
rocksusing
usingfluids
fluidsP1
P1totoP13
P13
Model
Model
Model
cMg = −16117 − 8518pH + 1756.39t − 21296IS + 35845TOC Model
+ 3511.7TOC22 2+ 30118pH × IS − 726.9t × TOC − 294G2 − 775G3
cMg==−16117
cMg −16117−−8518pH
8518pH++1756.39t
1756.39t−−21296IS
21296IS++35845TOC
35845TOC++3511.7TOC
3511.7TOC ++30118pH
30118pH××ISIS−−726.9t
726.9t××TOC
TOC−−294G2
294G2−−775G3
775G3
− 459Aw − 8.2CSBa + 1.6009CSMg − 0.1145CSSi ± [2311]
cMg = −16117 − 8518pH + 1756.39t
−−459Aw
459Aw 8.2CSBaBa+++1.6009CS
−−21296IS
−8.2CS 35845TOC
1.6009CS Mg−−+
Mg 3511.7TOC
0.1145CS
0.1145CS
2 + 30118pH × IS − 726.9t ×
SiSi±±[2311]
[2311]
TOC − 294G2 − 775G3 − 459Aw − 8.2CSBa + 1.6009CSMg − 0.1145CSSi ± [2311]
cMg = −8518pH + 1756.39t − 21296IS + 35845TOC + 3511.7TOC22 2+ 30118pH × IS − 726.9t × TOC
cMg==−8518pH
cMg −8518pH++1756.39t
1756.39t−−21296IS
21296IS++35845TOC
35845TOC++3511.7TOC
3511.7TOC ++30118pH
30118pH××ISIS−−726.9t
726.9t××TOC
TOC
cMg = −8518pH + 1756.39t − 21296IS + 35845TOC + 3511.7TOC2 + 30118pH × IS − 726.9t × TOC
R 2
2 22
RR 0.920.92
0.92 Residualanalysis
Residual analysis
p <0.000001
ppp <0.000001
<0.000001
<0.000001
a 0.079
aa 0.079
0.079
αa = arctan (a) 4.5°0.079
αα==arctan
arctan(a) (a) 4.5° ◦
4.5°
α
Pearson= arctan (a) 0.284.5
Pearson
Pearson 0.28
0.28
c'Pearson
min (t = 60 °C) 0.28
26676 Residual analysis
c'c'min
min(t(t==6060°C)
°C) 26676
26676
c'c’maxmin
c'c'max
(t (t =6060
= 60
max(t(t==60
°C)◦ C)
°C)
°C)
57888
26676
57888
57888
c'c’min (t =(t80 = °C)
60 ◦ 30668
max
c'c'min
min(t(t==80 °C) C)
80°C) 57888
30668
30668
c'max (t = 80 °C)◦ 92144
c'c’
c'max
min
max(t(t(t
= ==80
80 80°C)
°C) C) 30668
92144
92144
c
c’ Mg—concentration ◦ of
(t = 80 C) ofofmagnesium magnesium
92144 in leachates; rA—residual; a-directional coefficient; arctan-arcus tangent; Pearson-
cMgcmax
Mg —concentration
—concentration magnesium ininleachates;
leachates;rArA—residu
—residual;al;a-directional
a-directionalcoefficient
coefficient ; ;arctan-arcus
arctan-arcustangent;
tangent;Pearson-
Pearson-
cMgPearson correlation
—concentration coefficient for r A and cB; c’min(t = 60 °C); c’min(t = 80 °C); c’max(t = 60 °C); c’max(t = 80 °C)—explained
Pearson
Pearson correlationof
correlation magnesium
coefficient
coefficient forforrArin leachates;
and
Aand cBc;Bc’
; c’min
min r=A=60
(t(t —residual;
60°C);
°C);c’c’min
min(ta-directional
(t==80
80°C); coefficient;
°C);c’c’max(t(t==60
max °C);c’arctan-arcus
60°C); c’max(t(t==80
max tangent;
80°C)—explained
°C)—explained
before Table 5; CS
Pearson-Pearson Ba, CSMg, CS
correlation Si -Ba, Mg,
coefficient forSirAconcentrations
and cB ; c’min (t in = 60
shale ◦ C); c’min (t = 80 ◦ C); c’max (t = 60 ◦ C); c’max (t = 80
sample
beforeTable
before
◦ C)—explained Table5;5;CSCSBaBa, ,CS
CSMgMg, ,CS
CSSiSi-Ba,
-Ba,Mg,Mg,SiSi concentrations
concentrations ininshale
shalesample
sample
before Table 5; CSBa , CSMg , CSSi -Ba, Mg, Si concentrations in shale sample.
Energies 2019, 12, 1404 16 of 21

