Butkovskyi 2017

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Critical Review
Organic pollutants in shale gas flowback and produced waters: identification,
potential ecological impact and implications for treatment strategies.
Andrii Butkovskyi, Harry Bruning, Stefan A.E. Kools, Huub H.M. Rijnaarts, and Annemarie P. van Wezel
Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.6b05640 • Publication Date (Web): 05 Apr 2017
Downloaded from http://pubs.acs.org on April 6, 2017
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Page 1 of 44 Environmental Science & Technology
1 Organic pollutants in shale gas flowback and produced waters: identification, potential
2 ecological impact and implications for treatment strategies.
3 Andrii Butkovskyi,1* Harry Bruning,1 Stefan A.E. Kools,2 Huub H.M. Rijnaarts,1 Annemarie
4 P. Van Wezel2,3,
1
5 Department of Environmental Technology, Wageningen University, P.O. Box 17, 6700 AA
6 Wageningen, Netherlands
2
7 KWR Watercycle Research Institute, P.O. Box 1072, 3430 BB Nieuwegein, Netherlands
3
8 Copernicus Institute of Sustainable Development, Utrecht University, P.O. Box 80.115, 3508 TC
9 Utrecht, The Netherlands
10 * Phone: +31 317 483997; e-mail: andrii.butkovskyi@wur.nl
11 Abstract
12 Organic contaminants in shale gas flowback and produced water (FPW) are traditionally
13 expressed as total organic carbon (TOC) or chemical oxygen demand (COD), though these
14 parameters do not provide information on the toxicity and environmental fate of individual
15 components. This review addresses identification of individual organic contaminants in FPW,
16 and stresses the gaps in the knowledge on FPW composition that exist so far. Furthermore,
17 the risk quotient approach was applied to predict the toxicity of the quantified organic
18 compounds for fresh water organisms in recipient surface waters. This resulted in an
19 identification of a number of FPW related organic compounds that are potentially harmful
20 namely those compounds originating from shale formations (e.g. polycyclic aromatic
21 hydrocarbons, phthalates), fracturing fluids (e.g. quaternary ammonium biocides, 2-
22 butoxyethanol) and downhole transformations of organic compounds (e.g. carbon disulphide,
23 halogenated organic compounds). Removal of these compounds by FPW treatment processes
24 is reviewed and potential and efficient abatement strategies are defined.
25 1. Introduction
26 The worldwide depletion of conventional oil and gas reserves inspired growing attention to
27 alternative energy sources. However, the current gap between non-renewable (81.6%) and
1
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28 renewable (13.4%) energy sources in the global total primary energy supply remains too wide
29 to be closed in the coming decennia, as stated by market analysts1. Shale gas is here
30 considered as an additional non-renewable energy source for the transition period2. It can
31 partly substitute the depleting conventional gas resources and thus decrease the dependency of
32 many countries on these traditional supplies3, 4. At the same time, shale gas development has
33 become a source of controversies among researchers, policy makers and the general public
34 with respect to largely unknown environmental impacts2, 5-9. The suspected deterioration of
35 quality and quantity of water resources, air pollution, increased traffic, noise and light
36 pollution, induced seismic activity and adverse health impacts are the subjects of concern9.
37 The water-related issues deserve special attention. Hydraulic fracturing, which is a basic
38 technology for gas production from shale gas reservoirs, involves pumping of the fracturing
39 fluid into the well under high pressure in order to increase permeability of the shale10, 11. The
40 fracturing fluid contains chemicals added to facilitate shale gas recovery, including gelling
41 agents, surfactants, friction reducers, corrosion and scale inhibitors, biocides, acids and pH
42 adjusting agents12-16. A mixture of the fracturing fluid and formation water, generally known
43 as flowback water, returns to the surface within several days after fracturing with the daily
44 flows sometimes exceeding 1000 m3 17, 18. Flowback water is less saline than formation water
45 and contains chemicals from fracturing fluid as well as their transformation products11, 19.
46 Formation and connate water, generally known as produced water, continues flowing from the
47 well for months to years after fracturing, though its daily flow constitutes only a few cubic
48 meters. Produced water is generally more saline than flowback water and contains released
49 methane and constituents of the shale, such as organic hydrocarbons and naturally occurring
50 radioactive material (NORM)19.
51 Options for flowback and produced water (FPW) management include disposal in the
52 subsurface through deep injection wells, reuse for the next fracturing activity and/or treatment
2
53 with subsequent discharge to injection wells or surface waters20. Whereas disposal in the deep
54 injection wells was the main technology for FPW management in the initial years of the shale
55 gas boom in the USA, reuse of flowback and discharge of produced water after appropriate
56 treatment has become more often utilized recently21, 22. The development of the Marcellus
57 shale in the USA lacking deep injection wells in proximity of the shale gas play was the main
58 driver for searching for reuse alternatives21, 23.
59 The choice of the FPW management strategy in favour of treatment followed by reuse or
60 discharge is also expected in Europe due to the lack of deep injection wells and legislative
61 constraints24, 25. European legislative instruments, including amongst others the EU Water
62 Framework Directive, the associated Groundwater Directive and the Convention for the
63 Protection of the Marine Environment of the North-East Atlantic (OSPAR convention) aim at
64 zero environmental harmful discharge of oil and gas wastewater26. To date only general water
65 quality parameters and inorganic constituents of shale gas FPW are extensively characterized,
66 whereas knowledge on presence and effects of individual organic compounds is rather
67 scarce16, 20, 27-29.
68 Characteristics, potential toxicity and treatability of compounds, which are present in
69 fracturing fluids are evaluated in recent reviews12, 30. However, these compounds may and are
70 partly known to undergo structural changes downhole under high pressure, temperature and
71 salinity15, 31. Whereas fracturing fluids will reach the environment only as a result of
72 accidental events, such as surface spills, fracturing of the well casing or interconnection with
73 neighbouring wells, at least part of shale gas FPW will be inevitably discharged to open water
74 bodies after certain level of treatment. FPW treatment strategies focus on removal of oil,
75 grease and salts, while specific contaminants originating from fracturing fluids remain largely
76 unaddressed and may negatively influence and surface water ecosystems and drinking water
77 sources30. The aim of this paper is to identify organic contaminants in FPW potentially
3
78 hazardous to environment using a risk quotient approach. The paper presents the case of the
79 Dommel river in the Netherlands as an example calculation of the FPW impact on the
80 ecosystems of small rivers and streams, thus giving a wider applicable framework for further
81 calculations of such impacts for other watersheds. Furthermore, the efficiency of the FPW
82 treatment methods towards removal of the identified potentially hazardous compounds is
83 reviewed and the strategies for their elimination are proposed. Because the existing literature
84 on the composition of flowback and produced water currently does not provide sufficient data
85 on the concentrations of a vast number of compounds with proven human toxicity, which are
86 regulated by U.S. National Primary Drinking Water Regulations, WHO guidelines and EU
87 regulations (e.g. many chlorinated organic compounds), impact of FPW on drinking water
88 sources deserves additional research and is not covered by this review.
89 2. Identification of individual organic compounds in flowback and produced waters
90 The organic contaminants of shale gas FPW include compounds injected in the fracturing
91 fluid, compounds of the formation which are mobilized when being brought in contact with
92 fracturing fluid, and products of physico-chemical and biological transformation of organic
93 fracturing chemicals32. It is anticipated that fracturing chemicals dominate in early flowback,
94 whereas chemicals of formation dominate in late flowback and produced water17, 32, 33. In this
95 paper, ultimately the organic chemicals of both flowback and produced water are assessed.
96 Chemical characterisation of FPW addresses mostly inorganic chemicals including salts,
97 scalants and heavy metals. With respect to organic components, FPW is usually characterised
98 using general parameters, such as total and dissolved organic carbon (TOC and DOC), oil and
99 grease and the sum of concentrations of benzene, toluene, ethylbenzene and xylenes (BTEX).
100 For example, the U.S. Geological Survey National Produced Water Database contains data on
101 TOC, DOC, biological oxygen demand (BOD), chemical oxygen demand (COD) and several
4
102 individual organic compounds (methane, acetone, acetate, BTEX, phenols, ethylene glycol)
103 but only for limited number of shale gas producing wells34. At the same time reporting exact
104 composition of fracturing fluids is done by many shale gas production companies and the vast
105 amount of data are available on-line in a FracFocus database35. The presence of potentially
106 hazardous organic compounds in the fracturing fluids became one of the main reasons for
107 negative public and policy attitude in many countries towards shale gas production4, 36, 37.
108 Much uncertainty about the fate of this chemicals in the well under high pressure and high
109 temperature conditions exists. Data on the exact FPW composition with respect to organic
110 compounds are still scarce, mostly because the complex nature of these liquids remains a
111 challenge for analytical chemistry. The overview of original data on analytical detection of
112 individual organic compounds in shale gas FPW available in the open literature sources is
113 given in Table 1.
114 2.1. Detection of volatile and semi-volatile organic compounds using gas
115 chromatography
116 To date, the largest sources of information on quantitative determination of particular organic
117 compounds in shale gas FPW are the reports of Hayes (2009) and Hayes and Severin (2012)17,
38
118 . The reports cover sampling of 19 wells of Marcellus shale (Pennsylvania and West
119 Virginia, USA) and 5 wells of the Barnett Shale (Texas, USA) (Table 1). Fifteen volatile
120 organic compounds (VOCs) and seventeen semi-volatile organic compounds (sVOCs) were
121 detected by the authors in more than one FPW sample. The detected VOCs included BTEX
122 and their alkyl derivatives, carbon disulfide, acetone and halogenated compounds, including
123 trichlorobenzene and bromoform. Polycyclic aromatic hydrocarbons (PAHs), phthalates,
124 phenols and pyridine were present among analysed sVOCs. Most of the compounds were
125 found in µg/l levels, whereas BTEX, carbon disulfide and pyridine were determined in low
126 mg/l in the FPW from several wells. Pesticides, polychlorinated biphenyls (PCBs) and a
5
127 number of VOCs and sVOCs were occasionally detected in single samples. The authors
128 concluded that their detection is attributed rather to the sampling and analytical errors then to
129 the actual presence of these compounds in the FPW.
130 Lester et al. (2014) showed similar composition of flowback water from Denver-Julesburg
131 basin with respect to sVOCs39. Acetone was the dominating VOC in flowback water with a
132 concentration of 16 mg/l, thus two orders of magnitude higher than concentration reported by
133 Hayes (2009)17. Other VOCs, present in the FPW analysed by Hayes (2009), were not
134 reported by Lester et al. (2014), except for xylenes and 2-butanone17, 39. This difference can be
135 explained by the less sensitive sampling and analytical methods used in the latter study.
6
136 Table 1. The overview of original literature data on analysis of individual organic compounds in shale gas FPW
Analyzed Extraction Analytical

