Case Study: The Barnett Shale of North Texas U.S.A. · Sourcing elevated alcohols difficult...
Transcript of Case Study: The Barnett Shale of North Texas U.S.A. · Sourcing elevated alcohols difficult...
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Kevin A. Schug, Ph.D.
Department of Chemistry & Biochemistry
The University of Texas at Arlington, Arlington, TX 76019
Case Study:
The Barnett Shale of North Texas
U.S.A.
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Acknowledgements Zacariah Hildenbrand, Inform Environmental
Doug D. Carlton, Jr., UTA Chemistry & Biochemistry
Brian Fontenot, Independent Consultant
Laura Hunt, Independent Consultant
Jayme Walton, SWCA Environmental
Jonathan Thacker, UTA Chemistry & Biochemistry
Stephanie Korlie, UTA Chemistry & Biochemistry
Sabra Ramirez, UTA Chemistry & Biochemistry
Jesse Meik, Tarleton State University
Max Hu, UTA Earth & Environmental Sciences
Sandy Dasgupta, UTA Chemistry & Biochemistry
Dasgupta group
Jeff Williams, UTA Communications
Sabrina Habib, UTA Communications
Financial/Material Support
Dan Hopkins
Bryan Bjorndal Alexandra Osario
LANDOWNERS!
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2011: Lots of opinions, any data?
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Osborn, S. G., et al. Proc. Natl. Acad. Sci. 2011, 108, 8172-8176.
Elevated levels of methane; Marcellus shale, PA Geospatial relationship between methane concentration and distance to neighboring gas well Evidence of deep thermogenic methane contamination
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The Barnett Shale
5000 mi2
17 counties 1986 – 1st hydraulic frac 2002-2012 – most productive shale gas in the U.S. Jan. 2013 – 4.56 bcf/day, which was 6.8% of U.S. natural gas
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spring 2012, Arlington TX
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Ideal Experimental Approach
Baseline measurements for anthropogenic effects
Scheduled monitoring for changes/fluctuations over time
Targeted and untargeted analytical methods
Environmental forensics for sourcing
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Analytical Methodologies
• On-site water quality tests
• Total Organic Carbon/Total Nitrogen
• Gas Chromatography (Targeted and untargeted)
• Headspace – GC (Targeted and untargeted)
• ICP-OES Metals (Qualitative/Quantitative)
• ICP-MS Metals (Arsenic and Selenium)
• Ion Chromatography (Inorganic and Organic)
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Basic Water Quality
• pH
• Total Dissolved Solids
(TDS)
• Salinity
• Conductance
• Temperature
• Dissolved Oxygen (DO)
• Oxidation Reduction
Potential (ORP)
Wells purged at well head until pH and temperature stable, then samples collected and water quality measured.
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Gas Chromatography – Mass Spectrometry Method and QC
• Ethyl acetate extraction
• Enhanced sensitivity GC-MS (electron ionization) • SIM/Scan for Targeted/Untargeted • Rxi-5ms, standard • T program, 40 – 300 0C, 13 minute run Quality Control • Triplicate analysis of samples • Multi-level quality control spiked standards • Blanks • Secondary instruments and secondary laboratories
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Gas Chromatography Targets
Methanol
Ethanol
n-propanol
Isopropanol
n-Butanol
2-Ethylhexanol
2-Butoxy Ethanol
Propargyl Alcohol
Benzene
Toluene
Phenol
Benzylchloride
Ethylbenzene
0-, m-, & p-Xylenes
1,2,4-Trimethyl Benzene
1,3,5-Trimethyl Benzene
Isopropyl Benzene
d-Limonene
Naphthalene
1-Methyl Naphthalene
2-Methyl Naphthalene
1-Naphthol
2-Naphthol
Ethylene Glycol
Polyethylene Glycol
Propylene Glycol
Dipropylene Glycol
Monomethyl Ether
PEG 200
Glycerol
Acetophenone
Dimethylformamide
Glutaraldehyde
Acetaldehyde
Di(2-Ethylhexyl) Phthalate
Phthalic Anhydride
Bisphenol A
Dichloromethane
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ICP-OES Method
• Acidified (2% HNO3) and filtered water
• Qual/Semi-Quant/Quant method
– Up to 60 metals; UD relevant
– Matrix effects
– 5 min per sample, triplicate
– Standard addition, 3 points, multi-element std.