Energies Table
2018, 1113.
FORResults of leaching
PEER REVIEW samples A1 to A10 rocks using fluids P1 to P13 for Silicon (Si). 16
Table 13.
Table 13. Results
Results of
of leaching
leaching samples
samples A1A1 to
to A10
A10 rocks
rocks using
using fluids
fluids P1
P1 to
to P13
P13 for
for Silicon
Silicon (Si).
(Si).
Si concentrations
Table 13. Results inleaching
of samples after leaching
samples A1 to A10ofrocks
A1 to A10fluids
using rocksP1using
to P13fluids
for P1 to(Si).
Silicon P13
Si concentrations
Si concentrations in in samples
samples after
after leaching
leaching of
of A1
A1 to
to A10
A10 rocks
rocks using
using fluids
fluids P1
P1 to
to P13
P13
Si concentrations in samples after leaching of A1 to A10 rocks using fluids P1 to P13
Model
Model
Model
cSi = −298621 + 9229pH − 35067IS − 6556pH + 457TOC2 −− 338pH
c Si = −298621 + 9229pH − 35067IS − 6556pH22 + 457TOC 338pH ×× TOC
TOC ++ 324t
324t ×× IS
IS −− 151.6G1
151.6G1 −− 68G5
68G5 ++ 0.0555CS
0.0555CSSiSi ±±
2
Model
cSi =cSi = −298621
−298621 + 9229pH
+ 9229pH − 35067IS − 35067IS 457TOC2 +
− 6556pH−2 +6556pH
2 [2312]
457TOC
−[2312]
338pH
2 − 338pH × TOC + 324t × IS − 151.6G1 −
× TOC + 324t × IS − 151.6G1 − 68G5 + 0.0555CSSi ±
68G5 + 0.0555CS
[2312] Si ± [2312]
c Si = 92297pH − 35067IS − 6556pH22 + 457TOC22 − 338pH × TOC + 324t × IS
cSi = 92297pH − 35067IS − 6556pH
cSi =cSi92297pH 2 ++457TOC
457TOC2 − 338pH × TOC + 324t × IS
RR22 0.96
= 0.96
92297pH − 35067IS
− 35067IS−− 6556pH 2Residual
6556pHResidual
+ 457TOC − 338pH
analysis
2 − 338pH
analysis × TOC + 324t+× 324t
× TOC IS × IS
2
R2 ppR 0.96
<0.000001
0.96<0.000001 Residual analysis
p aap <0.000001
0.049
<0.000001
0.049
a ααa== arctan
arctan (a) (a) 2.8°
0.049
2.8°0.049
Pearson
α =Pearson
arctan (a) 0.30 ◦
2.8°0.30
α = arctan (a) 2.8
c'min
Pearson
c' min (t = 60 °C)
(t = 60 °C) 286589
0.30
286589
c'
c'min
c'maxmax=(t
(t (t60== °C)
60 °C)
60 °C) 316728
286589
316728
c’min
c'
c'max min
(t =(t 60
(t
= = 60
80
°C) °C)
◦ C) 286589
289889
316728
c'min (t = 80 °C) 289889
c'c’max
c'min max
(t
max (t80=(t
=(t = °C)
= °C)
80 60 ◦ C) 316728
320028
289889
c' 80 °C) 320028
c'maxc’(tmin = 80 ◦ C) 320028
(t °C)
= 80 289889
c Si—concentration of silicon in leachates; rA-residual; a—directional coefficient; arctan-arcus tangent; Pearson-
cc’Si—concentration of silicon in leachates; rA-residual; a—directional coefficient; arctan-arcus tangent; Pearson-
max (t =
◦
80 C) coefficient 320028
Pearson correlation
cSi—concentration
Pearson of silicon
correlation in leachates;
coefficient for and rccABB;-residual;
for rrAA and ; c’
c’min
min(t = 60 °C); c’
c’min
min(t = 80coefficient;
(t = 60a—directional
°C); °C); c’
(t = 80 °C); c’max
max(t = 60 °C);
°C); c’
c’max
(t =arctan-arcus
60 max(t
== 80
80 °C)—explained
°C)—explained
(ttangent; Pearson-
cSi —concentration
before Table 5;
5; CS
CS of siliconSr in–Ba,
B, CSMo, CS
leachates;
Mo, Sr r -residual; in
concentrations a—directional coefficient; arctan-arcus tangent;
Pearson
before correlation
Table coefficient
B, CSMo, CS for
Sr rA andMo,
–Ba, cB; c’Sr min (t =A 60 °C); c’minin
concentrations =shale
(t shale sample
80◦ °C); c’max(t = 60 ◦°C); c’max(t = 80 °C)—explained
sample
Pearson-Pearson correlation coefficient for rA and cB ; c’min (t = 60 C); c’min (t = 80 C); c’max (t = 60 C); c’max (t = ◦
before Table 5; CSB, CS
80 ◦ C)—explained
To derive Mo, CS
before
general Sr
Table –Ba,
5; CSMo,
equations, SrMo
B , CS
the concentrations
,entire
CSSr –Ba, Mo,inSrshale
available datasample
concentrations in shale
set for fluid sample. as well as rocks was
variables
To derive general equations, the entire available data set for fluid variables as well as rocks was
analyzed.
To derive
analyzed. Nine
Nine general
general
general equations
equations,
equations describing
thedescribing the shale
entire available
the shale
datarock
rock leaching
setleaching with
for fluidwith modelasfracturing
variables
model fracturing fluids
well as rocks
fluids were
was
were
To derive
obtained.
analyzed. general
For
Nine all
general equations,
equations, the
equations the entire available
determination
describing the shale dataleaching
coefficient
rock set forare
values fluid
in
with variables
the range
model as well
from
fracturing 0.86 as
to
fluids rocks
0.96.
were was
This
obtained. For all equations, the determination coefficient values are in the range from 0.86 to 0.96. This
analyzed.
means
obtained.Nine
For general
that equations
theequations,
all presented model
the describing
matches are
determination the
are ofshale rock leaching
are in with
high significance.
coefficientsignificance.
values model
the range fromfracturing fluids
0.86 to 0.96. Thiswere
means that the presented model matches of high
obtained. For
It
means that was all
the equations,
assumed
presented that the
model determination
correctly performed
matches are of coefficient
regression
high values
allows
significance. to are
obtainin the
a range
graph
It was assumed that correctly performed regression allows to obtain a graph of residues from of from
residues 0.86
fromtoreal
0.96.
real
values
This means
It was in
that the
the
assumedform of
that points
presented approximately
model
correctly matches
performed arranged
are of
regressionhigh on both sides
significance.
allows to obtain of
a a straight
graph of
values in the form of points approximately arranged on both sides of a straight line parallel to the line
residuesparallel
from to
real the
values
It wasinassumed
the formthat of points approximately
correctly performedarranged
regression onallows
both sides of a straight
to obtain a graphline parallel to
of residues the real
from
values in the form of points approximately arranged on both sides of a straight line parallel to the
Energies 2019, 12, 1404 17 of 21
abscissa, which represents the actual values. As an approximation, a straight line with the inclination
angle of less than 22.5◦ was drawn, since the position of the points on both sides of the line inclined
to abscissa at an angle of 45◦ means that a sufficient number of variables were not included in the
description of the model.
Pearson correlation coefficients between laboratory data and residuals (difference between
laboratory and model data) were lower than 0.5 (and higher than 0.5), which means that residuals
are poorly correlated with the result. Residual analysis gives information that the applied variables
describe the model in the tested range well enough and sufficiently. Moreover, no correlation occurrence
between residuals and measured values means that there are probably no methodological errors.
Table 14. Possible range of selected elements decreased in flowback fluid.
Concentration Operating Range (ppb) Analysed Concentration Range in MFF (ppb)