Source Shale basins Water Detection
compounds method method
Flowback and
Marcellus shale (19
Hayes, 2009; produced 70 VOC; 116 sVOC;
wells);
Hayes and (Marcellus shale); 22 Pesticides; 7 PCBs; Purge-and-trap GC-MS* Quantitative
Barnett shale
Severin, 2012 Flowback Ethylene glycol
(5 wells)
(Barnett shale)
Liquid\liquid
Maguire- Marcellus shale; Identification of organic extraction with
Boylee and Eagle Ford shale; Produced compounds using NIST chloroform (acidified GC-MS* Qualitative
Barron, 2014 Barnett shale library and non-acidified
conditions)
Identification of organic
Liquid\liquid
Orem et al., Marcellus shale; Flowback and compounds using NIST Semi-
extraction with GC-MS*
2014 New Albany shale produced library and standard quantitative
dichloromethane
compounds

Denver-Julesburg
Thurman et al., basin; Barnett shale; Flowback HPLC/

Ethoxylated surfactants Direct injection Qualitative
2014 Marcellus shale; and produced Q-TOF-MS**
Haynesville basin
Biocides (ADBAC,
glutaraldehyde); Surfactant
Ferrer and Denver-Julesburg Flowback HPLC/
(Cocamidopropyl Direct injection Qualitative
Thurman, 2015 basin and produced Q-TOF-MS**
dimethylamine); Thickener
(Guar gum)
Purge and trap Quantitative

VOC; GC-MS*;
Lester et al., Denver-Julesburg (VOC, sVOC); (VOC, sVOC);
Flowback sVOC; HPLC/
2015 basin Direct injection Qualitative
Surfactants Q-TOF-MS**
(trace organics) (trace organics)
Purge and trap

GC-MS;*
Thacker et al., VOC; sVOC; (VOC, sVOC);
Barnett shale Not specified HPLC- Qualitative
2015 non-volatile organics Direct injection
HRMS***
(trace organics)

Linear aliphatic
Regnery et al., Denver-Julesburg Solid-phase
Produced hydrocarbons (n-C10 to n- GC-MS* Quantitative
2016 basin extraction
C32); PAH-16
137
138 * - gas chromatography coupled with mass spectrometry;
139 ** - high pressure liquid chromatography coupled with quadrupole time-of-flight mass spectrometry;
140 *** - high performance liquid chromatography coupled to high resolution mass spectrometry;
141