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Sampling Map
• 91 Active wells • water well < 3 km of gas well
• 9 reference wells • In shale, > 20 km from gas well • Outside shale, ≈ 60 km from gas well
Fontenot et al. Environ. Sci. Technol. 2013, 47, 10032–10040.
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Does Unconventional Drilling Affect Private Well Water Quality in the
Barnett Shale?
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Elevated Levels of of Arsenic
29 of the 91 samples in active extraction areas contained arsenic >10 μg/L Highest concentration that was detected was 161 μg/L Arsenic was not found to be elevated in any of the reference sites
Fontenot et al. Environ. Sci. Tech. 2013, 47,
10032-10040.
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Geospatial analysis of TDS and Arsenic
Fontenot, B. E., et al. Environ. Sci. Tech. 2013, 47, 10032-10040.
TDS As
MCL (10 ppb)
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Explanations for Arsenic
Instances of arsenic contamination are highest
near hydraulic fracturing sites and in shallower
water wells
• Direct contamination not likely (e.g., flowback spills or
faulty casing)
• Indirect causes
• Scale/rust in wells – Increased pH and vibrations
• Lowered water table – Shallow wells shallower
More data needed Time-lapse analysis before, during and after drilling
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Selenium and Strontium
Fontenot, B. E., et al. Environ. Sci. Tech. 2013, 47, 10032-10040.
Se Sr
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Barium
Fontenot, B. E., et al. Environ. Sci. Tech. 2013, 47, 10032-10040.
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Comparison to historical data
Fontenot, B. E., et al. Environ. Sci. Tech. 2014, 48, 3597-3599
Se (1989 – 1999)
As (1989 – 1999)
As (TX Well Study)
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Significant Methanol and Ethanol
Dataf ile Name:78 02.gcdSample Name:78
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 min
0
1
2
3mV
FID2
MeOH 39 mg/L
EtOH 8.6 mg/L
Dataf ile Name:71 03.gcdSample Name:71
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 min
0
1
2
3
mVFID2
MeOH 54 mg/L
EtOH 11 mg/L
Sourcing elevated alcohols difficult (anticorrosive vs. microbial metabolism vs. other industrial waste) – Not correlated with distance to nearest well.
29 out of 91 wells had detectable MeOH and EtOH (range 1 – 329 mg/L)
? ?
? ?
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Ideal Experimental Approach
Baseline measurements for anthropogenic effects
Scheduled monitoring for changes/fluctuations over time
Targeted and untargeted analytical methods
Environmental forensics for sourcing
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Time-Lapse Analysis in the Cline Shale
NOLAN COUNTY SCURRY COUNTY
40+ water wells sampled before, during, and
after unconventional drilling in Nolan county
Dec. 2012 Summer, 2014
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Barnett Shale Rd. 2 550 samples
County # Collin 4 Cooke 40 Dallas 1
Denton 82 Ellis 25 Hill 14
Hood 60 Johnson 43
Montague 66 Parker 108
Somervell 19 Tarrant 47
Wise 41
63% Residential, 26% Municipal, 11% Agricultural
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Future Directions
Expand our reach into other shale formations
Across the United States, South America, Canada, and Europe
Expand our environmental analysis tool kit
Advance tailored analytical capabilities to characterize a wide range of
environmental events/catastrophes
Develop new technology and best management practices for
unconventional drilling
Remediation, recycling, appropriate waste disposal
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Thank You for Your Attention! [email protected]