Environmental Forensic Investigation of Hydraulic Fracturing Fluids used in Shale Gas Wells in the Eastern United States

1. Environmental Forensic Investigation of Hydraulic Fracturing Fluids used in Shale Gas Wells in the Eastern United States Frank L. Dorman, Jessica Westland Penn State University

2. Environmental Forensic Investigation of Hydraulic Fracturing Fluids used in Shale Gas Wells in the Eastern United StatesInitial Investigations Frank L. Dorman, Jessica Westland Penn State University

3. Shale Gas Wells in Eastern US: Marcellus Shale: Gas producing formation between 4000 to 8500 feet from surface �Reachable� in PA, NY, OH, WV, and part of Ontario Rapid increase in drilling in last three years Property owners are leasing land to drilling companies Receive money based on amount of extracted gas Drilling companies have received tax benefits Surge has out paced ability to understand and control potential impacts

12. Companies are �Self Reporting� Range Resources Halliburton What is actually reported is not specific

17. Sample Preparation VOC�s SPME SVOC�s QuEChERS extraction Liquid/Liquid ABN extraction Automated sample preparation (J2 Scientific)

18. QuEChERS Anastassiades and Lehotay developed the QuEChERS (�catchers�) method for high aqueous samples (foods) Quick Easy Cheap Effective Rugged Safe 18 J AOAC Int. 2003. 86, 412 The development of the QuEChERS method was designed to improve conventional sample preparation for multi-residue pesticide analysis Researchers were looking for a simple, effective, and inexpensive way to extract and clean pesticide residues from the many varied sample matrices that they worked with routinely The QuEChERS methodology was found to be an effective alternative Since the development of the QuEChERS method, its application has been introduced to a variety of analytes and matrices These other applications include the extraction of antibiotics, veterinary drugs, and pharmaceuticals in biological samples or food products Very recently the QuEChERS method has caught the attention of the forensic chemistry community�J AOAC Int. 2003. 86, 412 The development of the QuEChERS method was designed to improve conventional sample preparation for multi-residue pesticide analysis Researchers were looking for a simple, effective, and inexpensive way to extract and clean pesticide residues from the many varied sample matrices that they worked with routinely The QuEChERS methodology was found to be an effective alternative Since the development of the QuEChERS method, its application has been introduced to a variety of analytes and matrices These other applications include the extraction of antibiotics, veterinary drugs, and pharmaceuticals in biological samples or food products Very recently the QuEChERS method has caught the attention of the forensic chemistry community�

19. QuEChERSMethodology Procedure Sample (matrix) Extract with appropriate solvent (ACN) Phase separation Salt addition (pre-dispersive) Further matrix clean-up possible dispersive-Solid Phase Extraction (d-SPE) 19

20. Liquid/Liquid Extraction ~500 mL aqueous samples Acid preserved in field 3 X 60 mL separatory funnel shakes (2 min each) Collect extracts Adjust pH to 10 3 X 60 mL separatory funnel shakes (2 min each) Collect extracts and combine with above Reduce solvent volume to 1.0 mL using Kuderna-Danish concentration

21. Analytical Method? GC-MS or GCxGC-MS rather obvious Time-of-Flight would be preferred mass spectrometer Samples may be quite complex Much easier deconvolution

24. Gas Chromatograph Conditions Agilent 7890 Column: Restek Rxi-5Sil MS with integral guard 35M (5M guard) X 0.25 mm i.d. X 0.25 mm df Injector (splitless): Splitless, 1 minute hold, 4-mm Sky Uniliner (Restek), hole at top 250 C 1.2 mL/min, He, constant flow Injector (split): 10:1 split, 4-mm Split liner with SV wool (Restek), standard split seal 250 C 1.2 mL/min, He, constant flow Oven Programs: QuEChERS � 90 C (1), 12C/min 325 C (10) Liq/Liq � 40 C (1), 12 C/min 325 C (10)

25. Leco TruTOF Mass Spec Conditions Transfer line 250 C Source Temperature 250 C 400 sec filament delay 45 � 550 amu 10 spectra/sec ChromaTOF 4.34 used for all instrument control and data processing NIST 2008 Library for spectral searching

26. Data Analysis Sample complexity makes display difficult Surrogate recoveries were biased high in most samples 100-300% Large number of components Identified 400 to 1500 components/sample No reference standards All identifications are tentative, at best Match of 700 used for searching S/N of 10:1 used Likely too low for 500:1 enrichment

39. Mid-point Summary: Analytical methodology is acceptable, but generally results in chromatographic overload Sample preparation seems to require liquid/liquid extraction, but this is time-consuming Samples all appear different, but many, many more samples need to be evaluated Preparation technique must be adapted Automated Sample preparation, coupled with split injection?

40. Automated Liquid/Liquid ExtractionJ2 Scientific PrepLink 100 (up to 500) mL aqueous samples Acid preserved in field (same as previous) Acid Fraction and Base Fraction separated Sample split, and \pH of base fraction adjusted to 10 Each Fraction extracted using C18/DVB Dichloromethane elution (20 mL) each Point of further method developement Collect extracts and combine GPC cleanup (sulfur removal) Reduce solvent volume to 1.0 mL AccuVap module

45. Conclusions QuEChERS extraction was mildly successful in determination of very large differences Did not work well on high MW polar compounds Did provide some complimentary information Liquid/Liquid extraction produces extracts of high quality to allow for characterization PrepLink (J2 Scientific) will become method of choice Samples are relatively complex, but each shows differences Lower sample volumes, split injection Several of the cited compounds were found, along with many, many others GC-TOFMS worked well for sample characterization Quantification ongoing, requires standards! Replace the 5% diphenyl and cyano (225 and 2331) column combination with the more robust Rxi-5ms (5% diphenyl) and Rtx-Dioxin2.Replace the 5% diphenyl and cyano (225 and 2331) column combination with the more robust Rxi-5ms (5% diphenyl) and Rtx-Dioxin2.

46. Continued Work More samples need to be characterized Additional sources of blowback water will be investigated Post wastewater treatment samples under investigation VOC portion will be added Automated sample preparation under development Possible collaboration with the gas-drilling industry being sought GCxGC-TOFMS being explored Samples already analyzed

47. Acknowledgements: LECO Corporation Nick Hall, Joe Binkley, Mark Merrick, R.J. Warren Todd Barton, Ray Clifford J2 Scientific Jeff Wiseman, Tom Dobbs Restek Corporation Jack Cochran, Gary Stidsen Penn State University

48. Thank You Questions? fld3@psu.edu frank@peak-diagnostics.com