142 Several recent peer-reviewed publications were aiming at qualitative or semi-quantitative
143 detection of organic pollutants in shale gas FPW by non-target analysis32 29. The authors
144 identified a variety of saturated aliphatic and aromatic hydrocarbons present in the FPW.
145 Maguire-Boyle and Barron (2014) applying acidified conditions for polar compound
146 extraction from FPW detected large number of alkanes, resins, asphaltenes, heterocyclic and
147 halogenated compounds, which were not reported by Orem et al. (2014)29, 32. Also Maguire-
148 Boylee and Barron (2014) analysed produced rather than flowback water, where compounds
149 of formation typical for oil and gas produced waters are present in higher variety and
150 concentrations29. In contrast, Orem et al. (2014) reported presence of compounds originating
151 from fracturing fluids (solvent 2,2,4-trimethyl-1,3-pentanediol, biocide hexahydro-1,3,5-
152 trimethyl-1,3,5-triazine-2-thione, friction reducer ethylene glycol), which were not detected
153 by Maguire-Boylee and Barron (2014)32. Whereas some compounds were present in early
154 flowback samples in concentrations reaching low mg/l levels, the rapid decrease of
155 concentrations in samples taken during first 20 days after fracturing operation was observed.
156 2.2. Detection of non-volatile organic compounds using liquid chromatography
157 Several authors used HPLC/Q-TOF-MS for qualitative detection of non-volatile organic
158 compounds in shale gas FPW39-42. A number of constituents of fracturing fluids were detected
159 by these authors. Thus, presence of ethoxylated surfactants in flowback waters from different
160 shale gas basins in the USA was proven in two studies39, 41. Representative compounds of the
161 cocamidopropyl family of surfactants were detected in FPW samples by several authors40, 42.
162 Biocide alkyl dimethyl benzyl ammonium chloride (ADBAC) was found in 54% of analysed
163 FPW samples by Ferrer and Thurman (2015), whereas another biocide, glutaraldehyde, was
164 found in none of the samples40. Thacker et al. (2015) reported presence of alkyl amines (acid
165 dispersants/surfactants) and 2-butoxyethanol (solvent/acid dispersant/surfactant) in shale gas
166 wastewater without specifying the water type42.
10
167 2.3. Knowledge gaps in detection of organic compounds in FPW
168 Both quantitative and qualitative data on the presence of organic pollutants in shale gas FPW
169 are scarce, especially concerning the compounds used in fracturing fluids for shale gas
170 production. Thus, no research on the presence of corrosion inhibitors and clay stabilizers,
171 including toxic compounds such as propargyl alcohol, thiourea and tetramethyl ammonium
172 chloride, in FPW has been conducted yet. The knowledge on biocides presence and
173 concentrations in FPW is limited to few compounds (ADBAC, hexahydro-1,3,5-trimethyl-
174 1,3,5-triazine-2-thione and glutaraldehyde)32, 40. Little is known on the transformation
175 products of fracturing fluid additives that are formed downhole under high temperature and
176 high pressure and return to the surface with FPW. The low molecular weight organics such as
177 acetone, acetate and pyridine, which is not attributed to the compounds commonly present in
178 fracturing fluids and formation waters, were found in the FPW in high concentrations as
179 possible transformation products of more complex organic molecules17, 39. Formation of
180 halogenated organic compounds in FPW is predicted by several authors, given high chloride
181 and bromide content of FPW and possible decomposition of fracturing fluid additives that
182 contain Cl and Br atoms in their molecular structure29. However, knowledge on halogenated
183 organics in FPW is still limited to identification of few aliphatic structures17, 29.
184 3. Risk screening of individual organic compounds
185 The available literature data on concentrations of individual organic compounds in the shale
186 gas FPW were used for their environmental risk screening via Predicted Effect
187 Concentration/Predicted No Effect Concentration (PEC/PNEC) approach43. Briefly, the
188 environmental concentrations in the receiving surface water (PECs) were predicted for the
189 worst case scenario of FPW discharge with no removal of individual organic compounds
190 because of inadequate treatment. They were compared with PNECs for fresh water organisms
11
191 derived from literature or calculated from toxicity data using assessment factors. A resulting
192 risk quotient (RQ) above the value of 1 indicates potential risk of an organic compound to the
193 surface water ecosystems and implies the necessity of its removal prior to wastewater
194 discharge.
195 3.1. Determination of PEC for surface fresh waters
196 Small streams can be heavily impacted by the discharge of shale gas FPW, even after FPW
197 treatment. The river Dommel located in the province of Noord Brabant (the Netherlands) was
198 used as a model stream for calculation of the impact of FPW chemicals on aquatic
199 environment (Fig. 1). The Dommel has a total length of 120 km, with 85 km of downstream
200 flow located within the Netherlands. The average flow at the river mouth is 14 m3/s, dropping
201 to 3 m3/s in the dry periods44. The water is not directly abstracted for drinking water
202 production, nor intensively used for recreational purposes, therefore, direct negative impact of
203 treated produced water discharged to Dommel on human health is considered to be minimal
204 and is not reviewed further.
205 A possible shale gas production field located in the Dommel catchment basin within the
206 Netherlands has an area of 1510 km2 44. The development of shale gas resources within the
207 whole catchment basin was assumed, using a scenario with a well density of 1 well/km2 45. In
208 this scenario 329 wells are drilled over an area of 330.5 km2 within the Dommel catchment
209 basin. Though the drilling-free zones, such as nature and groundwater protection areas and
210 urban areas in the province of Noord Brabant are numerous, the drilling-free parcels are
211 dispersed with a radius of individual parcels not exceeding 2 km. The horizontal laterals of
212 each borehole can stretch up to 3 km, therefore, drilling-free areas were not considered as a
213 constrain for development of the whole field. An estimate number of 1510 wells was obtained
214 assuming the same well density in the whole Dommel catchment basin.
12
3
Qaverage = 14 m /s
3
Qdry periods = 3 m /s
2
S = 1510 km
Well density = 1
2
well/km
Nwells = 1510
(c) Waterschap De Dommel
(c) nlog.nl
215
216 Figure 1. River Dommel as a model stream for calculation of environmental impact of the FPW chemicals on aquatic environment
13

217 Average FPW volume of 2900 m3 is collected during 90 days after the fracturing event
218 according to data from Marcellus shale gas production facilities 17. The largest volumes of
219 flowback water are collected on the first day after the fracturing event with an average flow of
220 700 m3/day. However, on-site storage capacities for flowback water allows for equalization of
221 the FPW discharge. Therefore an average daily flow of 32 m3/well was calculated assuming
222 complete equalization of the FPW flow during initial 90 days of well operation.
223 The time-evolution of the shale gas production includes the rapid development of the field
224 during first 10-15 years followed by the decrease of the number of wells. Nicot et al. (2012)
225 estimated the total water use in the peak year of the shale development equal to 3.6% of the
226 total water use for Haynesville Shale, 3.1% for Eagle Ford Shale and 5.7% for Barnett
227 Shale18. The average peak year water use for the three shales is equal to 4.1% of the total
228 water demand for shale gas production. This figure can be also extrapolated into the number
229 of wells within a shale, hence Nicot et al. (2012) assumed the equal water use throughout a
230 shale18. With an estimate number of 1510 wells within the Dommel catchment basin
231 fracturing of 62 wells during a peak year is expected. A total daily generation of 1980 m3 of
232 FPW is estimated for these 62 wells based on the average daily flow of 32 m3/well. Possible
233 refracturing of the wells was not accounted for. The water reuse ratio of 70% similar to that
234 reported for Marcellus Shale was assumed21, therefore, decreasing predicted discharge of
235 treated FPW to Dommel to 600 m3/d. This value was compared with the lowest average river
236 flow of 3 m3/s (2.6 · 105 m3/d), resulting in a dilution factor of 435 for discharged FPW.
237 The maximal concentrations of organic compounds in FPW reported in the literature (see
238 Section 2) were divided by dilution factor to obtain their mean PECs. In total, PEC of 22
239 VOCs, 37 sVOCs and 3 non-volatile organic compounds were calculated (Table 2).
14
240 Table 2. Risk screening of organic compounds detected in FPW
Predicted
CMAX, PNEC, Assessment
Compound CAS # CMAX RQ Endpoint
µg/l µg/l factor
river, µg/l
Volatile organic compounds, µg/l
Reproduction of Daphnia magna,

1,2,4-Trimethylbenzene 95-63-6 400015 9.2 445 100 2.3
NOEC (21 d)

1,3,5-Trimethylbenzenea 108-67-8 190015 4.4 445 100 1.1
NOEC (21 d)
2-Butanone 78-93-3 24037 0.6 5580044 1 (SSD) 0.00001
Growth of Microcystis aeruginosa,

Acetone 67-64-1 1600037 36.7 1060044 50 0.003
NOEC (8 d)
Benzene 71-43-2 530015 12.2 190044 1 (SSD) 0.006

Benzothiazole 95-16-9 <2530 <0.1 1545 100 <0.007
NOEC (21 d)
Bromoform 75-25-2 9.315 0.0 2947 1000 0.001 Lepomis macrochirus, LC50
15

Number of hatched eggs of Danio rerio,

Carbon disulfide 75-15-0 730015 16.8 1044 100 1.7
NOEC (8 d)
Chloromethane Mobility of Daphnia magna,

74-87-3 15015 0.3 20044 1000 0.002
(Methyl chloride) EC50 (48h)
Reproduction of Ceriodaphnia dubia,

Ethylbenzene 100-41-4 67036 1.5 10044 10 0.02
NOEC (7 d)

Isopropylbenzene 98-82-8 16015 0.4 3544 10 0.01
NOEC (21 d)
Methylene chloride QSAR case study: Prediction of long-

75-09-2 5.515 0.0 31044 20 (QSAR) 0.00004
(dichloromethane) term NOEC for Daphnia magna (21 d)
n-Isopropyltoluene 99-87-6 5415 0.1 6.546 1000 0.02 Daphnia magna, LC50 (48h)
Toluene 108-88-3 810036 18.6 68044 1 (SSD) 0.03
Xylene 1330-20-7 650015 14.9 32744 1 (SSD) 0.05
Semi-volatile organic compounds, µg/l
Mortality of Pimephales promelas,

1,4-dioxane 123-91-1 6037 0.1 1000044 10 0.00001
NOEC (32 d)
16

Growth of Pseudokirchneriella
2-butoxyethanol (EGBE)b 111-76-2 6600051 151.5 88044 100 0.2
subcapitata, NOEC (72 h)
2,4-dimethylphenol 105-67-9 79037 1.8 2.1246 1000 0.9 Daphnia magna, LC50 (48h)

2-methylnaphthalene 91-57-6 2000036 45.9 2.345 100 20
NOEC (21 d)
Mortality of Daphnia magna,

2-Methylphenol (o-cresol) 95-48-7 15037 0.3 10044 10 0.003
NOEC (21 d)
3- & 4-Methylphenol (m- Mortality of Daphnia magna,

