energies

Review
Produced Water Treatment and Valorization:
A Techno-Economical Review
Ramon Sanchez-Rosario and Zacariah L. Hildenbrand *

Department of Chemistry and Biochemistry, The University of Texas at El Paso, 500 W. University Ave,
El Paso, TX 79968, USA; [email protected]
* Correspondence: [email protected]

Abstract: In recent years, environmental concerns have urged companies in the energy sector to
modify their industrial activities to facilitate greater environmental stewardship. For example, the
practice of unconventional oil and gas extraction has drawn the ire of regulators and various environ-
mental groups due to its reliance on millions of barrels of fresh water—which is generally drawn from
natural sources and public water supplies—for hydraulic fracturing well stimulation. Additionally,
this process generates two substantial waste streams, which are collectively characterized as flowback
and produced water. Whereas flowback water is comprised of various chemical additives that are
used during hydraulic fracturing; produced water is a complex mixture of microbiota, inorganic and
organic constituents derived from the petroliferous strata. This review will discuss the obstacles of
managing and treating flowback and produced waters, concentrating on the hardest constituents to
remove by current technologies and their effect on the environment if left untreated. Additionally,
this work will address the opportunities associated with repurposing produced water for various
applications as an alternative to subsurface injection, which has a number of environmental concerns.
This review also uses lithium to evaluate the feasibility of extracting valuable metals from produced
water using commercially available technologies.

Citation: Sanchez-Rosario, R.;

Keywords: produced water; hydraulic fracturing; shale energy; water treatment
Hildenbrand, Z.L. Produced Water
Treatment and Valorization: A
Techno-Economical Review. Energies
2022, 15, 4619. https://doi.org/
10.3390/en15134619
1. Introduction
Flowback-produced water (FP) is a waste fluid associated with hydraulic fracturing in
Academic Editors: Giorgio Bertanza
unconventional oil and gas development (UOG). Initially, FP reflects the composition of
and Sergey Zhironkin
the hydraulic fracturing fluid, which is referred as flowback water (FBW). After the initial
Received: 4 May 2022 months of well production, the waste fluid is predominantly representative of the formation
Accepted: 21 June 2022 and is known as produced water (PW) [1]. PW is primarily ancient groundwater which has
Published: 24 June 2022 been reacting with minerals, gases, and organic matter in the subsurface for thousands to
Publisher’s Note: MDPI stays neutral millions of years and contains most naturally occurring elements. The composition of FP
with regard to jurisdictional claims in is highly variable with respect to inorganic, organic, and biological constituents. In fact,
published maps and institutional affil- several studies have revealed that the relative abundance of certain elements and organic
iations. compounds found in FP is a reflection of where the respective production well is located
as well as the geological formation from which the fluid is derived [2–5]. Nevertheless,
extremely high levels of sodium (Na) and chlorine (Cl) ions are distinctive characteristics of
these brines. For example, studies have reported concentrations of 54,000 and 138,000 parts
Copyright: © 2022 by the authors. per million (ppm) in Permian Basin [6]. Naturally occurring radioactive materials (NORM)
Licensee MDPI, Basel, Switzerland. are within the inorganic species found in FP [7] in addition to iron (Fe), magnesium
This article is an open access article (Mg), strontium (Sr), calcium (Ca) and several other metal and nonmetal monoatomic
distributed under the terms and
and/or polyatomic species [8–11]. Some studies have reported significant concentrations of
conditions of the Creative Commons
radium isotopes [11,12] as well as trace levels of radionuclides of cesium, lead, plutonium,
Attribution (CC BY) license (https://
polonium, strontium, thorium and uranium in FP [13,14].
creativecommons.org/licenses/by/
4.0/).

Energies 2022, 15, 4619. https://doi.org/10.3390/en15134619 https://www.mdpi.com/journal/energies

Energies 2022, 15, 4619 2 of 18

The organic constituents found in FP can be classified in three major categories:

aliphatics, aromatics and drilling additives [15]. Aliphatics involve small-chain hydrocar-
bons (found in petroleum), alkylethoxylates [16], long-chain fatty acids and heterocyclic
compounds [17]. Alkyl halides and amines have also been reported [18]. Examples of
the aromatics in FP include polycyclic aromatic hydrocarbons (PAHs), xylenes, phenols
and alkyl benzenes [16–19]. Additionally, a wide range of other unknown volatile or
semivolatile compounds can be present in PW [20,21].
Chemical additives can be further divided into three major types: alcohols, biocides
and surfactants. Chen and Carter have suggested that the most common alcohols present
in wells are ethanol, isopropanol, methanol and propargyl alcohol [22]. Other reported
alcohols are phenols, ethylene glycol, and ethoxylated and tertbutyl alcohol, which serve
as solvents and surfactants and also inhibit corrosion in tubing and equipment [23]. Chen
and Carter also stated that “almost all of the added alcohols are considered to be toxic
chemicals”. Additionally, biocides are added in hydraulic fracturing fluid to control the
proliferation of bacteria in the formation of interest. These chaotropic agents function
by reacting with some functional groups in membrane proteins and damaging cell walls,
by disulfide bond cleavage and by inhibiting metabolic processes in microorganisms [24].
Some commonly used biocides include glutaraldehyde, quaternary ammonium compounds
(QACs), sodium hypochlorite, tetrakishydroxymethylprosphonium sulfate (THPS), various
brominated compounds, Tributyltetradecylphosphonium chloride dibromonitrilopropi-
onamide and a combination of 2-methyl-3(2H)-isothiazolone and 5-chloro-2-methyl-3(2H)-
isothiazolone. The biodegradability of these compounds varies from rapidly biodegradable
(i.e., THPS) to environmentally persistent (i.e., QACs) [17,22,23,25,26]. Lastly, surfactants
control the viscosity of fracturing liquids and increase fluid recovery. As many as 84 exam-
ples of these have been found in HF fluids [26]. For instance, some common surfactants
include alcohol ethoxylates (AEOs), alkylphenol ethoxylates (APEOs), ethoxylated alcohols
and phenols, cocamide compounds, sodium lauryl sulfate and dimethyl dihydrogenated
tallow ammonium chloride (DHTDMA) [22,23,25].
The biogeochemical richness of PW can often provide an optimal environment for the
proliferation of a vast range of microorganisms. Examples of these range from strictly aero-
bic to anaerobic microbes, including sulfate-reducing bacteria (SRB), iron-oxidizing bacteria
(IRB), acid-producing bacteria (APB), sulfur-oxidizing bacteria (SOB) and extremophiles.
The presence of SRB (e.g., desulfomicrobium, desulfovibrio, desulfohalubium, desulfobacter) may
lead to souring of natural gas, whereas IRB (e.g., desulfuromusa, pelobacter, malonomonas,
desulfuromonas) cause corrosion in metal infrastructure [27,28]. APB (e.g., halanaerobium)
generate metabolites that could affect the integrity of grout and the casing of wells [29]. A
recent study indicated that SOB (e.g., Acidithiobacillus caldus, A. thiooxidans and A. albertensis)
promote corrosion in carbon steel by triggering the oxidation of sulfur compounds to sulfate
and ultimately generating sulfuric acid [27]. Lastly, extremophiles can withstand extreme
conditions, such as very high or low pH or temperature, high salinity, and oil-bearing strata,
making them especially persistent. In a previous study, biocide resistance was exhibited
in microorganisms such as Arcobacter sp. and Pseudomonas balearica [30]. Other undesired
bacteria found in PW include Marinobacterium sp., which—under aerobic conditions—can
metabolize aliphatic and aromatic compounds for energy harvesting [31], as well as the
fungus Syncephalastrum racemosum, which degrades hydrocarbons in soil [32]. Also present
in these brines is the gas-souring Shewanella [33]. By contrast, Thermoanaerobacter exhibits
anticorrosive properties through the reduction of thiosulfate to elemental sulfur [34], which
might be of benefit to the oil and gas industry.
Numerous analytical techniques are required to comprehensively characterize the
chemical profile of FP. For example, gas chromatography coupled with mass spectrometry
(GC-MS) and liquid chromatography–mass spectrometry (LC-MS) is utilized to detect
and quantify the presence of volatile and semi-volatile organic compounds. Additionally,
LC-MS is applied for untargeted analysis of constituents yet to be identified. Inductively
coupled plasma-optical emission spectrometry (ICP-OES) and/or inductively coupled
Energies 2022, 15, 4619 3 of 18