Model
60 ◦ C 80 ◦ C min max
B 729 978 371 6044
Ba 1217 1371 25 4219
Sr 1210 1360 125 2687
Mo 626 89 25 760
Rb 101.6 101.6 25 249
Li 44.8 29.8 25 186
Ca 369608 663354 130 417450
Mg 31212 61476 4316 38782
Si 30139 30139 250 64153
For the obtained models it was calculated that appropriate control of the fracturing fluid parameters
can significantly reduce the amount of leached contaminants (Table 14). The maximum value of possible
changes in fixed temperature was named Concentration Operating Range (abr. COR). Concentration
range (min/max) in MFF (min/max) are given as minimum and maximum values of components
concentrations in analysed fluids after leaching tests. For boron, the possibility of lowering the
concentration in flowback fluid is over 10 to almost 15% at 80 ◦ C, while for lithium it is from 16 to
24% and for barium over 25%. Considerably greater COR was calculated for strontium, rubidium and
silica, about 50%, for calcium and magnesium, so it is theoretically possible to select the parameters of
the fluid giving no leaching of a given element. The biggest dependence on temperature was observed
for molybdenum where at 60 ◦ C the concentration could be increased by about 10% whereas at 80 ◦ C
by 80%. This is a direct argument that such a model development approach is justified and has a
potential for practical use. Similar research needs to be continued and more advanced models should
be developed according to scheme presented in Figure 3. Such models using data from many different
reservoirs, evaluated and improved using field data, could have important impact on designing
the flowback treatment technologies immediately after drilling. However using only fast and easy
procedures of rock analysis is crucial for this approach.
Energies 2019, 12, 1404 18 of 21
Figure 3. Possible directions of further studies on the development of proposed model.