17037 0.4 10044 10 0.004
cresol and p-cresol) NOEC (21 d)

Benzyl alcohol 100-51-6 75015 1.7 100044 50 0.002
NOEC (21 d)
Bis(2-ethylhexyl)
117-81-7 87015 2.0 0.249 1 (SSD) 10
phthalate (DEHP)
Butyl benzyl phthalate 85-68-7 11036 0.3 6.544 10 0.04 Pimephales promelas, NOEC (42 d)
Mortality of Oncorhynchus mykiss,

Dimethylphthalate 131-11-3 1537 0.03 22044 50 0.0002
NOEC (102 d)
17

Length of Oncorhynchus mykiss, NOEC

Di-n-butyl phthalate 84-74-2 13015 0.3 1044 10 0.03
(99 d)
Di-n-octyl phthalate 117-84-0 560030 12.9 6.446 50 19 Daphnia magna, LC50 (48h)
Growth of Pseudokirchneriella
Ethylene glycol 107-21-1 5815 0.1 1000044 10 0.00001
subcapitata, NOEC (72 h)
Fluorene 86-73-3 40.715 0.1 0.2546 100 0.22 Ictalurus punctatus, LC50 (48h)
Growth of Oncorhynchus gorbuscha

Naphthalene 91-20-3 140015 3.2 2.444 50 1.3
NOEC (40 d)
Changes in general physiology of

Phenanthrene 85-01-8 140036 3.2 2.5746 100 65.6
Lepomis macrochirus, EC50 (96 h)
Growth of Cirrhina mrigala,

Phenol 108-95-2 83037 1.9 844 10 0.2
NOEC (60 d)
Growth of Ceriodaphnia dubia,

Propylene Glycol 57-55-6 16015 0.4 26000044 50 0.000001
NOEC (7 d)
Pyrene 129-00-0 1315 0.03 0.62646 100 0.41 Growth of Daphnia magna, EC50 (24 h)
18

Mobility of Daphnia magna,

Pyridine 110-86-1 260015 6.0 30044 1000 0.02
EC50 (48 h)
Non-volatile organic compounds, µg/l
Alkyl dimethyl benzyl

68424-85- Reproduction of Daphnia magna,
ammonium chloride >1038 >0.02 0.41548 10 >0.05
1 NOEC (21 d)
(ADBAC)c
Hexahydro-1,3,5-
59887-80- Immobilization of Daphnia magna,
30 46
Trimethyl-1,3,5- 1500 3.4 0.114 1000 11.1
8 EC50 (48 h)
triazinane-2-thioned
2,2,4-Trimethyl-1,3- Growth of Pseudokirchneriella

144-19-4 47030 1.1 10944 1000 0.01
pentanediole subcapitata, EC50 (72 h)
241
a
242 - Compounds with PEC<1 are highlighted in bold
b
243 - The maximal concentration of 2-butoxyethanol in the effluent of wastewater treatment plant treating unconventional oil and gas wastewater by
244 combination of settling and chemical precipitation is used as CMAX42
c
245 - ADBAC was detected in 54% of FPW samples at concentrations above the LOD = 10 µg/l38
d
246 - EC50 data for 3,5-dimethyl-1,3,5-thiadiazinane-2-thione (dazomet) were used for PNEC calculation
e
247 - EC50 data for 2,2,4-Trimethyl-1,3-pentanediol diisobutyrate were used for PNEC calculation
248
249
19

250 3.2. PNEC assessment and RQ calculation
251 PNEC of a chemical compound in aquatic environment is an indicatory parameter calculated
252 by extrapolation of toxicological laboratory data for the most sensitive species to possible
253 field impact of the compound, using the assessment factors43. The PNECs for individual
254 organic compounds in FPW were either obtained from online databases or from peer-
255 reviewed literature sources46-51. Most of the PNECs in these databases were calculated from
256 chronic and acute toxicity data with assessment factors of 10 to 1000. PNECs of benzene,
257 toluene, xylenes and 2-butanone were calculated using the 5th percentile of a species
258 sensitivity distribution (SSD).
259 Risk quotients of three VOCs (1,2,4-Trimethylbenzene, 1,3,5-Trimethylbenzene and carbon
260 disulfide), three PAHs (naphthalene, 2-methylnaphthalene and phenanthrene), two phthalates
261 (DEHP and Di-n-octyl phthalate (DnOP)), and the transformation product of biocide dazomet
262 (hexahydro-1,3,5-trimethyl-1,3,5-triazinane-2-thione) exceeded 1. These compounds will be
263 further referred to as “prioritized shale gas-related organic compounds”.
264 PAHs and phthalates may originate from the connate water of formation, as well as the
265 fracturing fluid17, 29. Methylation of benzene rings which leads to the formation of 1,2,4-
266 trimethylbenzene and 1,3,5-trimethylbenzene possibly takes place downhole under high
267 temperature and high pressure conditions. Carbon disulfide is not used in fracturing fluid, but
268 is a degradation product of some components of fracturing fluid, such as friction reducers and
269 biocides17, 52.
270 Removal of 2-butoxyethanol is reviewed in this paper despite its comparatively low RQ (0.2)
271 because of its abundant utilization in fracturing fluids and numerous cases of groundwater and
272 surface water contaminations reported in the USA12, 53. ADBAC was detected in FPW only
273 semi-quantitatively with RQ>0.05. Giving the low acute toxicity of ADBAC and uncertainty
20
274 over the maximal concentrations of this biocide in FPW it is reviewed as prioritized shale gas-
275 related organic compound. Removal of halogenated organics is also considered in this study.
276 Despite 1,2,3-trichlorobenzene was the only organohalogen in FPW with RQ above 1, a
277 number of authors confirmed the presence of halogenated aliphatic and aromatic organics and
278 predicted their formation from high concentrations of Cl- and Br- in FPW29, 32. Removal of
279 hexahydro-1,3,5-trimethyl-1,3,5-triazinane-2-thione is not further reviewed as the data on its
280 behaviour in wastewater treatment systems were not found in the literature.
281 4. Treatment strategies for removal of prioritized shale gas-related organic
282 compounds
283 The treatment methods used for shale gas FPW include basic separation technologies
284 designed for removal of TSS, oil and grease, and advanced treatment technologies designed
285 for removal of dissolved organic compounds, inorganic ions and radioactive materials26, 54, 55.
286 Phase separation underlies basic separation technologies, which include centrifugation,
287 hydrocyclones, flotation, media filtration, coagulation/flocculation and evaporation.
288 Centrifugation and hydrocyclones provide separation of suspended solids from water by
289 gravity, but are less effective towards oil and grease removal55. Flotation and coagulation can
290 efficiently remove dispersed oil and grease, therefore, they are often utilized for produced
291 water treatment.
292 The most common advanced treatment technologies utilized for oil and gas produced water
293 treatment include membrane filtration, thermal distillation, adsorption, ion exchange and
294 advanced oxidation. Nanofiltration and reverse osmosis (RO) units are utilized for removal of
295 inorganic ions from produced water with TDS below 40 g/l56. However, TDS of shale gas
296 produced water can reach 200 g/l, therefore other technologies such as thermal distillation are
297 used instead of RO26. Mechanical vapour recompression is particularly suitable for
21
298 demineralized water recovery from shale gas produced water with high TDS57. Sorption to
299 activated carbon, advanced oxidation and biological treatment are used for removal of
300 dissolved organic compounds, often preceding reverse osmosis in order to remove potential
301 foulants from feed water58.
302 The detailed description of treatment technologies, their advantages and drawbacks, energy
303 consumption and cost efficiency can be found in a number of reviews on produced water
304 treatment26, 54, 55, 59-62. This review is focused instead on the ability of produced water
305 treatment technologies to remove prioritized shale gas-related organic compounds as defined
306 in Section 3. Influence of operational parameters and matrix effects, especially high salt
307 content, on organic compounds removal is also discussed.
308 4.1. Basic separation technologies
309 Basic separation technologies are not designed for removal of individual organic
310 contaminants. However, some of the compounds are removed through volatilization or
311 sorption to suspended particles. Stripping of VOCs and, to lesser extent, sVOCs, occurs in
312 dissolved air flotation (DAF) units63 (Table 3). In contrast, low (10%) removal of volatile and
313 semi-volatile chlorinated organic compounds, such as halomethanes and chloroethylenes in a
314 DAF unit was observed64. Removal of VOCs decreases when oil and grease content of
315 refinery wastewater increases from 100 to 500 mg/l, possibly because oil and grease
316 accumulation on the water surface reduces surface volatilization of these compounds64. With
317 oil and grease content being on average below 50 mg/l11 significant fraction of VOCs is
318 expected to be removed from shale gas FPW in DAF units.
319 Partial removal of hydrophobic semi-volatile and non-volatile compounds, such as high
320 molecular weight PAHs, can be accomplished by their distribution to dispersed oil droplets
22
321 with subsequent skimming of the droplets from water surface65. However, removal of PAHs
322 via this mechanism is quite low, e.g., Younker and Walsh (2014) reported naphthalene
23
323 Table 3. Removal of prioritized shale gas-related organic compounds via selected FPW treatment processes
Technology VOCs PAHs Phthalates ADBAC 2-BE Organohalogens
Flotation + to ++61 + to ++64 N.D. N.D. N.D. +62
Coagulation/flocculation ++65 ++64,65 ++66 N.D. -51 -69
Electrocoagulation N.D. ++73 +++72 N.D. N.D. -71
Membrane separation
+ to ++75 +++78 +++77 +++79 -80 + to +++75,76
(Nanofiltration & reverse osmosis)
Thermal distillation
++55 ++84 N.D. N.D. N.D. +++83
(VCD, MSF, dewvaporation)
MPPE +++96,97 +++96,97 N.D. N.D. N.D. +++96,97
+ to
Aerobic biodegradation + to ++65,114 + 118-120 ++ to +++121-123 +++125,126
65,115,116
++ ++127-129*
Anaerobic biodegradation + to ++113 - to ++115 + 119 ++121-123 +++125
MBR +++132,133,136 +++132,133 +120 N.D. N.D. + to +++134
324
325 - removal <20%; + removal 20-50%; ++ removal 50-90%; +++ removal >90%
326 * - removal attributed to the subsequent application of anaerobic and aerobic treatment
24