plasma mass spectrometry (ICP-MS) facilitate the analysis of metal and nonmetal ions [5].
In particular, ion chromatography (IC) is the “go-to” method for pertinent anions (i.e., chlo-
ride, sulfate, sulfide, nitrate, bromide). Methods for the characterization and quantitation
of microbial constituents include aerobic and anaerobic plate count (i.e., selective, and non-
selective media), Gram staining, microscopy, and molecular methods (i.e., immunological-
and nucleic-acid-based techniques). Common molecular methods include polymerase
chain reaction (PCR) and DNA sequencing [35]. Analysis of protein profiles by matrix-
assisted laser desorption ionization–time-of-flight-mass spectrometry (MALDI-TOF-MS)
is a relatively recent innovation that facilitates the rapid identification of microorganisms
compared to traditional methods [32]. Lastly, bulk water quality parameters, such as total
dissolved solids, total suspended solids, turbidity, organic and inorganic carbon content,
pH and oxidation reduction potential (ORP), are predominantly quantified through the use
of sensors, titration and gravimetric methods [20,36]. The use of these analytical techniques
in concert provides considerable insight into the complex composition of FP, which is
essential in developing and designing an effective treatment regimen.
Traditionally, large FP volumes are managed via disposal into the subsurface through
saltwater disposal wells (SWDs). This consists of transporting the waste fluid (i.e., trucking
or pipelines) to a designed site, where the fluid is pumped and sequestered into deep geo-
logic formations [37]. However, this practice comes with a series of environmental concerns.
For example, spills during the transport of FP to disposal sites can lead to groundwater and
surface water contamination. In 2017, a study modelled different spillage scenarios with
varying soil types, spill intensities and depth of ground water, concluding that benzene
and toluene—toxicity-inducing compounds—are the primary contaminants of concern [38].
Another study from 2019 reported an increase in bromide, radium, strontium, lithium and
boron downstream from a spill site in comparison to upstream, which translated into a
reduction in the growth of fish and the survival of mussels [39]. Additionally, spill events
can vary the concentration of ions and increase the total dissolved solids (TDS) in nearby
areas and natural water streams, respectively [40]. Overall, these are just a few examples of
the various threats to environment associated with the disposal of FP. Another key aspect
to consider is water management.
During the period from 2009 to 2017, a total of 11.43 billion barrels of water were used
for HF in the US, with the Permian Basin increasing its water intake by 1.26 billion barrels
since 2009. According to Scanlon et al., this represents 0.1% of the US water withdrawal in
2015 [41]. In 2017, Permian Basin reported an annual PW volume (106 ) of 1,663.21 barrels
(bbl) as well as a water demand for HF of (106 ) 1,322.26 bbl. By 2017, the Permian Basin had
an increment in PW volume approximately 20 times higher compared to 2011 [41,42]. In
view of this, the Permian region is a prime candidate to substantially benefit from recycling
PW, as it will reduce the demand of high volumes of fresh water, favoring the main urban
centers Lubbock and Midland-Odessa, with a total population of 466,200 individuals
(2010) [43]. In fact, far more FP is being produced than the required for HF, this could
be a major opportunity for the agricultural sector. For instance, from 2000–2014, 91% of
total water used in this area was destined for irrigation, followed by 6% for municipal
use and 2% for industry and livestock [43]. Another significant concern for residents in
shale regions is the increasing seismic events. Induced seismicity is a risk when injection is
performed into deep bedrock formations, as it may lubricate pre-existing geological faults
and provoke fault slips [44]. In 2020, Benson et al. concluded that extracting and injecting
fluids affects the natural seismicity of a given area. Furthermore, subsurface injection
has a particular association with earthquakes because it drives critically stressed faults to
failure by increasing pore pressure [45]. In recent years, seismicity rates have increased
12-fold since 2008 in West Texas [46]. Moreover, documented cases of induced earthquakes
have been observed in Canada, the United Kingdom, and China as well, with events of
up to 5.7 on the Richter scale [47]. For these reasons, the state of New Mexico no longer
grants permits for disposals as a preventative action that aims to decrease the occurrence
of seismicity in the area. Nevertheless, seismologists have difficulties in determining
Energies 2022, 15, 4619 4 of 18

exactly whether the earthquakes are naturally occurring, if they are caused by the hydraulic
fracturing processes or if they result from post-injection of wastewater.
Taken as a whole, the potential treatment and reuse of FP for HF would significantly
reduce the reliance on freshwater resource in shale energy regions, particularly in the
Bakken and Permian Basins, thus alleviating water stress in nearby communities and
retaining large volumes of water in the water cycle. Assuming that FP is treated to an
appropriate standard, a growing number of applications are available, such as agricultural
and surface water discharge, domestic usage and aquifer recharge. Ultimately, the fre-
quency of injection-well-induced earthquakes could be greatly attenuated by the utilization
of treated FP.
Current technologies applied in FP treatment include membrane and media filtration,
chemical oxidation and thermal and ion exchange methods. Typical setbacks for these
methods are membrane clogging, corrosion, high cost of chemicals, need of pre-treatment
and post-treatment, and solid separation [4]. Utilizing novel technologies in the treatment of
FP could reduce the negative impacts associated with SWDs, while making UOG operations
more sustainable and offering potential ancillary economic opportunities. For example, one
option for the industrial sector is the extraction of precious and semiprecious metals that are
in high demand, such as cobalt, nickel and particularly lithium. The mining and extraction
of precious metals found in FP represents a relatively unexplored opportunity for the energy
sector. This article reviews the current state of produced water characterization techniques
and treatment technologies. First, we discuss the efficacies of various treatment modalities
commonly used to remediate FP, including established and emerging technologies, and
how they are utilized to remove various classes of biogeochemical constituents found in FP.
Secondarily, we cover the costs of treatment and the options for extracting metals from FP
using Li extraction technologies and their associated costs as an example.

2. Challenges Associated with Produced Water Management

2.1. Technologies Utilized in Produced Water Treament
The major concern in treating FP for reuse, apart from the cost of treatment, is the
removal of pertinent constituents (see Table 1) that can negatively affect the production
of a given oil/gas well. For example, elevated levels Sr, Ca, Mg and Ba can contribute to
the formation of insoluble scales in production tubing, which can attenuate production
rates [48]. Elevated levels of sulfate can also contribute to scaling, as well as provide a
substrate for sulfate-reducing bacteria (SRB) to proliferate. Ultimately, this could lead to
the corrosion of tubing and, as a consequence, environmental contamination along with
the clogging of the wellbore, the degradation of hydrocarbons and the souring of natural
gas [16,17,25,32,49]. Additionally, significant concentrations of B and Fe (>10 mg/L) limit
effectiveness of cross-linkers polymerization in fracturing fluid [16,50]. Lastly, elevated
values of TOC, Na, Ca, Fe and phosphate reduce the viscosity of gel-based fracturing
fluids [48], which can have negative implications for production well stimulation.
The biogeochemical complexity of produced water requires the implementation of
multiple treatment modalities to effectively remove all the contaminants from microor-
ganisms and heavy metals to organic particulates and NORMs. The most widely utilized
procedures can be categorized as such: chemical oxidation, adsorption, membrane filtration,
electrocoagulation and distillations:
1. Chemical oxidation facilitates the flocculation of volatile and semi-volatile organics,
the precipitation of inorganic compounds, and the eradication of bacteria. Addi-
tionally, the use of oxidizing agents leads to the volatilization and remediation of
undesirable odors and colors, respectively. The oxidizing agents most commonly
used in FP treatment include ozone, hydrogen peroxide, chlorinated compounds and
permanganate [4]. Advanced oxidation processes (AOPs) comprise a set of chemical
treatments that remove organic matter by reaction and subsequent degradation with
a hydroxyl (OH) group. Furthermore, AOPs are thought to be environmentally sus-
tainable for chemical oxygen demand (COD) degradation [13]. Recent advances in
Energies 2022, 15, 4619 5 of 18

this technology involve the addition of nanoparticles to enhance the removal of major
organics from fracking wastewater [51].

Table 1. Inorganic constituents and other parameters of fracturing waste waters from Bakken Shale
and Permian Basin, the regulated concentration ranges for reuse in well stimulation [15] and in
agricultural and consumption use [52,53]. * represents the reported average of three measurements
in the study.

Permian Basin Agricultural Use Drinking Water

Bakken Shale Range Well Stimulation
Range (mg/L) (mg/L)
(mg/L) [13,40,54–57] (mg/L) [15]
(mg/L) [6,58,59] (EPA) (FAO & EPA)
METAL
Magnesium (Mg) 1530–3790 1630–1950 2000
Iron (Fe) 0.70–30.20 11 10.00 5.00 0.30
Manganese (Mn) 5.20–17.20 11.00–53.00 0.20 0.05
Aluminium (Al) <LOQ–8.30 5.00 0.05–0.20
Calcium (Ca) 13,140–41,160 10,000–15,000 2000
Sodium (Na) 89,100–189,000 48,000–54,000 69.00
Potassium (K) 3510–9530 570–1100
Barium (Ba) 6.40–26.30 0.00–16.00 20.00 2.00
Strontium (Sr) 709–2450 730.0–820.0
Cobalt (Co) 0.030–0.20 N/A 0.050
Nickel (Ni) <LOQ–3.80 0.020 0.20 0.07
Lithium (Li) 34.50–89.70 18.80 2.50
Chromium (Cr) 0.10 0.10
Radium 226 (Ra) 527.1–1211 pCi/L 5.000 pCi/L
Uranium (U) 30.00 µg/L
Copper (Cu) 4.60–16.90 0.20 1.00
Zinc (Zn) 2.50–10.10 2.00 5.00
Arsenic (As) 1.1 0.10 0.01
Beryllium (Be) 0.10 0.004
Lead (Pb) 0.00–3.50 5.00 0.015
Silver (Ag) 0.10
Molybdenum (Mo) 0.01
Cadmium (Cd) 0.001–0.031 0.01 0.005
Vanadium (V) 0.60–1.00 0.10
Thallium (Tl) 0.00–0.20 0.002
Antimony (Sb) 0.006
Rubidium (Rb) 0.30–12.90
Mercury (Hg) 0.002
NON-METAL
Chloride (Cl− ) 21,728–136,220 111,000–138,000 30,000–50,000 92.00 250.0
Bromide (Br− ) 91.6–558 1370–1650
Silicon (Si) 32 35.00
Fluoride (F− ) 1.00 4.00
Boron (B) 25.0–260.1 10.00 0.70
Selenium (Se) 0.10–1.00 0.02 0.05
POLYATOMIC IONS
2− 0.000–293.0 515–743 500 250
Sulfate SO4 )
Bicarbonate (HCO3 − ) 35.00–856.0 92–160 300 91.50
Nitrite (NO2 − ) 1.00
Nitrate (NO3 − ) 5.000 10.00
Phosphate (PO4 3 ) 584 *
Ammonium (NH4+ ) 44.8–2520 655
Cyanide (CN− ) 0.200
OTHER PARAMETERS
pH 4.1–7.2 7.30 6.0–8.0 6.5–8.4 6.5–8.5
TDS 128,300–388,600 174,213–212,984 450 500
TSS 7040 * 6850–21,820 500
Total nitrogen
TOC 311 * 86.25–184.21
Alkalinity (CaCO3 ) 0–562.8 2345
Turbidity (NTU) 13 53.4
DOC 80 * 63.45–145.71
Conductivity (mS/cm) 201.2
Nonvolatile dissolved organic
1.13–3.31
carbon (NVDOC)
Total Hardness
31,000–59,000
(mg/L CaCO3 )
Chemical Oxygen demand
20,000–79,000
(COD)
Energies 2022, 15, 4619 6 of 18