Figure 3. Possible directions of further studies on the development of proposed model.
4. Conclusions
4. Conclusions
The The
results of mineralogical
results of mineralogical andand elemental
elemental analysis
analysisas aswell
wellasasthethedetermination
determinationofoforganic organiccarbon
carbon
in the
in the studied shale rock samples from various sections of the horizontal section of the explorationwell,
studied shale rock samples from various sections of the horizontal section of the exploration well,
indicate highhigh
indicate heterogeneity
heterogeneity of the deposit
of the deposit at aatmacroscopic
a macroscopic scale.
scale.AA high
high divergence
divergenceininthe thecomposition
composition
made it possible
made to make
it possible a model
to make with awith
a model widearange
wideofrange
applications. Unfortunately,
of applications. in the shale
Unfortunately, in systems,
the shale
a high heterogeneity of the mineral and elemental composition along
systems, a high heterogeneity of the mineral and elemental composition along the created fracturesthe created fractures may occur.
Thismaycan occur.
strongly This limit
can the presented
strongly limit theandpresented
other models and always
and other models has and to be considered
always before its
has to be considered
application as a developed industry tool. Nevertheless, using cross-sectional
before its application as a developed industry tool. Nevertheless, using cross-sectional samples samples from whole
from
fractured parts of the wellbore deliver the most technical/economical
whole fractured parts of the wellbore deliver the most technical/economical possible approximations possible approximations of the
shaleofcomposition in a chosen
the shale composition inpart of thepart
a chosen reservoir.
of the reservoir.
For For
the the
model, fracturing fluid-shale
model, fracturing fluid-shale rock, rock, mathematical
mathematical relationships
relationships based
based onon T,T,ionic
ionicstrength,
strength,
TOC, pH pH
TOC, of fracturing
of fracturing fluid andand
fluid elemental
elemental composition,
composition,mineralogical
mineralogical composition,
composition, andandsurface areaarea
surface of
shale rock were derived. This approach allows one to predict the concentration
of shale rock were derived. This approach allows one to predict the concentration of selected metals of selected metals in a
wide range of variables. Nine equations were obtained, the coefficient
in a wide range of variables. Nine equations were obtained, the coefficient of determination over of determination over 0.85 was
obtained
0.85 wasfor obtained
the wholefor setthe
with
wholeconfidence
set withlevel above level
confidence 0.99. above
For chosen
0.99. Formodel the standard
chosen model thedeviation
standard
wasdeviation
always the lowest among other taken into consideration and its value
was always the lowest among other taken into consideration and its value justifies the justifies the correctness of
application of R 2 as a crucial parameter 2 to choose most adequate
correctness of application of R as a crucial parameter to choose most adequate model. Residual model. Residual analysis gives
information that applied
analysis gives informationvariables describes
that applied the model
variables in the the
describes tested
model range welltested
in the enough. range Moreover,
well enough.no
correlation between residuals and measured values means that there
Moreover, no correlation between residuals and measured values means that there are probably no are probably no methodological
errors. Selected parameters
methodological errors. of the model
Selected fracturingoffluid
parameters and rock
the model properties
fracturing are and
fluid sufficient to predict the
rock properties are
composition of the flowback fluid in the laboratory system. In the next research
sufficient to predict the composition of the flowback fluid in the laboratory system. In the next research other shale rock samples
should
otherbeshale
testedrock andsamples
data from analysis
should of flowback
be tested and datafluid for attempts
from analysis of to flowback
develop industrial version of
fluid for attempts to
the model
develop need to be carried.
industrial version of the model need to be carried.
Unfortunately,
Unfortunately, a comparison
a comparison with other
with models
other modelsin in
thethe
literature
literature is is
notnotpossible
possibledue duetotounnormalized
unnormalized
character off the data and a lack of model description from other
character off the data and a lack of model description from other sources. However, sources. However, the presented paper
the presented
maypaper
become may a significant contribution
become a significant in the modelling
contribution development
in the modelling approach approach
development in the shales leaching
in the shales
systems. Test results can be a good basis for developing a commercial tool
leaching systems. Test results can be a good basis for developing a commercial tool for predicting the for predicting the treatment
fluidtreatment
at the designfluidstage
at theofdesign
hydraulic
stagefracturing.
of hydraulic fracturing.
Author Contributions: Conceptualization, A.R.; Data curation, A.R.; Formal analysis, A.R.; Funding acquisition,
Author Contributions: Conceptualization, A.R.; Data curation, A.R.; Formal analysis, A.R.; Funding acquisition,
A.R.;A.R.;
Investigation, A.R.;
Investigation, Methodology,
A.R.; Methodology, A.R.; Project
A.R.; administration,
Project administration, J.H.;
J.H.;Resources,
Resources,J.H.;
J.H.;Software,
Software,A.R.;
A.R.;
Validation, K.K. and J.H.; Visualization, A.R.; Writing-original draft, A.R.; Writing-review & editing,
Validation, K.K. and J.H.; Visualization, A.R.; Writing-original draft, A.R.; Writing-review & editing,K.K. and
K.K. J.H.
and J.H.
Funding: This This
Funding: research received
research no external
received funding
no external funding.
Conflicts
Conflicts The The
of Interest:
of Interest: authors
authors declare
declare no conflict
no conflict of interest.
of interest.
Energies 2019, 12, 1404 19 of 21
Appendix A
Table A1. Detailed results of XRD analysis of shales samples.
No. Shale Mineral (%)

