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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

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 O 2 ‡ 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 O 2 ‡ 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 (Ca 2+) 6.7 – 2,990 32.9 1,440 – 23,500 4,950 Magnesium (Mg 2+) 1.2 - 235 6.7 135 – 1,550 559 Iron (Fe 2+) ND – 14.3 1.2 10.8 – 180 39 Barium (Ba 2+) 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 (HCO 3-) < 1 – 188 49.9 29.8 - 162 74.4 Ammonia (NH 4+) 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 O 2 ‡ 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 46

### For more information Contact Tom Hayes (847.768.0722) Email: tom.hayes@gastechnology.org48