2. Adsorption is applied for the sequestration of organics and metal contaminants.

However, it is more of a polishing step for other preceding treatment modalities
instead of being a sole separation technique on its own. It is important to note
that the adsorption efficiency of various media is mediated by salinity. Activated
carbon media are effective for organic contaminants, whereas, activated zeolite is an
effective adsorbent for the removal of scaling ions such as Ca2+ and Mg2+ [60] that
are generally present in elevated concentrations in FP (see Table 1). Other possible
absorbents include alumina and organoclays [4]. In recent studies, Sun et al. achieved
the removal of several metal pollutants; for instance, Cu(ll), As(V), Cr (Vl), Cr(ll) and
Zn(ll) on Fe-impregnated biochar, a carbon-rich fine-grained pyrolysis residue [61].
3. Membrane filtration consists of the separation of a fluid from dissolved substances by
a porous surface. This includes reverse osmosis (RO), microfiltration (MF), nanofiltra-
tion (NF), ultrafiltration (UF) and forward osmosis (FO). RO removes solids by the
application of hydraulic pressure to move water molecules through a semi-permeable
membrane; MF allows the physical separation of suspended solids and turbidity
depletion via the retention of particles larger than the micropores in the membranes.
UF reduces odor, organic matter and color with pore membranes on the order of
microns. NF offers selective particle rejection based on size and charge, which lessens
multivalent ions, and FO lowers TDS in high-saline brines, benefiting from osmotic
pressure and transporting water molecules through a semipermeable membrane from
the less-concentrated feed to the highly concentrated solution [62]. Some modalities
could be applied as treatment technologies on their own, such as MF and UF; others
are steps in a more complex separation process. The obstacles to overcome include the
membrane fooling/clogging due to interactions with VOCs in NF/RO, fouling caused
by high Fe concentration in MF/UF, and scaling in RO [4,13,63,64] as well as RO’s
limitation to ionic strengths lower than that of sea water (approx. 40,000 ppm) [65].
4. Electrocoagulation (EC) promotes the precipitation of metals in the form of hydroxides
by the addition of direct current through a metal electrode. This has been shown
to be efficient and economically feasible for wastewater [66]. Previous studies have
demonstrated high removals of turbidity, COD, oils and greases by EC. For example,
Kausley et al. reported efficacy in the removal of total organic carbon (TOC) and
scaling-causing ions, particularly Ca2+ , Mg2+ , CO3 2− and HCO3 - , from synthetic PW
and PW [66,67]. The precipitation of metal cations in the form of hydroxides could
be further exploited to make the treatment of FP more economically viable to the
industrial sector through the generation and commercialization of Cu2+ , Mn2+ , Zn2+ ,
Al3+ , Fe3+ , Ni2+ , Mg2+ , Ca2+ , Na+ and several other metal hydroxides. Moreover, HCl
could be produced by hydrolysis of Cl2 gas generated during the process [67–70].
(Greater details will be discussed in subsequent sections of this review).
5. Distillation is a thermal process in which solid particles are separated from liquid
matrix by boiling point differences. One of the promising variations for brine desalina-
tion is multistage flash distillation (MSF). In MSF, the saline solution is converted into
a vapor state and then goes through successive units in which the solution evaporates
and condensates. In each unit, a fraction of the original feed remains as a highly
concentrated brine (see Figure 1) [62]. The technique produces high-quality fresh
water [71] and is efficient in the treatment of brackish/sea water. Nevertheless, for
future applications in PW treatment, it is suggested to pretreat the inlet water with
chemical softeners, filtrations and/or ion exchange technologies to avoid scaling and
fouling, as well as to upgrade the infrastructure material to stainless steel to prevent
corrosion [62]. The latter increases capital costs. Additionally, the salts produced
by this treatment modality can serve as a feedstock for electrocatalytic processes to
produce acids (HCl) and caustic agents (NaOH).
 fresh water [71] and is efficient in the treatment of brackish/sea water. Neverthe
for future applications in PW treatment, it is suggested to pretreat the inlet w
with chemical softeners, filtrations and/or ion exchange technologies to avoid sc
and fouling, as well as to upgrade the infrastructure material to stainless steel to
vent corrosion [62]. The latter increases capital costs. Additionally, the salts prod
Energies 2022, 15, 4619 by this treatment modality can serve as a feedstock for electrocatalytic
7 of 18 process
produce acids (HCl) and caustic agents (NaOH).

Figure 1. Schematics for multistage flash distillation (MSF). Extracted from Panagopoulos et al.,
Figure 1. Schematics for multistage flash distillation (MSF). Extracted from Panagopoulos et al.
2019 [62]. [62].

Many ongoing efforts for the treatment of FP incorporate separation and desalina-
Many ongoing efforts for the treatment of FP incorporate separation and desalin
tion [72]. Similarly, a common practice is the utilization of powdered activated carbon
[72]. Similarly, a common practice is the utilization of powdered activated carbon (P
(PAC) for the depletion of dissolved organic carbon (DOC), turbidity and organic compo-
for the depletion of dissolved organic carbon (DOC), turbidity and organic compon
nents. Other operations include softening hardness ions by the addition of caustic soda [54],
Other operations include softening hardness ions by the addition of caustic soda [54
demineralization through membrane distillation [73] and removal of organic components
mineralization through membrane distillation [73] and removal of organic compon
by coagulation followed by ultrafiltration [74]. Furthermore, biologically active membranes
by coagulation followed by ultrafiltration [74]. Furthermore, biologically active m
help remove organics and salinity [13]. The use of these techniques in tandem is generally
branes help remove organics and salinity [13]. The use of these techniques in tande
required to remediate FP to a reusable and/or recyclable standard.
generally required to remediate FP to a reusable and/or recyclable standard.
The commercial methods implemented in desalination of seawater, typically membrane-
The commercial
based and thermal-based [62], fail tomethods
meet the implemented
requirements for in desalination of seawater,
processing wastewater fromtypically m
brane-based and thermal-based [62], fail to meet the requirements
UOG. However, the elevated values of TDS (>50,000) in FP can lead to difficult scenarios for proce
when treating the approximately 250 million barrels produced globally each day [75]. ForFP can le
wastewater from UOG. However, the elevated values of TDS (>50,000) in
example, the difficult scenarios
FP in the Permianwhen treating
Basin has TDSthevalues
approximately
three to 250
five million barrelswhen
times higher produced glo
each day [75]. For example, the FP in the Permian Basin has TDS
compared to those of seawater (see Table 1) [76]. Common challenges include corrosion, values three to five t
higher when compared to those of seawater (see Table
fouling and scaling of the membrane when precipitation conditions are met [77].1) [76]. Common challenges inc
corrosion, fouling and scaling of the membrane when precipitation
Forward osmosis allows the separation of water from dissolved solids by employing conditions are
a semipermeable[77]. membrane and the difference in osmotic pressure as driving force. In
contrast to RO, it is believed to be more appropriate for high-TDS matrices, such as FP [78].
Additionally, FO is a cost-competitive and reliable alternative for wastewater treatment [79]
that exhibits great potential in removing heavy metal ions, including Cr2 O7 2− , HAsO4 2− ,
Pb2+ , Cd2+ , Cu2+ and Hg2+ [80].
A previous study suggested that reusing PW in the energy sector is a better option
than surface discharge due to safety concerns. Alternatively, its authors suggested thermal
distillation (TD) as the appropriate treatment modality [42]. Regardless of being one of
the most utilized operations for saline water recycling, TD’s energy consumption must be
addressed when treating PW since scaling may lead to a to insulation of heat exchangers
and, consequently, inefficient heat transfer. Again, the elevated price of anticorrosion
materials to build this facility should be considered, since high costs affect the feasibility at
an industrial scale. Similarly, osmotic properties constrain the application of membrane
technologies in highly saline brines [62].
Recent advances in membrane technology, as well as integration of existing procedures,
show promising results in processing high-TDS watersIn 2018, Sardari et al. demonstrated
that electrocoagulation (EC) pre-treatment followed by direct contact membrane (DCMD)
was effective in recovering up to 57% from a sample with a TDS of 135 g/L. However,
they suggested a reduction in the sedimentation time for practical applications [81]. Fur-
thermore, pretreatment with antiscalants such as 1-hydroxyethylidene-1,1-diphosphonic
acid (HEDP) increased the performance of carbon-nanotube-immobilized membranes in
membrane distillation (MD) [82]. Additionally, Ahmad et al. (2020) proposed a hybrid
technology that incorporates assisted reverse osmosis (ARO), microfiltration and reverse
osmosis—introduced as MF-ARO-RO—for which individual operations enhanced the abil-
 tions [81]. Furthermore, pretreatment with antiscalants such as 1-hydroxyethylidene-1,1-
diphosphonic acid (HEDP) increased the performance of carbon-nanotube-immobilized
membranes in membrane distillation (MD) [82]. Additionally, Ahmad et al. (2020) pro-
posed a hybrid technology that incorporates assisted reverse osmosis (ARO), microfiltra-
Energies 2022, 15, 4619 8 of 18
tion and reverse osmosis—introduced as MF-ARO-RO—for which individual operations
enhanced the ability to withstand different salinity effects and profiles. Although the ad-
dition of ARO to the MF-RO system represented an increase in the total cost, it was pre-
ity to withstand different salinity effects and profiles. Although the addition of ARO to the
sented as the cheapest alternative for high-salinity FP [83].
MF-RO system represented an increase in the total cost, it was presented as the cheapest
Recent studies developed a combined membrane system consisting of an electrodi-
alternative for high-salinity FP [83].
alysisRecent
chamber followed
studies developedby ananofiltration and membrane
combined membrane distillation
system consisting of an(ED-NF-MD),
electrodial- rep-
resented in Figure
ysis chamber followed2. The system facilitated
by nanofiltration zero liquid
and membrane discharge
distillation and allowed
(ED-NF-MD), rep-a water
recovery
resented inofFigure
up to 99.8%
2. The with
systemnofacilitated
need for chemical
zero liquidantiscalants
discharge and[84].allowed
Regardless
a waterof being a
laboratory-scale experiment,
recovery of up to 99.8% with nothe novel
need method antiscalants
for chemical has underlying
[84]. potential
Regardlessinofhigh-TDS
being wa-
a laboratory-scale
ters experiment,
treatment at industrial the novel method has underlying potential in high-TDS
scale.
waters treatment at industrial scale.