Sample
Quarz Alb Micr Ort Calc Dol Pir Bar Chl Ill Mon Kao Mus Bio Par Gla
A1 15.89 2.93 1.58 1.10 9.38 2.56 6.70 2.43 4.75 1.10 0.00 9.38 38.29 0.36 2.56 0.98
A2 21.58 1.83 1.10 0.74 2.93 0.74 0.00 0.08 7.19 0.74 0.00 2.81 57.48 1.58 0.61 0.61
A3 12.74 2.07 2.68 0.61 28.67 8.53 0.00 0.12 3.77 0.48 10.73 5.85 18.64 2.93 1.83 0.36
A4 19.58 3.10 5.08 0.37 21.52 3.97 0.00 0.25 7.81 8.80 0.00 1.86 2.61 22.81 1.11 1.11
A5 23.73 0.98 0.86 0.37 22.81 4.80 0.00 0.12 9.34 2.83 0.12 11.55 19.17 0.62 0.86 1.85
A6 22.57 3.44 2.59 0.74 13.05 30.67 1.73 0.12 4.06 1.73 0.00 0.37 13.29 0.24 3.32 2.09
A7 13.60 2.70 3.19 0.12 12.86 33.97 0.12 0.12 5.03 3.19 0.24 0.36 17.27 4.53 0.50 2.20
A8 25.66 4.16 2.08 0.62 8.44 16.50 0.00 0.12 4.88 0.74 0.00 0.36 33.76 0.48 1.72 0.48
A9 34.97 6.67 3.52 1.00 9.17 11.19 0.76 0.12 5.04 2.13 0.00 2.13 5.53 3.77 1.51 12.47
A10 21.81 2.18 1.09 0.48 9.82 12.13 0.12 0.00 7.52 0.48 0.00 1.21 41.45 0.36 0.97 0.36
Alb—albite, Micr—microclase, Ort—orthoclase, Calc—calcite, Dol—dolomite, Pir—pyrite, Bar-barite, Chl—chlorite, Ill—illite, Mon—montmorillonite, Kao—kalonite, Mus—muscovite,
Bio—biotite, Par—paragonite, Gla—glaukonite
Energies 2019, 12, 1404 20 of 21
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energies

