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Characterization of Marcellus 

and Barnett Shale Flowback 

Waters and Technology 

Development for Water Reuse

Tom Hayes, GTI

Hydraulic Fracturing Technical Workshop #4

USEPA Meeting Facilities

Arlington, VA

March 30, 2011


Major R&D Efforts on Produced 

Water Management

 Industry Water Conservation Consortia 

Barnett Shale (BSWCMC)

Appalachian Shale (ASWCMC)

 Marcellus Shale Coalition

 Individual Developer Company Testing 

of Available Know-How

 RPSEA Program

 NETL-DOE Program 

 NYSERDA Project on Shale Gas Issues

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Components in Flowback Water 

Constituents of Produced Water

Frac Job Additives

+
Natural Gas Industry Water Use in 

the Appalachian and Barnett Shale

Frac Jobs Drilling Other

5%

94%

(2010 Estimate)

<1%
Chemistry and 

Composition of 

Flowback Water

Components in Flowback Water 

Constituents of Produced Water

Frac Job Additives

+
Sampling and Analysis of 

Flowback Water 
Data on Sampling and Analysis of 

Flowback Water

 Marcellus Shale Water Characterization 

Funded by MSC and ASWCMC Consortia

Sampling from 19 locations

Includes general chemistry and detailed 

analysis of constituents of interest

Lists of Constituents of Interest provided by 

the WV-DEP and PA-DEP

Over 250 determinations performed on samples

 Barnett Shale Water Characterization

Sampling from 5 locations

Same sampling and analysis approach as 

Marcellus

Funded by RPSEA-DOE / Coord w/ BSWCMC
Marcellus Shale Approach

 Samples taken at 0, 1, 5, 14, and 90 days 

following the frac job at each location

 Sampling at Day 0:

 Raw Water without additives

 Raw Water with chemical additives before sand addn.

 Uniformity of sampling and analysis 

Standardized Plans (FSAP, QAPP)

Sampling performed by URS

Analyses performed by one lab (Test America)

 Two lists of constituents for analysis

Extensive List applied to one sample/location

Less extensive list applied to other samples
General Chemistry of Influent and 

5-Day Flowback (FB) Water Samples

Parameter Range Median Range Median Units

pH 6.7 – 7.4 7.2 5.8 – 7.2 6.6 -

Alkalinity * 6.2 – 88.8 52.5 48.8 - 327 138 mg/l

TDS ** 35 – 5,510 334 38,500-

238,000

67,300 mg/l

Tot Susp Solids ** <2‡ – 24 9.6 10.8 –

3,220

99 mg/l

Tot Org Carbon ** 1.8 – 202 3.8 3.7 - 388 62.8 mg/l

Biochemical 

Oxygen Demand ¥

<2.0‡- 110 149 794 2.8 mg/l

Oil & Grease ** 19 31 NA ⁫ < 5 mg/l

5-Day Flowback

* mg/l as CaCO3 ¥ mg/l as O2

‡ ND = Nondetect ⁫ 

Influent
Comparison of 14-Day FB Water with 

Conventional Produced Water

Parameter Range Median Ranges₣

pH 4.9-6.8 6.2 5 – 8

Alkalinity * 26.1-121 85.2 NA

TDS ** 3,010 –

261,000

120,000 3,000 -

350,000

Tot Susp Solids ** 17 - 1,150 209 0-250

Tot Org Carbon ** 1.2 – 509 38.7 NA

Biochemical Oxygen 

Demand ¥

2.8 – 2,070 2.8 NA

Oil & Grease ** < 0.5 - 103 7.4 mg/l 3 – 100

14-Day Flowback

* mg/l as CaCO3

** mg/l

¥ mg/l as O2

‡ ND = Nondetect

⁫ NA = Not Available

₣ IPEC, 2004; GRI, ‘94

Conv. PW
Cations and Anions in Influent and FB 

Water Samples from Two Locations

Parameter ** Range Median Range Median

Sodium (Na+) 25.7 -

6,190

67.8 10,700 –

65,100

18,000

Calcium (Ca2+) 6.7 – 2,990 32.9 1,440 –

23,500

4,950

Magnesium (Mg2+) 1.2 - 235 6.7 135 – 1,550 559

Iron (Fe2+) ND – 14.3 1.2 10.8 – 180 39

Barium (Ba2+) 0.06 – 87.1 0.4 21.4 –

13,900

686

Chloride (Cl-) 4.1 – 3,000 42.3 26,400 –

148,000

41,850

Bicarbonate (HCO3

-

) < 1 – 188 49.9 29.8 - 162 74.4

Ammonia (NH4

+

) 0.58 - 441 5.9 15 - 242 82.4

Influent Blend 5-Day Flowback

** mg/l
Concentration of TDS in Flowback Water with 

Time During Well Completion: Location A
Concentration of TDS in Flowback Water with 