Figure 2. Diagram of the integrated ED-NF-MD system. CM: cation exchange membrane; AM: anion
exchange membrane; ED: electrodialysis; NF: nanofiltration; VMD: vacuum membrane distillation.
Reproduced with permission from Zhao et al., 2020 [84].

To summarize, the utilization of different adsorbents and novel materials to prevent

scaling and corrosion, as well as the tandem use of existing commercially available tech-
nologies, can facilitate the effective treatment of FP. Enhancement in the performance of
the more sophisticated methods can be achieved by pretreatment with the well-known
membrane filtrations.

2.2. Costs Associated with Produced Water Treatment

As previously mentioned, the efficacy of FP treatment is inherently important when
determining the terminal destination for the treated water. However, the more influential
aspect of assessing the feasibility and sustainability of FP reuse and/or recycling is oper-
ational cost. The cost of deep-well injections ranges from approximately USD $0.25/bbl
in private wells to approx. USD $0.50 to 2.50/bbl in commercial wells [85]. Adding the
price of transportation to disposal sites (approx. USD $0.03/bbl/mile) may increase the
cost significantly depending on the location of the storage [86]. In fact, transportation costs
can range from USD $2.00–20.00/bbl [87]. Moreover, these values are expected to become
higher due to distances of disposal sites possibly increasing. Additionally, permitting SWDs
is becoming more contentious because of earthquake issues could increase costs. On the
other hand, FP can also be transported via pipeline at an approximate cost of USD $0.25/bbl
(personal correspondence with water treatment provider), yet this requires considerable in-
frastructure that is generally not established in most shale energy basins. Typical treatment
Energies 2022, 15, 4619 9 of 18

costs range from USD $3.00 to $30.00/bbl, including storage and transport [88]. Recently,
MD modalities were studied for reuse waste waters of HF operations, resulting in costs
ranging from USD $0.11 to $0.90/bbl of treated fluid [89]. Operational costs of RO and FO
typically stand at USD ~$1.00/bbl. Providing an initial cost for the acquisition of these
membranes is challenging due to their performance dependency on influent TDS levels
and throughput requirements. In Table 2, the annual cost for FP disposal in Permian and
Bakken is compared to treatment costs, assuming treatment take place in situ based on
mobile treatment modalities.

Table 2. Annual cost for disposal and treatment of FP in Permian Basin and Bakken Shale, assuming
both are performed on-site. * Based on USD $0.03/bbl/mile trucking cost and an average distance of
20 miles from the source to the nearest disposal site.

Unit Bakken Region Permian Region Reference

Saltwater Disposal (SWD) cost
Disposal volume bbl/year 3.43 × 108 1.6 × 109 [41,42]
Transportation Cost * USD/bbl $0.60 $0.60 [86]
Well Injection Cost USD/bbl $0.5 $0.5 [43]
Well disposal Cost USD/year $171,730,000 $831,605,000
Water management Cost—Scenario 1 USD/year $377.30 M $1.76 B
Treatment and reuse
(Correspondence w/water treatment
Chemical oxidation USD/bbl $0.20 $0.20
company)
Chemical precipitation & (Correspondence w/water treatment
USD/bbl $0.24 $0.24
nanofiltration company)
Water management Cost—Scenario 2 USD/year $150.92 M $704.00 M

3. Opportunities in Produced Water Management

3.1. Technologies/Processes, and Their Respective Costs, Used to Extract Precious Metals
The recovery of elements with added values (Li, K, Sr, Mg, Mn, etc.) from FP represent
a great advantage for the energy sector. The rapidly increasing demand for precious
metals such as Li is challenging, however, as the reservoirs of Li are limited worldwide.
Various industries, including batteries, pharmaceuticals and ceramics, need Li for their
operations [54]. Global efforts are pursuing the acquisition of Li from seawater [90,91],
although compared to FP, the concentration in seawater is orders of magnitudes lower.
Alternatively, several other metals and critical minerals are also found in FP, including Co
and Ni (refer to Table 1), which are also relevant for the manufacturing of batteries. Based
on the annual production of FP in the Bakken and Permian Basin Region, a comparison in
the economics of extractable metals is provided in Table 3.
Previous studies involved the nano-sized zerovalent iron (n-ZVI) catalytic oxidation
and adsorption for the recovery of elements such as Sr, Mg, Na, Al, Ca, K and P, as well as
the degradation of organic matter in FP. The cost associated with these operations is ap-
proximately USD 1355.80 per barrel per hour [51]. In other studies, the analysis of the costs
for FP desalination in the Marcellus Shale applying direct contact membrane distillation
(DCMD) resulted in USD $35.87/bbl. Moreover, there is opportunity to decrease the costs
to as low as USD $4.66/bbl of water fed if the waste heat is recycled into the treatment [92].
Additionally, Zendejas et al. compared chemical coagulation and electrocoagulation for
the treatment of FP for reuse in the Permian Basin, estimating costs of USD $2.33/bbl
and $2.77/bbl of treated water (Zendejas et al., 2020). Lastly, a combined osmosis system
consisting of FO, RO and NF presented a total water management cost of USD $2.32/bbl of
pit water [86].
Energies 2022, 15, 4619 10 of 18

Table 3. Quantities and values of extractable metals from Permian Basin and Bakken.

Value of Value of
Total Extractable Total Extractable
Industry/Terminal Price (USD/kg) Extractable Metals Extractable Metals
Element Mass in FP, kg Mass in FP, kg
Uses [93] in Millions, M in Millions, M
(Bakken) * (Permian) *
(Bakken) (Permian)
Sodium salts
Na $2.57–3.43 7.59 ×109 $22,776.39 1.35 × 1010 $40,453.20
production
Li Batteries $81.40–85.60 3.39 × 106 $283.12 4.97 × 106 $415.06
K Fertilizer/saltproduction $12.10–13.60 3.56 × 108 $4574.50 2.21 × 108 $2836.95
Sr Firework $6.50–6.70 8.62 × 107 $569.01 2.05 × 108 $1352.41
Cement
Ca fabrication/reducing $2.21–2.35 1.48 × 109 $3379.85 3.31 × 109 $7535.40
agent
Mg Alloying agent $2.30 1.45 × 108 $334.04 4.73 × 108 $1088.53
Mn Steel making $1.80 6.12 × 105 $1.10 8.46 × 106 $15.23
Co Batteries $32.8 6.28 × 103 $0.21 0 $0.00
Ni Batteries $13.90 1.04 × 105 $1.44 5.29 × 103 $0.07
B Glass and ceramics $3.68 7.78 × 106 $28.63 0 $0.00
* Calculations based on amount of FP generated per annum (54.6 × 109 L for Bakken and 264.4 × 109 L for
Permian) multiplied by the average ion concentration, as illustrated in Table 1.