327 removal of <15% in the DAF unit with initial naphthalene concentration of 1 mg/l66. Phenol
328 removal was not observed in the same study, therefore, removal of water soluble organic
329 compounds, including 2-butoxyethanol, is not expected, if absorption to dispersed oil with
330 subsequent skimming is the major mechanism of their removal66.
331 Removal of PAH reached 20% (initial concentration - 19.1 µg/l) in the pilot-scale
332 coagulation-flocculation unit treating oil plant produced water with comparatively low
333 salinity (5 g/l of NaCl) with aluminium sulphate used as a coagulant67. Younker and Walsh
334 (2014) observed increase of naphthalene removal from 20% to 50% after addition of FeCl3 to
335 DAF unit as a coagulant66 Removal of phthalates (DEHP, di-butyl-phthalate, di-ethyl-
336 phthalate) in the full-scale installation treating landfill leachate by coagulation with FeCl3 was
337 below 50%68. Correlation between removal of phthalates and removal of DOC exists, with
338 higher phthalate removal observed when higher fraction of DOC is removed69. Higher
339 phthalate removal is achieved with aluminium ions used as coagulant instead of iron70. Gopal
340 (2007) reported low removal of halogenated disinfection by-products in coagulation processes
341 used in drinking water treatment71. Combination of charge neutralization, adsorption,
342 entrapment and complexation with coagulant ions are responsible for removal of organic
343 compounds in coagulation unit. Therefore removal efficiencies depend on physico-chemical
344 characteristics of compounds but also on operational parameters of the process72.
345 Electrocoagulation is the variation of coagulation process, where coagulant is generated in
346 situ by oxidation of electrode material. Besides generation of coagulant, the process promotes
347 degradation of organic matter by generation of oxidative species, such as hydroxyl ions,
348 hypochlorite and hypochlorous acid73. Kabdasli et al. (2009) reported complete mineralization
349 of aqueous DEHP (50-100 mg/l) in NaCl solution74. Nassef (2014) achieved complete
350 removal of PAHs (β-naphthols) from NaCl solution of 1 – 7 g/l by electrocoagulation, with
351 higher removal efficiencies at higher NaCl concentrations75. However, the author did not
25
352 study the mechanisms of β-naphthols removal and formation of halogenated transformation
353 products. At the same time, halogenation of organic compounds in highly saline produced
354 water can be expected during electrocoagulation73
355 4.2. Advanced treatment technologies
356 4.2.1. Membrane separation
357 Membrane separation is often employed for produced water treatment in oil and gas industry,
358 either as a combination of membranes with different retention properties (microfiltration and
359 ultrafiltration for removal of suspended matter followed by nanofiltration and reverse osmosis
360 for desalination) or as a desalination technology (reverse osmosis). The membranes in oil and
361 gas wastewater are preceded by different pre-treatment technologies (media filtration,
362 dissolved air flotation or biological treatment), because they are not resistant to oil
363 constituents, such as BTEX56. Microfiltration and ultrafiltration membranes are designed for
364 removal of suspended and colloidal matter, bacteria, viruses and high molecular weight
365 hydrocarbons and have low to moderate efficiency towards removal of low molecular weight
366 organic contaminants76.
367 Removal of VOCs, chlorinated organics and phthalates by nanofiltration and reverse osmosis
368 (RO) is reviewed by Agenson et al (2003) and Rodriguez et al (2012). Rejection of these
369 organic compounds is more effective with high desalting membranes with molecular weight
370 cut-off (MWCO) ≤ 100 Da, then low desalting membranes with MWCO = 200 Da 77, 78.
371 Consistently low removal of dichloroethylenes (<40%), halogenated methane (<50%) and
372 benzene (<55%) was observed with different types of high desalting RO membranes.
373 Removal of molecules with higher molecular weight, such as toluene (> 65%) and xylenes (>
374 90%) was considerably higher77. The authors concluded that membrane material, as well as
375 size, dimensions and logKow of organic molecules appeared to be important parameters
26
376 governing removal of organic compounds via RO with low rejection of volatile non-branched
377 low molecular weight compounds.
378 Removal of high molecular weight phthalates, including DEHP, exceeded 90% with RO, but
379 also nanofiltration (MWCO = 300 Da) and ultrafiltration (MWCO = 8000 Da) membranes
380 independent of the concentrations of phthalates79 Sorption to membrane surface is possible
381 mechanism for phthalate removal by ultrafiltration. Removal of 8 PAHs, including
382 naphthalene and phenanthrene exceeded 95% in a pilot-scale RO system applied to shale gas
383 produced water.80 DBNPA, a biocide, often used in hydraulic fracturing operations, is also
384 efficiently removed by RO membranes (rejection of 98.5 to 99.5%)81. DBNPA is even
385 recommended for usage as an anti-fouling agent in drinking water treatment81. At the same
386 time, low molecular weight semi-volatile 2-butoxyethanol was not rejected with ASF-99 RO
387 membrane characterized by high NaCl rejection82.
388 In summary, reverse osmosis can remove most of the organic compounds of concern from
389 FPW, except of low molecular weight chlorinated hydrocarbons and 2-butoxyethanol, which
390 are not rejected even by high-desalting RO membranes (Table 3).
391 4.2.2. Thermal distillation
392 The operational costs of thermal distillation technologies are several times higher than that of
393 reverse osmosis because of the high energy consumption26. At the same time, thermal
394 distillation is often utilized for FPW treatment in the full-scale installations, though it is
395 justified rather by the need to handle produced water with high salinity (TDS > 40 g/l) then by
396 cost efficiency26, 83, 84. Multistage flash (MSF), multi-effect distillation (MSD), mechanical
397 vapour recompression (MVR) and dew-vaporation are four most common thermal distillation
398 technologies, with MVR being most often used for shale gas FPW treatment26, 57.
27
399 High removal of VOCs in thermal distillation units is achieved mainly due to volatilization
400 with vapour being removed from the system during degassing events (Table 3). Thus, Hayes
401 et al. (2014) observed 94% removal of VOCs in full scale MVR plant treating shale gas FPW
402 through degassing and pressure-relief valves throughout the separator tank. The rest of VOCs
403 (6% of the initial concentration) was found in distillate, being condensed from vapour
404 together with distilled water, while brine did not contain VOCs57. Removal of chlorinated
405 disinfection by-products (trihalomethanes and haloacetic acids) from sea water with high
406 bromide content reached 99% in a MSF unit85. Whereas trihalomethanes were completely
407 vented to the air, 82% of less volatile haloacetic acids were found in brine. PAH removal by
408 distillation is less effective, with 8% of naphthalene and >30% of methylnaphthalene
409 recovered in the distillate of the circulation evaporator treating oil field produced water86. No
410 data on removal of phthalates, 2-butoxyethanol and quaternary ammonium compounds were
411 found in the literature, though high solubility and moderate volatility of 2-butoxyethanol
412 indicate that this compound can be partly condensed from vapour.
413 The available literature implies that thermal distillation technologies do not abate VOCs and
414 sVOCs, but rather transform them from liquid to gas phase, followed by partial condensation
415 in treated distillate (Table 3). The vapour thus needs to be treated before being released to the
416 atmosphere in order to prevent environmental and human health risks related to VOCs.
417 4.2.3. Adsorption to activated carbon
418 Adsorption to activated carbon is usually utilized as a polishing step in wastewater treatment,
419 because carbon can be easily overloaded with organics, especially with oil and grease26.
420 Granular activated carbon (GAC) is preferred to powdered activated carbon (PAC) for oil and
421 gas industry applications because of the lower carbon usage rate and associated operational
422 costs87. Adsorption to activated carbon is efficient towards wide variety of organic
28
423 compounds, but strongly depends on many factors, including dose and contact time, intrinsic
424 properties of activated carbon, size, chemical structure and polarity of the adsorbates and
425 solution properties, such as presence of competing organic matter, pH and salinity.
426 Efficient removal of PAHs, including naphthalene and phenanthrene, quaternary ammonium
427 compounds, 2-butoxyethanol and chlorinated organic compounds via sorption to activated
428 carbon was reported in the literature88-92 However, removal of phthalates by activated carbon
429 is inefficient, especially at basic pH, because of the increased electrostatic resistance between
430 negatively charged activated carbon surface and phthalate anions, produced under basic
431 conditions93, 94. Low affinity of phthalates to activated carbon will ultimately result in low
432 performance of full scale installation, as shown by Asakura and Matsuto (2009), who
433 predicted 50-70% removal of DEHP from leachate, based on carbon utilization rate of 1
434 kg/m3*d and initial DEHP concentration of 50 µg/l68.
435 It should be noted, that most of the experiments on sorption of organic contaminants were
436 performed in distilled water or distilled water with artificial addition of organic matter or