Keywords: fracturing fluid; flowback fluid; leaching; solid-liquid extraction

Energies 2019, 12, 1404; doi:10.3390/en12071404 www.mdpi.com/journal/energies

Fracturing Fluid Flowback Fluid

2. Materials and Methods

2.3. Shale Samples Analysis

2.4. Preparation of Model Fracturing Fluids

2.5. Leaching Tests

t (◦ C) pH IS (mol/L) TOC (g/L)

3. Results and Discussion

No. of Element Concentration in the Shale Sample (CS) (ppm) Aw TOCS

Group of Minerals (%)

tangent which explainedisPearson

CSB , CSMo , CSSi- B, Mo, Si concentrations in shale sample.

Energies 2018, 11 FOR PEER REVIEW 9

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cSr = 11995 − 4001pH + 273.6pH2 + 12.1TOC2 + 2.2pHModel × Model

= −4001pH + 2 + 12.1TOC2 + 2.2pH ×analysis

Energies 2018, 11 FOR PEER REVIEW 11

Mo concentrations in samples after leaching of A1 to A10 rocks using fluids P1 to P13

cMo = −1002.7 + 37.82t − 15576IS + 207.9TOC + 17.68pHModel 2Model

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Rb concentrations in samples after leaching of A1 to A10 rocks using fluids P1 to P13

cRb = −77.42 + 1.05t + 462.79 IS + 27.92 pH × IS − 6.49t

Energies 2018, 11 FOR PEER REVIEW 13

LiTable 10. Results in

cLi = 500.56 + 78.85pH + 150.00IS − 7.51pH2 + 0.38pH Model

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CaTable 11. Results of

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Table 14. Possible range of selected elements decreased in flowback fluid.

Concentration Operating Range (ppb) Analysed Concentration Range in MFF (ppb)

Figure 3. Possible directions of further studies on the development of proposed model.

Table A1. Detailed results of XRD analysis of shales samples.

No. Shale Mineral (%)

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