The feasibility of mining precious metals relies on: (1) the location of the play;
(2) the cost of the treatment modality; (3) the market price of the element. In particu-
lar, the Permian Basin has levels of K of 1100 mg/L (see Table 1), and the combined osmosis
system has a cost of USD $2.32/bbl. The recovery of 1 kg of K would require the treatment
of approximately 5.72 bbl of FP (USD $13.34); as shown in Table 3, the market price for
K is USD ~$12.10/kg, which shows that it is not economically viable to extract K from
the Permian region. Similarly, the expenditures for the acquisition of Li and Sr are USD
$776.27 and $17.80, respectively. Meanwhile, the cost of K extraction in Bakken utilizing the
previous analogy is USD $1.53 for 1 kg of K, which could be further sold for USD $12.10,
producing a significant profit margin. The cost of recovery of Sr in Bakken is approximately
USD $5.96, which also makes it viable. Additional costs involving possible purification
steps should be considered. According to the USGS National Mineral Information Center,
the domestic production of salt satisfies 85.11% of the reported salt consumption in the
US (excluding Puerto Rico) [94]. The estimated extractable value for sodium chloride in
the Permian Basin alone represents approximately 73% of the salt demand in 2021. Other
outlets for these byproducts are to be explored.
The challenges associated with treating FP, along with the variety of modalities avail-
able for this purpose, steer the efforts into a combined technologies approach as shown
in Figure 3. This FP valorization process integrates: (1) an oxidation step; (2) chemical
coagulation/precipitation; (3) filtration; (4) a membrane system; (5) electrocoagulation.
The first three steps achieve the removal of microorganisms and part of the organic matter
found in FP. The membrane system target the ions, and the EC polishes the metal for its
recovery. The utilization of embedded membranes aids in the removal of persistent ions
such as B. The resulting treated water could be used for crop irrigation or to replenish
natural sources, or it could be recycled in UOG operations depending on the attained
parameters and the requirements set by FAO, EPA or the oil and gas industry.

3.2. Feasibility of Extracting Precious Metals in Certain Shale Energy Basins

The U.S. Geological Survey (USGS) is a national agency that collects data of natural
resource conditions. The USGS provides a database with information about the abundance
of certain elements typically present in FP, their origin and other bulk parameters [95].
According to the database, metals like Na, K, Mg, Ca and Sr are common in most shales
at elevated concentrations. However, there is limited information about ions with more
industrial relevance, such as Co, Ni and Li. More studies are needed in the characterization
of FP to establish a better foundation when dabbling into this field. The feasibility of metal
extraction relies on a minimum threshold of ion concentration. In Table 4, these values are
 The challenges associated with treating FP, along with the variety of modalities avail-
able for this purpose, steer the efforts into a combined technologies approach as shown in
Figure 3. This FP valorization process integrates: (1) an oxidation step; (2) chemical coag-
ulation/precipitation; (3) filtration; (4) a membrane system; (5) electrocoagulation. The
Energies 2022, 15, 4619 first three steps achieve the removal of microorganisms and part of the organic matter 11 of 18
found in FP. The membrane system target the ions, and the EC polishes the metal for its
recovery. The utilization of embedded membranes aids in the removal of persistent ions
such as B. The resulting treated water could be used for crop irrigation or to replenish
shown for certain elements along with viable locations for their extraction. The threshold
natural sources, or it could be recycled in UOG operations depending on the attained pa-
calculations are based on the concentrations reported for Permian Basin (refer to Table 1)
rameters and the requirements set by FAO, EPA or the oil and gas industry.
and a treatment cost of USD $2.32 per bbl of FP.

Figure 3. Schematic of the valorization process for FP. Step-by-step methodologies are applied to
Figure 3. Schematic of the valorization process for FP. Step-by-step methodologies are applied to
extractprecious
extract preciousmetals
metals from
from FP,
FP, adding
adding an
an aggregated
aggregated value
value to
to this
this waste.
waste.
As previously mentioned, the interest in finding alternative sources of lithium has
3.2. Feasibility of Extracting Precious Metals in Certain Shale Energy Basins
triggered a race in the study of various technologies for Li extraction from brines. As shown
The U.S.
in Figure Geological
4, these Survey
techniques (USGS)
range fromistypical
a national
solventagency that collects
extractions data chemically
to novel of natural
resource
modifiedconditions.
surfaces forThe USGS provides a database with information about the abun-
adsorption.
danceTheof certain elements
conventional typically
solar present
evaporation in FP,
method is their
a veryorigin and other
cost-effective bulk parameters
procedure; however,
[95]. According to the database, metals like Na, K, Mg, Ca and Sr are common
the extensive land area required hinders its application, as does the limited selectivity in most
for a
shales at elevated concentrations. However, there is limited information about
particular ion of interest. Whilst solvent extraction and phosphate precipitation facilitate ions with
more industrial
the recovery of relevance,
lithium, the such as Co, Ni and
environmental Li. Morecosts
concerns, studies
andare needed in thesteer
coprecipitation charac-
the
terization
industrialofefforts
FP to toward
establish a better
less foundation
polluting options.when Some dabbling
adsorptiveinto materials
this field. containing
The feasi-
bility of metal
aluminum andextraction
titanium relies on a minimum
each offered promisingthreshold
results offorion
Li concentration. In Tablethe
extraction. However, 4,
these values on
dependence arepHshown
mustfor
be certain elements
overcome, as mustalong with viable
the challenges in locations for their
the desorption extrac-
mechanism
tion.
of LiThe
fromthreshold calculations
the Al surface and theare based on the
competition concentrations
of cations reported for
on titanium-based Permian [96].
adsorbents Ba-
sin
As (refer to Table 1)
for manganese and amaterials,
based treatmentthecost of USD $2.32
conversion fromper bbl of FP.to industrial-scale and
laboratory-
the limited understanding of the adsorption/desorption process represent a challenge [97].
Nanofiltration and ion exchange technologies have been utilized in industrial scenarios for
the removal of ions with great results. Nevertheless, metal extraction requires a combination
of resins at different stages if not targeted to a particular metal. Additionally, matrices such
as FP require further separation processes, compromising the feasibility on an industrial
scale. Recently, encouraging results proposed a highly selective polymer for the efficient
extraction of lithium in presence of other ions, such as Na and K. More importantly, Li can
be easily released by increasing temperature; this is particularly interesting for possible
industrial applications [98].
The “E3 Metals Corp” agency operates within the Leduc Formation in Alberta, Canada.
They are able to recover >90% of Li from oilfield brines with Li concentrations of 74.6 mg/L
in the form of hydrated lithium hydroxide (LiOH·H2 O), with an annual production capacity
of 20,000 mt. The reported capital expenditure (CapEx) for this infrastructure is USD
$602,000 MM, and the operation expenditure (OpEx) is USD $73,200 MM [100]. The
magnitude of the initial investment for the construction of a similar structure in the United
States frustrates the acquisition of these treatment sites in the shales. As a possible solution,
a centralized facility should be considered to which the FP from the regional shales could be
transported and treated via pipelines or trucks, resulting in a minimized economic impact
that this strenuous investment may cause to the UOG industry.
Energies 2022, 15, 4619 12 of 18

Table 4. Metal thresholds and abundance. Minimum concentration of metals required for feasible
extractions and their abundance. Calculations are based on treatment costs of USD 2.32/bbl, further
isolation processes not included.

Metal Minimum Concentration (mg/L) Formation Basin State

Na 5678.58 Multiple
Ca 6603.60 Multiple
Mg 6345.20 Multiple
K 1206.11 Multiple
Marcellus Sh
Helderberg Ls
Appalachian PA
Cambrian
Oriskany Ss
Onondaga Ls
Dakota
Powder River Wyoming
Parkman
Smackover Gulf coast
Arkansas
Smackover lime Arkla
Mississippian Las Animas Arch Colorado
Smackover Gulf Coast Mississippi
Ratcliffe
Dwyer Charles Williston Montana

Duperow
Li 179.29
Unknown Permian New Mexico
Oriskany Ss Appalachian New York
Madison Williston
Duperow Williston
Grenora Charles Williston North Dakota

Madison Charles Williston

Rival Williston
Devonian Duperow Williston
Canyon Permian
Smackover East Texas
Unknown Amarillo Arch Texas
Unknown Palo Duro
Unknown Anadarko
Edwards Gulf coast
Miocene Gulf coast
Sr 2245.22 Multiple
Mn 8107.75 N/A
Co 444.94 N/A
Ni 1050.59 N/A
B 3965.75 N/A
 dustrial scenarios for the removal of ions with great results. Nevertheless, metal extraction
requires a combination of resins at different stages if not targeted to a particular metal.
Additionally, matrices such as FP require further separation processes, compromising the
feasibility on an industrial scale. Recently, encouraging results proposed a highly selective
polymer for the efficient extraction of lithium in presence of other ions, such as Na and K.
Energies 2022, 15, 4619 13 of 18
More importantly, Li can be easily released by increasing temperature; this is particularly
interesting for possible industrial applications [98].

Figure 4. Available technologies for extracting Li from brines. Description of the mechanism of
extraction for Li of the several commercial technologies and their developers [99].

4. Conclusions
The reuse of treated FP will relieve the water stress caused by HF in arid regions such as
the Permian Basin. Due to more FP being produced than is required for injection, recycling
in agriculture is an attractive option for this excess, as most of the water consumption in the
Permian region is dedicated to irrigation. Remaining challenges in FP sanitation include the
complete characterization of FP, the high cost of the materials used to build facilities and the
lack of methods for removing difficult ions such as boron. Whilst a variety of technologies
are available for the treatment of highly saline brines, the appropriate strategy should be a
combination of sequential steps. Although promising a sustainable solution, the high CapEx
associated with the development of a facility with these requirements is not economically
Energies 2022, 15, 4619 14 of 18

favorable. The intensive capital cost of such investment demands joint efforts from the
involved industries for the construction of a centralized treatment facility that facilitates
the purification of water as well as the extraction of these valuable metals (Figure 4). The
recuperation of Li is possible in Permian, Palo Duro, the Gulf Coast, Williston, Appalachia
and many other regions, as is the recovery of Sr, Ca, Mg, Na and K. In this sense, based
on the numerous studies available and the growing demand by the energy sector, lithium
should be the candidate for the development of this pilot strategy. A drawback to treating
FP down to reuse standards is the generation of extremely salty brines/sludge. Although
found in low concentrations in the Permian Basin, the accumulation of radionuclides
in these brines can generate low-level nuclear waste. Furthermore, assuming all the
produced water is treated in both Bakken and Permian Basin, the sum of extractable salt
will represent approximately 116% of the domestic consumption in 2021 with these plays
alone (USGS, 2022). Other outlets for these surplus materials have yet to be explored.

