Monitoring and Remediation in Shale energy plays. Dr. Zacariah L. Hildenbrand, Inform Environmental, LLC

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1 Monitoring and Remediation in Shale energy plays Dr. Zacariah L. Hildenbrand, Inform Environmental, LLC

2 Monitoring and Remediation in Shale energy Basins Zacariah L. Hildenbrand 1,2, Doug D. Carlton 2, Brian E. Fontenot 2, Jeff Williams 2, Sabrina Habib 2, Kevin A. Schug 2 1 Inform Environmental, LLC, Dallas, TX Collaborative Laboratories for Environmental Analysis and Remediation, UT-Arlington, Arlington, TX

3 What is unconventional drilling? Hydraulic Fracturing large amounts of water, sand and chemicals Shale Acidization Hydrochloric and Hydrofluoric acids Underground Injection Wells (Salt Water Disposal)

Composition of Fracturing Fluid Water -3-5 million gallons per well Chemical

corrosion inhibitors, BTEX compounds (benzene, toluene, ethylbenzene, xylene)

$some information is available at www.fracfocus.$

4 Composition of Fracturing Fluid Water -3-5 million gallons per well Chemical additives (up to 2%)* Biocides, surfactants, gelling agents, emulsifiers, corrosion inhibitors, BTEX compounds (benzene, toluene, ethylbenzene, xylene) *The exact recipe is highly variable and proprietary to each company although some information is available at Proppants (sand and/or ceramics) Large quantities of Hydrochloric and Hydrofluoric acids (shale acidization)

5 Waste water can vary in composition Wastewater can be placed in containment pits, treated at wastewater plants, stored in underground injection wells or recycled (many new technologies are emerging) J.B. Thacker, et al. 2015, Water

Elevated Levels of Arsenic 29 of the 91 samples collected with active extraction areas contained elevated levels of arsenic (>10 μg/l) Drinking water with arsenic levels above 10 μg/l has been shown

6 Elevated Levels of Arsenic 29 of the 91 samples collected with active extraction areas contained elevated levels of arsenic (>10 μg/l) Drinking water with arsenic levels above 10 μg/l has been shown to increase the risk for bladder cancer (Chu et al., Int. J. Environ. Res. Public Health, 2006) Highest concentration that was detected was 161 μg/l Arsenic was not found to be elevated in any B.E. of Fontenot, the control et sites al. Environ. Sci. Tech. 2013, 47, D.D. Carlton, Jr., et al. Inter. J. Environ. Sci. Tech

7 Comparison to historical data 10μg/L 10μg/L Instances of arsenic contamination are in higher frequency near gas wells and arsenic concentrations have increased since the year 2000 B.E. Fontenot, et al. Environ. Sci. Tech.2013,47,

8 Z.L. Hildenbrand, et al. Environ. Sci. Tech Study #Data points 550 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 #Residential wells 350 #Municipal/Pu blic Water supply wells 141 #Agricultural wells 59

9 Detected Abnormalities Methanol (35) Ethanol (240) n-propanol Isopropanol (8) n-butanol 2-Ethylhexanol 2-Butoxy Ethanol Propargyl Alcohol (155) Benzene (34) Toluene (240) Phenol Benzylchloride Trichloroethylene (14) Ethylbenzene (22) 0-, m-, & p-xylenes (183) 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 Dichloromethane (121) PEG 200 Glycerol Acetophenone Dimethylformamide Glutaraldehyde Acetaldehyde (35) Di(2-Ethylhexyl) Phthalate Pthalic Anhydride BisphenolA Chloroform (296) Cyclohexane (221) Detections above respective EPA Maximum Contaminant Limit (MCL) Detections at levels below MCL need to monitor as these can fluctuate with gas well stimulation Detections, no MCL value established No Detections Z.L. Hildenbrand, et al. Environ. Sci. Tech.

10 Bioremediation? Acinetobacter haemolyticus Pseudomonas stutzeri Chloroform Toluene I. Santos, et al. in preparation

11 Dissolved methane in the major shale plays of Texas J.P. Nicot, et al. in review PNAS L. Bai, et al. J. Chromat. A, 2015, 1388, A time-series analysis of compromised sub-region within the Barnett shale Z.L. Hildenbrand, et al. In Progress.

12 In situ detection of methane

In situ detection of methane 40 30 20 10 0 Methane mg/l Methane mg/l 40 35 30 25 20 15 10

13 In situ detection of methane Methane mg/l Methane mg/l :00 9:00 10:00 11:00 12:00 13:00 14:00 15:00 16:00 17:00 18:00 19:00 20:00 21:00 22:00

14 Time-series analyses in the Cline Z.L. Hildenbrand, et al. in review PLoS One

15 Time-series Analysis in the Cline shale 40+ samples collected before, during and after unconventional drilling in the Cline shale of west Texas over 13 months. Sampling will continue in this region for the foreseeable future. Z.L. Hildenbrand, et al. in review PLoS One

16 Time-series Analysis in the Cline Shale Z.L. Hildenbrand, et al. in review PLoS One

17 Soil Analysis: Aromatic Compounds (BTEX) BTEX (Benzene, Toluene, Ethyl Benzene, Xylenes) Found in natural gas, crude oil, gasoline, diesel, etc. Carcinogenic: Benzene Only compounds noted in 2014 proposed legislation (CO, IL)

18 Saltwater Disposal Truck Discharge Runoff Wet sand was collected in the runoff areas of the truck discharge hookups Samples analyzed February 2015 D.D. Carlton, et al. unpublished.

19 Eagle Ford Case Study Large ranch in the Eagle Ford region with 8 pad sites facilitating 28 horizontal oil wells with gas flaring.

20 Eagle Ford Case Study Highly localized to pad activities, specifically gas flares

21 Eagle Ford Case Study White dots denote 0 BTEX detections, yellow dots denote 1 BTEX detection, orange dots denote 2 BTEX detections, red dots denote 3 BTEX detections, and blue dots denote that all 4 BTEX species were detected.

activity Flaring is likely the primary source of air

22 Conclusions BTEX compounds are more prevalent than previously predicted in and around unconventional drilling activity Flaring is likely the primary source of air contamination with accumulation occurring in the surrounding soil Gas flare

Future Directions Develop new technology and best

drilling-related contamination events Remediation and

Environmental Solutions-Calgary, CAN In situ

23 Future Directions Develop new technology and best management practices for instances of drilling-related contamination events Remediation and recycling American Water Recycling-El Paso Pure Life Environmental Solutions-Calgary, CAN In situ detection of environmental abnormalities Eosense-Halifax, CAN (dissolved methane)

All Content Copyright 2015, CLEAR at The University of Texas at

25 Please remember to fill out the conference survey. This will be sent to you by . Conference participants are eligible for up to 13 contact hours 1.3 CEUs. Forms will be available after lunch on Wednesday at the registration are. Return completed forms at the conclusion of the conference.

26 Monitoring and Remediation in Shale energy plays Dr. Zacariah L. Hildenbrand, Inform Environmental, LLC

Considerations for hydraulic fracturing and groundwater and surface water protection: lessons learned in the U.S.

$Considerations for hydraulic fracturing and groundwater and surface water protection: lessons learned in the U.S.$ Considerations for hydraulic fracturing and groundwater and surface water protection: lessons learned in the U.S. Robert W. Puls, Ph.D. Director, Oklahoma Water Survey University of Oklahoma Hydraulic