Time During Well Completion: Location B
Typical Profile of Flowback Water Flow and

Dissolved Solids Versus Time 

Days from Hydraulic Fracture Event

Flowback Water Total Dissolved Solids, mg/l

1000

0

3000

Ave Flow* in the Interval, Bbl/d

2000 14 - 90 Day

Interval

•Average Daily Flow of the Flowback Water Output within Each Interval
Categories of Chemicals of Concern

 Volatile Organics

 Semivolatile Organics

 Pesticides

 Organophosphorus Pesticides

 PCBs

 Metals

 Radiological Determinations 
Volatile Organics
Volatile Organics

 71 Species

 A few sought after constituents are 

often found in conventional produced 

waters: benzene, toluene, xylenes, 

ethylbenzene

 Most of the volatiles on the list were 

man made chemicals not found in 

conventional produced waters
Examples

 Chlorinated benzenes

 Chlorinated alkanes

 Chlorinated alkenes

 Ketones

 MTBE

 Brominated benzenes

 Acrolein

 Chloroform

 Methylene chloride 

 Styrenes

 Vinyl acetate

 Vinyl chloride

 Ethylbenzene

 Trichloroethylene

 Chloromethane

 Acrylonitrile

 Carbon Disulfide

 Carbon Tetrachloride
Number of Volatile Constituents

Locations

Summary of Results of Volatiles 

Measurements in 14-Day Samples

BTEX, Acetone

1, 2, 4 – Trimethylbenzene

1, 3, 5 - Trimethylbenzene Zero 

Constituents
Semivolatile Organics
Semivolatile Compounds

 113 Species

 A few sought after constituents are 

occasionally found in conventional 

produced waters: naphthalene, 2-

methyl naphthalene, phenanthrene, 

phenol

 Many of the semivolatiles on the list 

were man made chemicals not found in 

conventional produced waters

 Many of the semivolatiles are derived 

from or constituents of coal or coal tar
Examples

 Benzo (a) pyrene

 Chlorinated phenols

 Chrysene

 Chlorinated Benzenes

 Nitrophenols

 Fluorene

 Methylphenols

 Naphthalene

 1,4 - Naphthoquinone 

 Phenol

 Pyrene

 Phthalates

 Fluoranthene

 Diphenylamine

 Acenaphthylene

 Bis (2-Chloroethyl) 

ether

 Dibenzofuran
Number of Semivolatile Constituents

Locations

Summary of Results of Semivolatile 

Measurements in 14-Day Samples

Naphthalene

2-Methylnaphthalene

Phenanthrene

Pyridine

(* < 0.5 μg/l for Most Constituents)

*

Zero 

Constituents
Pesticides
Examples

 Chlordane

 Alpha-BHC

 Beta-BHC

 Delta-BHC

 Gamma-BHC

 Heptachlor

 Aldrin

 Heptachlor epoxide

 Endosulfan I 

 Dieldrin

 4, 4’ - DDE

 Endrin

 Endrin ketone

 Endrin aldehyde

 Endosulfan II

 4, 4 - DDT

 Endosulfan sulfate

 Toxaphene
Number of Chlorinated Pesticide Constituents

Locations
Organophosphorus 

Pesticides

& 

PCB’s

All Non-Detect
Metals
Examples

 Mercury

 Arsenic

 Boron

 Trivalent Chromium

 Hexavalent Chromium

 Copper

 Nickel

 Zinc

 Lead

 Selenium

 Cobalt

 Iron

 Manganese

 Lithium

 Tin
Selected Metals in 5-Day Flowback 

Water Compared to Muni Sludges

Metals * Range Median Median 95th %ile

Chromium 

(Cr3+)