Author Contributions: Conceptualization, Z.L.H. methodology, R.S.-R.; software, R.S.-R.; validation,

R.S.-R. and Z.L.H.; formal analysis, R.S.-R.; investigation, R.S.-R.; resources, R.S.-R.; data curation,
R.S.-R.; writing—original draft preparation, R.S.-R.; writing—review and editing, Z.L.H.; visualiza-
tion, R.S.-R.; supervision, Z.L.H.; project administration, Z.L.H. All authors have read and agreed to
the published version of the manuscript.
Funding: This research received no external funding.
Acknowledgments: We wish to thank Mark Engle for his time and consideration critiquing this review.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Davarpanah, A. Feasible analysis of reusing flowback produced water in the operational performances of oil reservoirs. Environ.
Sci. Pollut. Res. 2018, 25, 35387–35395. [CrossRef]
2. Miller, H.; Dias, K.; Hare, H.; Borton, M.A.; Blotevogel, J.; Danforth, C.; Wrighton, K.C.; Ippolito, J.A.; Borch, T. Reusing oil and
gas produced water for agricultural irrigation: Effects on soil health and the soil microbiome. Sci. Total Environ. 2020, 722, 137888.
[CrossRef]
3. Al-Ghouti, M.A.; Al-Kaabi, M.A.; Ashfaq, M.Y.; Da’Na, D.A. Produced water characteristics, treatment and reuse: A review.
J. Water Process Eng. 2019, 28, 222–239. [CrossRef]
4. Igunnu, E.T.; Chen, G.Z. Produced water treatment technologies. Int. J. Low-Carbon Technol. 2014, 9, 157–177. [CrossRef]
5. Jiang, W.; Lin, L.; Xu, X.; Cheng, X.; Zhang, Y.; Hall, R.; Xu, P. A Critical Review of Analytical Methods for Comprehensive
Characterization of Produced Water. Water 2021, 13, 183. [CrossRef]
6. Thiel, G.P.; Lienhard, J.H. Treating produced water from hydraulic fracturing: Composition effects on scale formation and
desalination system selection. Desalination 2014, 346, 54–69. [CrossRef]
7. Fisher, R.S. Naturally Occurring Radioactive Materials (NORM) in Produced Water and Scale from Texas Oil, Gas, and Geothermal
Wells: Geographic, Geologic, And Geochemical Controls. In Geological Circular; The University of Texas at Austin: Austin, TX,
USA; Bureau of Economic Geology: Austin, TX, USA, 1995; 43p. [CrossRef]
8. McLaughlin, M.C.; Borch, T.; McDevitt, B.; Warner, N.R.; Blotevogel, J. Water quality assessment downstream of oil and gas
produced water discharges intended for beneficial reuse in arid regions. Sci. Total Environ. 2020, 713, 136607. [CrossRef]
9. Abualfaraj, N.; Gurian, P.L.; Olson, M.S. Characterization of Marcellus Shale Flowback Water. Environ. Eng. Sci. 2014, 31, 514–524.
[CrossRef]
10. Lauer, N.E.; Harkness, J.; Vengosh, A. Brine Spills Associated with Unconventional Oil Development in North Dakota. Environ.
Sci. Technol. 2016, 50, 5389–5397. [CrossRef]
11. Shih, J.-S.; Saiers, J.E.; Anisfeld, S.C.; Chu, Z.; Muehlenbachs, L.A.; Olmstead, S.M. Characterization and Analysis of Liquid Waste
from Marcellus Shale Gas Development. Environ. Sci. Technol. 2015, 49, 9557–9565. [CrossRef]
12. McDevitt, B.; McLaughlin, M.C.; Blotevogel, J.; Borch, T.; Warner, N.R. Oil & gas produced water retention ponds as potential
passive treatment for radium removal and beneficial reuse. Environ. Sci. Process. Impacts 2021, 23, 501–518. [CrossRef]
13. Sun, Y.; Wang, D.; Tsang, D.C.; Wang, L.; Ok, Y.S.; Feng, Y. A critical review of risks, characteristics, and treatment strategies for
potentially toxic elements in wastewater from shale gas extraction. Environ. Int. 2019, 125, 452–469. [CrossRef]
14. Jiang, W.; Xu, X.; Hall, R.; Zhang, Y.; Carroll, K.C.; Ramos, F.; Engle, M.A.; Lin, L.; Wang, H.; Sayer, M.; et al. Characterization
of produced water and surrounding surface water in the Permian Basin, the United States. J. Hazard. Mater. 2022, 430, 128409.
[CrossRef]
15. Liden, T.; Santos, I.C.; Hildenbrand, Z.L.; Schug, K.A. Treatment modalities for the reuse of produced waste from oil and gas
development. Sci. Total Environ. 2018, 643, 107–118. [CrossRef]
Energies 2022, 15, 4619 15 of 18

16. Oetjen, K.; Chan, K.E.; Gulmark, K.; Christensen, J.H.; Blotevogel, J.; Borch, T.; Spear, J.R.; Cath, T.Y.; Higgins, C.P. Temporal
characterization and statistical analysis of flowback and produced waters and their potential for reuse. Sci. Total Environ. 2018,
619–620, 654–664. [CrossRef]
17. Ferrer, I.; Thurman, E.M. Chemical constituents and analytical approaches for hydraulic fracturing waters. Trends Environ. Anal.
Chem. 2015, 5, 18–25. [CrossRef]
18. Akyon, B.; McLaughlin, M.; Hernández, F.; Blotevogel, J.; Bibby, K. Characterization and biological removal of organic compounds
from hydraulic fracturing produced water. Environ. Sci. Process. Impacts 2019, 21, 279–290. [CrossRef]
19. Thacker, J.B.; Carlton, J.D.D.; Hildenbrand, Z.L.; Kadjo, A.F.; Schug, K.A. Chemical Analysis of Wastewater from Unconventional
Drilling Operations. Water 2015, 7, 1568–1579. [CrossRef]
20. Santos, I.C.; Hildenbrand, Z.L.; Schug, K.A. A Review of Analytical Methods for Characterizing the Potential Environmental
Impacts of Unconventional Oil and Gas Development. Anal. Chem. 2019, 91, 689–703. [CrossRef]
21. Danforth, C.; Chiu, W.A.; Rusyn, I.; Schultz, K.; Bolden, A.; Kwiatkowski, C.; Craft, E. An integrative method for identification
and prioritization of constituents of concern in produced water from onshore oil and gas extraction. Environ. Int. 2020, 134, 105280.
[CrossRef]
22. Chen, H.; Carter, K.E. Characterization of the chemicals used in hydraulic fracturing fluids for wells located in the Marcellus
Shale Play. J. Environ. Manag. 2017, 200, 312–324. [CrossRef]
23. Luek, J.L.; Gonsior, M. Organic compounds in hydraulic fracturing fluids and wastewaters: A review. Water Res. 2017, 123,
536–548. [CrossRef]
24. Kahrilas, G.A.; Blotevogel, J.; Stewart, P.S.; Borch, T. Biocides in Hydraulic Fracturing Fluids: A Critical Review of Their Usage,
Mobility, Degradation, and Toxicity. Environ. Sci. Technol. 2015, 49, 16–32. [CrossRef]
25. Stringfellow, W.T.; Domen, J.K.; Camarillo, M.K.; Sandelin, W.L.; Borglin, S. Physical, chemical, and biological characteristics of
compounds used in hydraulic fracturing. J. Hazard. Mater. 2014, 275, 37–54. [CrossRef]
26. Stringfellow, W.T.; Camarillo, M.K.; Domen, J.K.; Sandelin, W.L.; Varadharajan, C.; Jordan, P.D.; Reagan, M.T.; Cooley, H.;
Heberger, M.G.; Birkholzer, J.T. Identifying chemicals of concern in hydraulic fracturing fluids used for oil production. Environ.
Pollut. 2017, 220, 413–420. [CrossRef]
27. de Oliveira, E.S.D.; Roseana, F.; Pereira, C.; Alice, M.; Lima, G.D.A. Study on Biofilm Forming Microorganisms Associated with
the Biocorrosion of X80 Pipeline Steel in Produced Water from Oilfield. Mater. Res. 2021, 24, e20210196. [CrossRef]
28. Mohan, A.M.; Bibby, K.; Lipus, D.; Hammack, R.W.; Gregory, K.B. The Functional Potential of Microbial Communities in
Hydraulic Fracturing Source Water and Produced Water from Natural Gas Extraction Characterized by Metagenomic Sequencing.
PLoS ONE 2014, 9, e107682. [CrossRef]
29. Cluff, M.A.; Hartsock, A.; MacRae, J.D.; Carter, K.; Mouser, P.J. Temporal Changes in Microbial Ecology and Geochemistry in
Produced Water from Hydraulically Fractured Marcellus Shale Gas Wells. Environ. Sci. Technol. 2014, 48, 6508–6517. [CrossRef]
30. Bedoya, K.; Niño, J.; Acero, J.; Cabarcas, F.; Alzate, J.F. Assessment of the microbial community and biocide resistance profile
in production and injection waters from an Andean oil reservoir in Colombia. Int. Biodeterior. Biodegrad. 2021, 157, 105137.
[CrossRef]
31. Handley, K.M.; Lloyd, J.R. Biogeochemical implications of the ubiquitous colonization of marine habitats and redox gradients by
Marinobacter species. Front. Microbiol. 2013, 4, 136. [CrossRef]
32. Hildenbrand, Z.L.; Santos, I.; Liden, T.; Carlton, D.D.; Varona-Torres, E.; Martin, M.S.; Reyes, M.L.; Mulla, S.R.; Schug, K.A.
Characterizing variable biogeochemical changes during the treatment of produced oilfield waste. Sci. Total Environ. 2018, 634,
1519–1529. [CrossRef]
33. Tiburcio, S.R.G.; Macrae, A.; Peixoto, R.S.; Rachid, C.T.C.D.C.; Mansoldo, F.R.P.; Alviano, D.S.; Alviano, C.S.; Ferreira, D.F.;
Venâncio, F.d.Q.; Ferreira, D.F.; et al. Sulphate-reducing bacterial community structure from produced water of the Periquito and
Galo de Campina onshore oilfields in Brazil. Sci. Rep. 2021, 11, 20311. [CrossRef]
34. Ers, S.; Faisal, A.S.; Re, B.N.K. Thermoanaerobacter spp. recovered from hot produced water from the Thar Jath oil-field in South
Sudan. Afr. J. Microbiol. Res. 2013, 7, 5219–5226. [CrossRef]
35. Emerson, D.; Agulto, L.; Liu, H.; Liu, L. Identifying and Characterizing Bacteria in an Era of Genomics and Proteomics. BioScience
2008, 58, 925–936. [CrossRef]
36. Liden, T.; Santos, I.C.; Hildenbrand, Z.L.; Schug, K.A. Analytical Methods for the Comprehensive Characterization of Produced
Water. In Separation Science and Technology; Academic Press: New York, NY, USA, 2019; pp. 199–217. [CrossRef]
37. EPA, 2022. Available online: https://www.epa.gov/uic/general-information-about-injection-well (accessed on 27 April 2022).
38. Shores, A.; Laituri, M.; Butters, G. Produced Water Surface Spills and the Risk for BTEX and Naphthalene Groundwater
Contamination. Water Air Soil Pollut. 2017, 228, 435. [CrossRef]
39. Wang, N.; Kunz, J.L.; Cleveland, D.; Steevens, J.A.; Cozzarelli, I.M. Biological Effects of Elevated Major Ions in Surface Water
Contaminated by a Produced Water from Oil Production. Arch. Environ. Contam. Toxicol. 2019, 76, 670–677. [CrossRef]
40. Akob, D.M.; Mumford, A.C.; Orem, W.H.; Engle, M.A.; Klinges, J.G.; Kent, D.B.; Cozzarelli, I.M. Wastewater Disposal from
Unconventional Oil and Gas Development Degrades Stream Quality at a West Virginia Injection Facility. Environ. Sci. Technol.
2016, 50, 5517–5525. [CrossRef]
41. Scanlon, B.R.; Ikonnikova, S.; Yang, Q.; Reedy, R.C. Will Water Issues Constrain Oil and Gas Production in the United States?
Environ. Sci. Technol. 2020, 54, 3510–3519. [CrossRef]
Energies 2022, 15, 4619 16 of 18