437 NaCl, therefore, knowledge on sorption of individual organic contaminants in real FPW is
438 missing. Moreover, different conditions of the experiments, reported in the literature, did not
439 allow comparison of the adsorption capacity of activated carbon for all prioritized shale gas-
440 related compounds from shale gas FPW.
441 High water salinity has several opposite effects on the adsorption of organic compounds. It is
442 widely accepted that increased salinity improves sorption of organic compounds to activated
443 carbon decreasing their solubility in the solution (so-called “salting out effect”) and
444 supressing electrostatic repulsions between organic compounds and activated carbon89, 95.
445 Thus, adsorption of benzyltriethyl ammonium chloride in presence of NaCl (Freundlich
446 adsorption constant Kf = 285 mg/g) is higher than its adsorption in fresh water solution (Kf =
29
447 235 mg/g)90. Increased adsorption of PAH to different adsorbents with increased salt
448 concentration was reported by several authors 95. At the same time, high salinity does not
449 influence or may even enhance the adsorption of strongly hydrophobic compounds with low
450 solubility, such as naphthalene or di-n-butyl phthalate, at low concentrations89, 96. Negative
451 effect of increased salinity was also observed by some authors. Thus, adsorption of
452 phenanthrene at low concentrations (3-10 µg/l) is lower in salt water, than in fresh water,
453 whereas at high concentration (50-200 µg/l) the effect is opposite88. High salinity may induce
454 formation of water clusters on surface hydrophilic oxygen and carbonyl group, thus, directly
455 competing with sorption of organics and hindering access to the graphitic basal planes of
456 activated carbon97. Thus, sorption of toluene in controlled pH solution decreased from 750 to
457 350 mg/g with increase of KCl concentration from 0.05 M to 0.7 M97.
458 Other parameters, influencing sorption of organic compounds from FPW to activated carbon
459 include dispersed oil content, temperature and pH. Dispersed oil decreases sorption of low
460 molecular weight organic matter by competing with sorption sites on the surface of activated
461 carbon and blocking access of low molecular weight organics to the inner micropores89. Thus,
462 addition of 100 mg/l emulsified crude oil decreased BET surface area of powdered activated
463 carbon from 907.7 m2/g to 3.8 m2/g89. Consequently, adsorption to GAC in oil and gas
464 produced water treatment always follows pre-treatment step designed for oil and grease
465 removal, e.g., DAF or coagulation.
466 4.2.4. Macro porous polymer extraction (MPPE)
467 MPPE is a liquid-liquid extraction technique developed for hydrocarbon removal from oil and
468 gas produced water with extraction liquid immobilized in porous polymer particles98. The
469 particles are immobilized in columns and periodically regenerated in-situ by stripping with
470 low pressure steam followed by condensation of recovered hydrocarbons in a concentrated
30
471 solution. The pilot field tests and results obtained from full scale installations proved that 95-
472 99% removal of BTEX, PAHs, CS2 , aliphatic and aromatic chlorinated hydrocarbons,
473 including volatile chlorinated hydrocarbons with low molecular weight, is achieved with this
474 technology (Table 3)98, 99. MPPE performance towards removal of fracturing fluid chemicals
475 has not been studied so far.
476 4.2.5. Advanced oxidation
477 Advanced oxidation processes are used in oil and gas produced water treatment for removal
478 of organic and some inorganic compounds, disinfection and removal of odour and colour26.
479 Commonly used oxidants include ozone, hydrogen peroxide, chlorine and Fenton’s reagent
480 (combination of hydrogen peroxide with ferrous iron). Flowback water treatment technology
481 based on the combination of hydrodynamic cavitation, ozonation, acoustic cavitation and
482 electrochemical oxidation is used for removal of organic matter, bacteria and scalants either
483 for flowback reuse or as a pre-treatment for reverse osmosis aiming at water discharge100.
484 Advanced oxidation processes remove vast majority of organic compounds present in FPW
485 (Table 3)70, 101. PAHs, including naphthalene and phenanthrene are efficiently removed by
486 ozonation with reaction rate being higher at acidic and neutral conditions102, 103. Combination
487 of ozonation with hydrogen peroxide, ultraviolet (UV) or both does not enhance PAH
488 removal102, Photocatalytic oxidation of PAH in produced water is much slower than
489 ozonation, probably, because of the light scavenging effect by turbidity103. Contrary to PAH
490 removal, only moderate removal of phthalates (30%) is achieved with ozone70 Combination of
491 ozone with catalysts (Cr3+, GAC) or alkalination of solution increases removal efficiency of
492 phthalates to 65-80% due to the higher decomposition of ozone into hydroxyl radicals70.
493 Ozonation is efficient towards removal of quaternary ammonium compounds, as shown by
494 Hernandez Leal et al. (2011), who achieved >98% removal of benzalkonium chloride (initial
31
495 concentration 1 mg/l) in aerobically treated grey water after application of 1.22 mg/l of
496 ozone104. Removal of 2-butoxyethanol by ozonation is not reported in the literature. However,
497 its removal by Fenton oxidation (combination of H2O2 and Fe(II)) from water-based food
498 paint wastewater (COD = 18 g/l, Cl- = 3.9 g/l) was above 95%105.
499 Halogenated aliphatic compounds (e.g., trichloromethane, trichloroethylene
500 tetrachloroethylene), as well as halogenated aromatic compounds and phthalates do not react
501 readily with ozone, therefore, combination with other oxidation processes, such as O3-UV and
502 O3-H2O2 systems generating OH˙ and other strong oxidants, are required for their
503 destruction106, 107. Additionally, ozonation of FPW with high chloride and bromide
504 concentration will promote formation of chlorinated and brominated organic compounds that
505 can be more toxic than parent compounds since ozone enhances formation of Cl˙ and Br˙
506 radicals107.
507 The rate constant of OH˙ reaction with chloride (kOH = 7.5 · 104 M-1 s-1) is significantly lower
508 than the rate constants of OH˙ reaction with organic compounds (kOH > 1 · 107 M-1 s-1) 39, 108.
509 Therefore increase of Cl- concentrations from 0 to 50 g/l only slightly decreases ozonation
510 efficiency catalysing ozone destruction by high salinity109. The presence of chloride also
511 slightly enhances ozone decomposition and radical formation, thus, decreasing ozone
512 selectivity110, 111. In contrast, significant negative influence of salinity on Fenton’s oxidation
513 process was found with Fenton’s reaction being inhibited by complexation of Fe3+ with Cl-
514 and scavenging of OH˙ radicals by chloride112.
515 Contrary to chloride, bromide with kOH of 8.5 · 108 M-1 s-1 may compete with organic
516 compounds significantly decreasing efficiency of ozonation in FPW by high concentrations of
517 bromide39. Whereas organic compounds with kOH >1 · 109 M-1 s-1 including BTEX, PAHs
518 and chloroethylenes will be targeted by hydroxyl radicals, oxidation of common low
32
519 molecular weight degradation products, such as acetate (kOH = 1.9 · 107 M-1 s-1), methanol
520 (kOH = 4.6 · 108 M-1 s-1) and trichloroacetate (kOH = 6 · 107 M-1 s-1) will be scavenged by
521 bromides39, 108. Application of ozonation for partial destruction of high molecular weight
522 organic compounds with high kOH followed by biological treatment or adsorption to activated
523 carbon can be implemented for removal of intermediates from FPW with high bromide
524 content113.
525 4.3. Biological treatment
526 Biological aerobic and anaerobic treatment of FPW was successfully implemented both in the
527 lab and industrial scale39, 58, 114. Aerobic biological treatment in sequencing batch reactor is
528 suitable for shale gas FPW with moderate salinity (TDS = 22.5 g/l) and high acetic acid
529 content (16 mg/l)39. Combination of anaerobic and aerobic treatment and a membrane
530 bioreactor is used as pre-treatment for organic matter removal prior to a membrane unit at the
531 Pinedale Anticline FPW treatment facility58, 114.
532 Low to moderate removal of VOCs, PAHs and phthalates during aerobic and anaerobic
533 treatment of industrial wastewaters is reported by several authors67, 115-117. Thus 40% of the
534 sum of PAHs present at initial concentrations of 15.2 µg/l were degraded in pilot-scale
535 aerobic SBR treating petrochemical wastewater at long hydraulic retention time (HRT = 22
536 d.)67. Two to three ring PAHs are more amenable to biodegradation under both aerobic and
537 anaerobic conditions when compared to PAH with >3 rings117. Thus, naphthalene removal
538 reached 61% in the aeration tank of the municipal sewage treatment plant (HRT = 3 h),
539 whereas removal of phenanthrene was <40% and removal of benzo(a)pyrene did not exceed
540 15%118. Selection of bacteria responsible for degradation of PAH might occur with increased
541 SRT after long-term reactor operation115, 119
33
542 Biodegradation of phthalates depends on their molecular weight, with high removal observed
543 for low molecular weight phthalates, such as dimethyl phthalate and diethyl phthalate, under
544 both aerobic and anaerobic conditions120, 121. Aerobic biological removal of high molecular
545 weight phthalates, such as DEHP, is negligible at different HRT and SRT.120, 122. DEHP and
546 DnOP are not degraded under anaerobic conditions either121.
547 Aerobic conditions are more favourable for biodegradation of quaternary ammonium