ND – 0.15 0.015 35 314

Copper ND – 4.15 ND 511 1,382

Nickel ND – 0.187 ND 22.6 84.5

Zinc 0.068 – 2.93 0.16 705 1,985

Lead ND – 0.606 ND 65 202

Cadmium ND – 0.009 ND 2.3 7.4

Mercury ND - 0.00024 ND 1.5 6.0

Arsenic ND – 0.124 0.029 3.6 18.7

5 – Day Flowback

* mg/l

ND = Non Detect

Muni Sludges**

** Penn State, 2000 (Survey of POTW’s)
Barnett Flowback Water 
General Chemistry of Influent and 

5-Day Flowback (FB) Water Samples

Parameter Range Median Range Median Units

pH 6.6 – 8.0 7.1 5.8 – 7.2 6.6 -

Alkalinity * 238–1630 610 48.8 - 327 138 mg/l

TDS ** 23,600 –

98,900

36,100 38,500-

238,000

67,300 mg/l

Tot Susp Solids ** 36.8 – 253 133 10.8 –

3,220

99 mg/l

Tot Org Carbon ** 9.5 – 99.1 18.1 3.7 - 388 62.8 mg/l

Biochemical 

Oxygen Demand ¥

92.6 -

1480

319 794 2.8 mg/l

Oil & Grease ** < 4.8-1720 < 5 NA ⁫ < 5 mg/l

Marcellus 5-Day

* mg/l as CaCO3 ¥ mg/l as O2

‡ ND = Nondetect ⁫ 

Barnett 5-Day FB
Summary of Results

 Flowback water characteristics are 

consistent with ranges observed with 

conventional produced water

 Low suspended solids and TOC

 Man-made chemicals of concern are at 

non-detect levels.

 BTEX and PAHs are at trace levels.

 Oils and greases are at non-problem levels, 

but some control may be needed

 Soluble organics are highly biodegradable

 Heavy metals are lower than in Mun Sludge
Possible Treatment Needs

 Brine Volume Reduction with Water 

Recovery (for reuse in future frac jobs)

 Removal of Polymers (Friction Reducer 

Compounds)

 Scale Control (Including NORM Scale)

 Oil and Grease Control 

 Soluble Organics: Decrease Total 

Organic Carbon

 Control of suspended solids

 Microbial Control 
Water Reuse

 Two Schools of Thought

1. Condition brines to control SS, O&G, scaleforming potential, microbes, etc. --- without 

demineralization --- and blend for reuse

2. Employ Demineralization to generate a low 

TDS water that can be recovered for reuse

Demineralization can be achieved with 

thermal systems or with membranes. 

Pretreatment is used to protect the 

demineralization processing stage.

Prevention of fouling of heat exchangers 

and membranes is important. 

 Each of the above options has 

advantages and disadvantages
Water Reuse Flowsheet 

PreTreatMent

DeMineralization

Disposal of

Salt Brines 

and Solids:

By-Prod Rec

DWI

LF

Make-up

Water

Well A

Well B

Conc’d

Brine

Residuals

To Landfill Recovered

Water

Brine

Water

Blend

Brine

Bypass
Water Reuse Flowsheet 

PreTreatMent

DeMineralization

Disposal of

Salt Brines 

and Solids:

By-Prod Rec

DWI

LF

Make-up

Water

Well A

Well B

Conc’d

Brine

Residuals

To Landfill Recovered

Water

Brine

Water

Blend

Removal of Susp Solids and 

Oil & Grease and Friction Reducers, 

Microbial Control, etc.

Brine

Bypass
Water Reuse Flowsheet 

PreTreatMent

DeMineralization

Disposal of

Salt Brines 

and Solids:

By-Prod Rec

DWI

LF

Make-up

Water

Well A

Well B

Conc’d

Brine

Brine

Bypass Residuals

To Landfill Recovered

Water

Brine

Water

Blend

Process Examples:

Thermal Processing

Membrane Separation (RO)
Fountain Quail Mechanical Vapor 

Recompression Unit for Flowback 

Water Treatment and Reuse

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• At Devon Sites

• > 6,000 bbls/d/site

• AquaPure Mfgr

• Operated by 

Fountain Quail

• Obtaining field

Performance 

Information

• Over 70% Water 

Recovery

• Handles wide 

feed variations
Reverse Osmosis Trials in the Barnett
Examples of Currently Available Innovative 

Brine Management Technology Options

 Fountain Quail (Thermal Processing for 

Water Recovery)

 212 Resources (Thermal Processing for 

Water Recovery)

 GE Thermal Processing (Thermal 

Processing for Water Recovery)

 Intevras (Heat Recovery from 

Compressor Engines for Brine Evap)

 GeoPure (UF / Reverse Osmosis)

 Ecosphere Technologies (Ozonation 

and Reverse Osmosis)
Rapidly Moving Shale Gas Industry 

Solutions

 Evolving Methods for Improved Shale Gas 

Completions and Operations Impact 

Water Demands and Treatment Needs

 Improved Understanding of the Water Life 

Cycle of Development Areas is Important

 No Single Silver Bullet

 Field Experience and Relevance is Critical

Solution Providers / Service Companies

Developers

Technologists 

 Need to Avoid Prescriptive Remedies

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For more information

Contact Tom Hayes (847.768.0722)

Email: tom.hayes@gastechnology.org
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