42. Scanlon, B.R.; Reedy, R.C.; Xu, P.; Engle, M.; Nicot, J.; Yoxtheimer, D.; Yang, Q.; Ikonnikova, S. Can we beneficially reuse produced
water from oil and gas extraction in the U.S.? Sci. Total Environ. 2020, 717, 137085. [CrossRef]
43. Scanlon, B.R.; Reedy, R.C.; Male, F.; Walsh, M. Water Issues Related to Transitioning from Conventional to Unconventional Oil
Production in the Permian Basin. Environ. Sci. Technol. 2017, 51, 10903–10912. [CrossRef]
44. Kappel, W.M.; Williams, J.H.; Szabo, Z. Water Resources and Shale Gas/Oil Production in the Appalachian Basin—Critical Issues and
Evolving Developments; US Department of the Interior, US Geological Survey: Washington, DC, USA, 2013.
45. Benson, P.M.; Austria, D.C.; Gehne, S.; Butcher, E.; Harnett, C.E.; Fazio, M.; Rowley, P.; Tomas, R. Laboratory simulations of
fluid-induced seismicity, hydraulic fracture, and fluid flow. Geomech. Energy Environ. 2020, 24, 100169. [CrossRef]
46. Lemons, C.R.; McDaid, G.; Smye, K.M.; Acevedo, J.P.; Hennings, P.H.; Banerji, D.A.; Scanlon, B.R. Spatiotemporal and stratigraphic
trends in salt-water disposal practices of the Permian Basin, Texas and New Mexico, United States. Environ. Geosci. 2019, 26,
107–124. [CrossRef]
47. Schultz, R.; Skoumal, R.J.; Brudzinski, M.R.; Eaton, D.; Baptie, B.; Ellsworth, W. Hydraulic Fracturing-Induced Seismicity. Rev.
Geophys. 2020, 58. [CrossRef]
48. Rosenblum, J.; Nelson, A.W.; Ruyle, B.; Schultz, M.; Ryan, J.N.; Linden, K.G. Temporal characterization of flowback and produced
water quality from a hydraulically fractured oil and gas well. Sci. Total Environ. 2017, 596–597, 369–377. [CrossRef]
49. Khalil, C.A.; Prince, V.L.; Prince, R.C.; Greer, C.W.; Lee, K.; Zhang, B.; Boufadel, M.C. Occurrence and biodegradation of
hydrocarbons at high salinities. Sci. Total Environ. 2021, 762, 143165. [CrossRef]
50. Mauter, M.S.; Palmer, V.R. Expert Elicitation of Trends in Marcellus Oil and Gas Wastewater Management. J. Environ. Eng. 2014,
140, B4014004. [CrossRef]
51. Abass, O.; Zhuo, M.; Zhang, K. Concomitant degradation of complex organics and metals recovery from fracking wastewater:
Roles of nano zerovalent iron initiated oxidation and adsorption. Chem. Eng. J. 2017, 328, 159–171. [CrossRef]
52. USEPA. National Primary Drinking Water Guidelines. EPA 816-F-09-004, 1, 7. 2009. Available online: https://www.epa.gov/
sites/production/files/2016-06/documents/npwdr_complete_table.pdf (accessed on 21 April 2022).
53. Crook, J.; Ammerman, D.; Okun, D.; Matthews, R. EPA Guidelines for Water Reuse. Guidelines for Water Reuse; EPA: Washington,
DC, USA, 2012; 643p.
54. Xiao, F. Characterization and treatment of Bakken oilfield produced water as a potential source of value-added elements. Sci.
Total Environ. 2021, 770, 145283. [CrossRef]
55. Shrestha, N.; Chilkoor, G.; Wilder, J.; Gadhamshetty, V.; Stone, J.J. Potential water resource impacts of hydraulic fracturing from
unconventional oil production in the Bakken shale. Water Res. 2017, 108, 2859–2868. [CrossRef]
56. Wang, H.; Lu, L.; Chen, X.; Bian, Y.; Ren, Z.J. Geochemical and microbial characterizations of flowback and produced water in
three shale oil and gas plays in the central and western United States. Water Res. 2019, 164, 114942. [CrossRef]
57. Shrestha, N.; Chilkoor, G.; Wilder, J.; Ren, Z.; Gadhamshetty, V. Comparative performances of microbial capacitive deionization
cell and microbial fuel cell fed with produced water from the Bakken shale. Bioelectrochemistry 2018, 121, 56–64. [CrossRef]
58. Rodriguez, A.Z.; Wang, H.; Hu, L.; Zhang, Y.; Xu, P. Treatment of Produced Water in the Permian Basin for Hydraulic Fracturing:
Comparison of different coagulation processes and innovative filter media. Water 2020, 12, 770. [CrossRef]
59. Khan, N.A.; Engle, M.; Dungan, B.; Holguin, F.; Xu, P.; Carroll, K.C. Volatile-organic molecular characterization of shale-oil
produced water from the Permian Basin. Chemosphere 2016, 148, 126–136. [CrossRef]
60. Chang, H.; Liu, T.; He, Q.; Li, D.; Crittenden, J.; Liu, B. Removal of calcium and magnesium ions from shale gas flowback water
by chemically activated zeolite. Water Sci. Technol. 2017, 76, 575–583. [CrossRef]
61. Sun, Y.; Yu, I.K.; Tsang, D.C.; Cao, X.; Lin, D.; Wang, L.; Graham, N.J.; Alessi, D.; Komárek, M.; Ok, Y.S.; et al. Multifunctional
iron-biochar composites for the removal of potentially toxic elements, inherent cations, and hetero-chloride from hydraulic
fracturing wastewater. Environ. Int. 2019, 124, 521–532. [CrossRef]
62. Panagopoulos, A.; Haralambous, K.-J.; Loizidou, M. Desalination brine disposal methods and treatment technologies—A review.
Sci. Total Environ. 2019, 693, 133545. [CrossRef]
63. Shang, W.; Tiraferri, A.; He, Q.; Li, N.; Chang, H.; Liu, C.; Liu, B. Reuse of shale gas flowback and produced water: Effects of
coagulation and adsorption on ultrafiltration, reverse osmosis combined process. Sci. Total Environ. 2019, 689, 47–56. [CrossRef]
64. Coday, B.D.; Xu, P.; Beaudry, E.G.; Herron, J.; Lampi, K.; Hancock, N.T.; Cath, T.Y. The sweet spot of forward osmosis: Treatment
of produced water, drilling wastewater, and other complex and difficult liquid streams. Desalination 2014, 333, 23–35. [CrossRef]
65. Gregory, K.B.; Vidic, R.D.; Dzombak, D.A. Water Management Challenges Associated with the Production of Shale Gas by
Hydraulic Fracturing. Elements 2011, 7, 181–186. [CrossRef]
66. Khor, C.M.; Wang, J.; Li, M.; Oettel, B.A.; Kaner, R.B.; Jassby, D.; Hoek, E.M.V. Performance, Energy and Cost of Produced Water
Treatment by Chemical and Electrochemical Coagulation. Water 2020, 12, 3426. [CrossRef]
67. Kausley, S.B.; Malhotra, C.P.; Pandit, A.B. Treatment and reuse of shale gas wastewater: Electrocoagulation system for enhanced
removal of organic contamination and scale causing divalent cations. J. Water Process Eng. 2017, 16, 149–162. [CrossRef]
68. Sahu, O.; Mazumdar, B.; Chaudhari, P.K. Treatment of wastewater by electrocoagulation: A review. Environ. Sci. Pollut. Res. 2014,
21, 2397–2413. [CrossRef] [PubMed]
69. Hanay, Ö.; Hasar, H. Effect of anions on removing Cu2+, Mn2+ and Zn2+ in electrocoagulation process using aluminum electrodes.
J. Hazard. Mater. 2011, 189, 572–576. [CrossRef] [PubMed]
Energies 2022, 15, 4619 17 of 18