548 compounds, including ADBAC, when compared to anaerobic conditions123-125. Apart from
549 biodegradation, sorption to sludge contributes significantly to removal of QAC126. Decrease
550 of benzalkonium chloride concentrations in sludge of UASB reactor, operated on a mixture of
551 black water and kitchen waste for more than 2 years without sludge removal, was observed
552 over one year period, indicating that adaptation of anaerobic bacterial consortium with
553 subsequent increase of QAC biodegradation might occur126.
554 2-butoxyethanol was readily biodegradable both under aerobic and anaerobic conditions in
555 batch experiments with saline water and marine sediments127. Similar results were obtained in
556 an aeration tank of sewage treatment plant, with 2-butoxyethanol concentrations decreasing
557 from 140.6 µg/l to <0.1 µg/l128.
558 Biological removal of halogenated organic compounds under aerobic conditions is generally
559 low129. Co-metabolic removal by several groups of aerobic bacteria, including methane-
560 oxidizing methanotrophs, toluene oxidizers and phenol oxidizers is achieved, therefore, high
561 concentrations of methane, toluene and phenols observed in FPW will promote aerobic
562 degradation of halogenated organic compounds130. Combination of subsequent anaerobic
563 treatment for de-halogenation and aerobic treatment for ring cleavage of aromatic structures
564 and complete mineralization is the most efficient strategy for mineralization of haloorganic
565 compounds129-131.
34
566 Removal of organic pollutants is generally higher in membrane bioreactors (MBR) than in
567 conventional activated sludge treatment systems132. Membrane bioreactors (MBR) are
568 effective towards polar organic compounds that are removed by combination of sorption and
569 biodegradation, whereas removal of hydrophilic compounds is variable and depends on their
570 structure133. Removal of six PAHs, including naphthalene and phenanthrene, from synthetic
571 petrochemical wastewater in two aerobic MBR with sidestream filtration based on cross-flow
572 and semi dead-end filtration systems respectively, exceeded 90%134. Biological degradation
573 was the main removal mechanisms, responsible for at least 50% removal of each investigated
574 compound. Volatilization was responsible for removal of <15% of low molecular weight
575 PAH, whereas >20% of high molecular weight PAH were removed by adsorption134. Aerobic
576 submerged MBR is also suitable for removal of aliphatic hydrocarbons, monoaromatic
577 hydrocarbons, aliphatic acids, aromatic acids, and PAH from oil produced water with high
578 salinity135. However, phthalates are poorly removed in membrane bioreactor, as shown by
579 Llop et al (2009), who observed negligible removal of DEHP in the submerged-filter MBR
580 treating wastewater from chemical industry122. The data on QAC and 2-butoxyethanol
581 removal in MBR were not found, though high removal of these compounds is expected based
582 on the results achieved in conventional aerobic activated sludge reactors.
583 Removal of halogenated organic compounds in MBR depends not only on biodegradation
584 and/or volatilization, but also on sorption. Compounds with high log D (>3.2) and high
585 halogen content (>0.3), as well as compounds with low logD (<3.2) and low halogen content
586 (<0.1) are well removed (>85%) when compared to other organohalogens136. Combination of
587 anaerobic and aerobic MBR promote biodegradation of halogenated compounds, as
588 mentioned earlier129, 130.
589 High salinity of produced water is the main challenge for application of biological processes
590 for FPW treatment, because TDS concentrations above 10 g/l can negatively influence
35
591 biological activity by plasmolysis and loss of cell activity62. However, removal of organic
592 compounds in anaerobic and aerobic treatment systems are observed even at much higher
593 salinity. Thus, Belkin et al. (1993) reported DOC removal of 70% at TDS of 32 g/l and 40%
594 at TDS of 100 g/l in the combination of anaerobic and aerobic SBRs with HRTs of 20 days
595 and 6 days respectively treating wastewater from chemical industry131. TOC removal
596 decreased from 90% to 40% and COD removal – from 90% to 17% in the MBR treating real
597 oilfield produced water at 16 and 250 g/l TDS respectively137. The impact of FPW salinity on
598 biological removal of PAH, phthalates and QAC in activated sludge systems and MBR
599 requires further investigation, since available literature mainly reports biological removal of
600 these compounds from municipal and industrial wastewaters with low salinity.
601 5. Prospects for removal of prioritized shale gas-related organic compounds with
602 selected technologies
603 The main objectives for FPW treatment aimed at discharge to surface water include removal
604 of suspended matter, oil and grease, dissolved organic compounds and salts. Removal of
605 NORM is also required for the FPW with enhanced NORM content. The review of
606 technologies supports the choice in favour of DAF with coagulation followed by MBR,
607 ultrafiltration and reverse osmosis for FPW with low salinity and ozonation, GAC filtration
608 and thermal distillation for FPW with high salinity.
609 DAF assisted with coagulant addition achieves the best performance among the basic
610 separation technologies removing particles down to 0.3 µm, though removing only a minor
611 fraction of prioritized shale gas-related organic compounds mostly by stripping. Collection
612 and treatment of the generated off-gases is required to minimize negative impacts on the
613 environment and human health4.
36
614 Removal of organic compounds should precede the salt removal, because main methods
615 utilized for desalination are either negatively influenced by organic matter (reverse osmosis)
616 or cannot provide adequate removal of organic compounds with low molecular weight
617 (thermal distillation). Application of subsequent anaerobic and aerobic biological treatment,
618 where aerobic treatment stage can be designed as a submerged-filter MBR, is desired for
619 removal of organohalogens, naturally present in the produced water. MBR is more efficient in
620 removal of PAHs then conventional activated sludge, whereas its submerged-filter
621 configuration is characterized by lower volatilization of organic compounds, when compared
622 to the sidestream filtration134, 138. MBR can be followed by ultrafiltration and RO for removal
623 of TDS and, eventually, radioactive materials, such as radium-226139.
624 Fraction of low molecular weight hydrophilic organic compounds is often dominating DOM
625 of FPW making biological treatment feasible32, 39. However, presence of refractory organic
626 compounds, such as phthalates and certain transformation products of fracturing chemicals
627 may require application of alternative treatment strategies, such as adsorption to activated
628 carbon or ozonation either in combination with biological treatment or as a stand-alone
629 processes.
630 Treatment of FPW with high salinity (TDS > 40g/l) requires another strategy, as both
631 biological treatment and RO are not applicable at such salt concentrations. Thermal
632 distillation is normally used for treatment of FPW with high salinity. Apart from high energy
633 costs and significant amount of solid waste created, thermal distillation processes have several
634 disadvantages with respect to removal of prioritized shale gas-related organic compounds.
635 They transfer the VOCs and sVOCs mostly to the gas phase, concentrate organic compounds
636 with high molecular weight in brine, which can constitute up to 30% of initial water volume,
637 whereas low-molecular weight VOCs and sVOCs end up in the distillate. Pre-ozonation of
37
638 high-molecular weight organics coupled to adsorption to activated carbon or adsorption to
639 activated carbon alone can be used as a pre-treatment step before thermal distillation.
640 Source control measures, such as substitution of prioritized shale gas-related organic
641 compounds in frack fluids by less hazardous alternatives should be considered9. Thus, QAC
642 biocides should be substituted by easily biodegradable and less hazardous compounds, such
643 as glutaraldehyde52. The separation and multiple reuse of early flowback may be an effective
644 measure for prevention of environmental contamination, because prioritized shale gas-related
645 organic compounds originating from frack fluid will remain within the shale gas production
646 cycle, with only minor portion entering the environment5, 8, 9.
647 Finally, the impact of organic compounds from shale gas FPW on drinking water sources
648 deserves special attention. The existing uncertainties include the human toxicity thresholds,
649 the fate of organic contaminants in surface waters, their dilution before water intake for
650 drinking water production and capacity of various drinking water treatment technologies for
651 removal of these specific compounds. More elaborated studies on human toxicity assessment
652 of FPW chemicals, including analysis of organic compounds with proven human toxicity in
653 FPW and potential formation of disinfection by-products from FPW-originated precursors in
654 drinking water sources are needed.
655 Acknowledgement
656 This work was funded by the Netherlands Organisation for Scientific Research (NWO) Earth
657 and Life Sciences (ALW), project number 859.14.001, and the water utilities Brabant Water,
658 Oasen and WML.
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43
OH
O
CH3
H CH 3
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+
R
Reverse osmosis
Fracturing H CH 3
Cl
Thermal distillation