70. Moradi, M.; Vasseghian, Y.; Arabzade, H.; Khaneghah, A.M. Various wastewaters treatment by sono-electrocoagulation process:
A comprehensive review of operational parameters and future outlook. Chemosphere 2021, 263, 128314. [CrossRef] [PubMed]
71. Chua, H.T.; Rahimi, B. Low Grade Heat Driven Multi-Effect Distillation and Desalination; Elsevier: Amsterdam, The Netherlands, 2017.
72. Mohammad-Pajooh, E.; Weichgrebe, D.; Cuff, G.; Tosarkani, B.M.; Rosenwinkel, K.-H. On-site treatment of flowback and produced
water from shale gas hydraulic fracturing: A review and economic evaluation. Chemosphere 2018, 212, 898–914. [CrossRef]
73. Kim, J.; Kim, J.; Hong, S. Recovery of water and minerals from shale gas produced water by membrane distillation crystallization.
Water Res. 2018, 129, 447–459. [CrossRef]
74. Kong, F.-X.; Chen, J.-F.; Wang, H.-M.; Liu, X.-N.; Wang, X.-M.; Wen, X.; Chen, C.-M.; Xie, Y.F. Application of coagulation-UF
hybrid process for shale gas fracturing flowback water recycling: Performance and fouling analysis. J. Membr. Sci. 2017, 524,
460–469. [CrossRef]
75. Fakhru’L-Razi, A.; Pendashteh, A.; Abdullah, L.C.; Biak, D.R.A.; Madaeni, S.S.; Abidin, Z.Z. Review of technologies for oil and
gas produced water treatment. J. Hazard. Mater. 2009, 170, 530–551. [CrossRef]
76. Boerlage, S.F.E. Measuring salinity and TDS of seawater and brine for process and environmental monitoring—Which one, when?
Desalination Water Treat. 2012, 42, 222–230. [CrossRef]
77. Kaplan, R.; Mamrosh, D.; Salih, H.H.; Dastgheib, S.A. Assessment of desalination technologies for treatment of a highly saline
brine from a potential CO2 storage site. Desalination 2017, 404, 87–101. [CrossRef]
78. Liden, T.; Carlton, D.D.; Miyazaki, S.; Otoyo, T.; Schug, K.A. Forward osmosis remediation of high salinity Permian Basin
produced water from unconventional oil and gas development. Sci. Total Environ. 2018, 653, 82–90. [CrossRef] [PubMed]
79. Lutchmiah, K.; Verliefde, A.; Roest, K.; Rietveld, L.; Cornelissen, E. Forward osmosis for application in wastewater treatment: A
review. Water Res. 2014, 58, 179–197. [CrossRef]
80. Cui, Y.; Ge, Q.; Liu, X.-Y.; Chung, N.T.-S. Novel forward osmosis process to effectively remove heavy metal ions. J. Membr. Sci.
2014, 467, 188–194. [CrossRef]
81. Sardari, K.; Fyfe, P.; Lincicome, D.; Wickramasinghe, S.R. Combined electrocoagulation and membrane distillation for treating
high salinity produced waters. J. Membr. Sci. 2018, 564, 82–96. [CrossRef]
82. Humoud, M.S.; Roy, S.; Mitra, S. Enhanced Performance of Carbon Nanotube Immobilized Membrane for the Treatment of High
Salinity Produced Water via Direct Contact Membrane Distillation. Membranes 2020, 10, 325. [CrossRef]
83. Ahmad, N.A.; Goh, P.S.; Yogarathinam, L.T.; Zulhairun, A.K.; Ismail, A.F. Current advances in membrane technologies for
produced water desalination. Desalination 2020, 493, 114643. [CrossRef]
84. Zhao, S.; Hu, S.; Zhang, X.; Song, L.; Wang, Y.; Tan, M.; Kong, L.; Zhang, Y. Integrated membrane system without adding
chemicals for produced water desalination towards zero liquid discharge. Desalination 2020, 496, 114693. [CrossRef]
85. Dolan, F.C.; Cath, T.Y.; Hogue, T.S. Assessing the feasibility of using produced water for irrigation in Colorado. Sci. Total Environ.
2018, 640–641, 619–628. [CrossRef]
86. Coday, B.D.; Miller-Robbie, L.; Beaudry, E.G.; Marr, J.M.; Cath, T.Y. Life cycle and economic assessments of engineered osmosis
and osmotic dilution for desalination of Haynesville shale pit water. Desalination 2015, 369, 188–200. [CrossRef]
87. Maloney, K.O.; Yoxtheimer, D.A. Research Articles: Production and Disposal of Waste Materials from Gas and Oil Extraction
from the Marcellus Shale Play in Pennsylvania. Environ. Pract. 2012, 14, 278–287. [CrossRef]
88. Dong, X.; Trembly, J.; Bayless, D. Techno-economic analysis of hydraulic fracking flowback and produced water treatment in
supercritical water reactor. Energy 2017, 133, 777–783. [CrossRef]
89. Chang, H.; Li, T.; Liu, B.; Vidic, R.D.; Elimelech, M.; Crittenden, J.C. Potential and implemented membrane-based technologies for
the treatment and reuse of flowback and produced water from shale gas and oil plays: A review. Desalination 2019, 455, 34–57.
[CrossRef]
90. Li, Z.; Li, C.; Liu, X.-W.; Cao, L.; Li, P.; Wei, R.; Li, X.; Guo, D.; Huang, K.-W.; Lai, Z. Continuous electrical pumping membrane
process for seawater lithium mining. Energy Environ. Sci. 2021, 14, 3152–3159. [CrossRef]
91. Swain, B. Recovery and recycling of lithium: A review. Sep. Purif. Technol. 2017, 172, 388–403. [CrossRef]
92. Tavakkoli, S.; Lokare, O.; Vidic, R.D.; Khanna, V. A techno-economic assessment of membrane distillation for treatment of
Marcellus shale produced water. Desalination 2017, 416, 24–34. [CrossRef]
93. Prices of Chemical Elements. Available online: https://en.wikipedia.org/wiki/Prices_of_chemical_elements (accessed on
20 April 2022).
94. National Minerals Information Center. Mineral Commodity Summaries 2022 Data Release; U.S. Geological Survey: Reston, VA,
USA, 2022. [CrossRef]
95. Blondes, M.S.; Gans, K.D.; Engle, M.A.; Kharaka, Y.K.; Saraswathula, V.; Thordsen, J.J.; Morrissey, E.A.; Rowan, E.L.; Reidy, M.E.
U.S. Geological Survey National Produced Waters Geochemical Database; Version 2.3; U.S. Geological Survey: Reston, VA, USA, 2018.
[CrossRef]
96. Jang, Y.; Chung, E. Adsorption of Lithium from Shale Gas Produced Water Using Titanium Based Adsorbent. Ind. Eng. Chem. Res.
2018, 57, 8381–8387. [CrossRef]
97. Weng, D.; Duan, H.; Hou, Y.; Huo, J.; Chen, L.; Zhang, F.; Wang, J. Introduction of manganese based lithium-ion Sieve—A review.
Prog. Nat. Sci. 2020, 30, 139–152. [CrossRef]
98. Oral, I.; Abetz, V. A Highly Selective Polymer Material using Benzo-9-Crown-3 for the Extraction of Lithium in Presence of Other
Interfering Alkali Metal Ions. Macromol. Rapid Commun. 2021, 42, 2000746. [CrossRef]
Energies 2022, 15, 4619 18 of 18

99. Kumar, A.; Fukuda, H.; Hatton, T.A.; Lienhard, J.H.V. Lithium Recovery from Oil and Gas Produced Water: A Need for a Growing
Energy Industry. ACS Energy Lett. 2019, 4, 1471–1474. [CrossRef]
100. Warren, I. Techno-Economic Analysis of Lithium Extraction from Geothermal Brines Techno-Economic Analysis of Lithium Extraction from
Geothermal Brines; National Renewable Energy Lab.: Golden, CO, USA, 2021.