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Environmental Science & Technology is published by the American Chemical Society.

2 ecological impact and implications for treatment strategies.

15 components. This review addresses identification of individual organic contaminants in FPW,

21 hydrocarbons, phthalates), fracturing fluids (e.g. quaternary ammonium biocides, 2-

22 butoxyethanol) and downhole transformations of organic compounds (e.g. carbon disulphide,

23 halogenated organic compounds). Removal of these compounds by FPW treatment processes

24 is reviewed and potential and efficient abatement strategies are defined.

50 radioactive material (NORM)19.

58 driver for searching for reuse alternatives21, 23.

66 whereas knowledge on presence and effects of individual organic compounds is rather

67 scarce16, 20, 27-29.

68 Characteristics, potential toxicity and treatability of compounds, which are present in

82 treatment methods towards removal of the identified potentially hazardous compounds is

88 sources deserves additional research and is not covered by this review.

89 2. Identification of individual organic compounds in flowback and produced waters

92 fracturing fluid, and products of physico-chemical and biological transformation of organic

93 fracturing chemicals32. It is anticipated that fracturing chemicals dominate in early flowback,

96 Chemical characterisation of FPW addresses mostly inorganic chemicals including salts,

113 given in Table 1.

123 trichlorobenzene and bromoform. Polycyclic aromatic hydrocarbons (PAHs), phthalates,

129 the actual presence of these compounds in the FPW.

Analyzed Extraction Analytical

Maguire- Marcellus shale; Identification of organic extraction with

Barron, 2014 Barnett shale library and non-acidified

ACS Paragon Plus Environment

Thurman et al., basin; Barnett shale; Flowback HPLC/

Purge and trap Quantitative

Purge and trap

ACS Paragon Plus Environment

ACS Paragon Plus Environment

142 Several recent peer-reviewed publications were aiming at qualitative or semi-quantitative

151 from fracturing fluids (solvent 2,2,4-trimethyl-1,3-pentanediol, biocide hexahydro-1,3,5-

156 2.2. Detection of non-volatile organic compounds using liquid chromatography

165 dispersants/surfactants) and 2-butoxyethanol (solvent/acid dispersant/surfactant) in shale gas

166 wastewater without specifying the water type42.

167 2.3. Knowledge gaps in detection of organic compounds in FPW

173 concentrations in FPW is limited to few compounds (ADBAC, hexahydro-1,3,5-trimethyl-

174 1,3,5-triazine-2-thione and glutaraldehyde)32, 40. Little is known on the transformation

184 3. Risk screening of individual organic compounds

187 Concentration/Predicted No Effect Concentration (PEC/PNEC) approach43. Briefly, the

195 3.1. Determination of PEC for surface fresh waters

204 and is not reviewed further.

(c) Waterschap De Dommel

ACS Paragon Plus Environment

240 Table 2. Risk screening of organic compounds detected in FPW

Volatile organic compounds, µg/l

Reproduction of Daphnia magna,

Reproduction of Daphnia magna,

2-Butanone 78-93-3 24037 0.6 5580044 1 (SSD) 0.00001

Growth of Microcystis aeruginosa,

Benzene 71-43-2 530015 12.2 190044 1 (SSD) 0.006

Reproduction of Daphnia magna,

ACS Paragon Plus Environment

Number of hatched eggs of Danio rerio,

Chloromethane Mobility of Daphnia magna,

Reproduction of Ceriodaphnia dubia,

Reproduction of Daphnia magna,

Methylene chloride QSAR case study: Prediction of long-