Frank L. Dorman , Jessica Westland Penn State University

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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

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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. - PowerPoint PPT Presentation

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Page 1: Frank L. Dorman , Jessica Westland Penn State University

Environmental Forensic Investigation of Hydraulic Fracturing Fluids used in

Shale Gas Wells in the Eastern United States

Frank L. Dorman, Jessica WestlandPenn State University

Page 2: Frank L. Dorman , Jessica Westland Penn State University

Environmental Forensic Investigation of Hydraulic Fracturing Fluids used in

Shale Gas Wells in the Eastern United States

Initial InvestigationsFrank L. Dorman, Jessica Westland

Penn State University

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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 OntarioRapid increase in drilling in last three yearsProperty owners are leasing land to drilling

companies Receive money based on amount of extracted gas

Drilling companies have received tax benefitsSurge has out paced ability to understand and

control potential impacts

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Chemicals Used by Hydraulic Fracturing Companies in Pennsylvania For Surface and Hydraulic Fracturing Activities (PA DEP website)1,2,4-Trimethylbenzene Glycol Ethers (includes 2BE)

1,3,5 Trimethylbenzene Guar gum2,2-Dibromo-3-Nitrilopropionamide Hemicellulase Enzyme2.2-Dibromo-3-Nitrilopropionamide Hydrochloric Acid2-butoxyethanol Hydrotreated light distillate2-Ethylhexanol Hydrotreated Light Distilled2-methyl-4-isothiazolin-3-one Iron Oxide5-chloro-2-methyl-4-isothiazotin-3-one Isopropanol

Acetic Acid Isopropyl AlcoholAcetic Anhydride KerosineAcie Pensurf Magnesium Nitrate

Alchohol Ethoxylated Mesh Sand (Crystalline Silica)

Alphatic Acid MethanolAlphatic Alcohol Polyglycol Ether Mineral SpiritsAluminum Oxide Monoethanolamine

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Ammonia Bifluoride NaphthaleneAmmonia Bisulfite NitrilotriacetamideAmmonium chloride Oil MistAmmonium Salt Petroleum Distallate BlendAmmonia Persulfate Petroleum DistillatesAromatic Hydrocarbon Petroleum NaphthaAromatic Ketones Polyethoxylated Alkanol (1)Boric Acid Polyethoxylated Alkanol (2)Boric Oxide Polyethylene Glycol MixtureButan-1-01 PolysaccharideCitric Acid Potassium CarbonateCrystalline Silica: Cristobalite Potassium ChlorideCrystalline Silica: Quartz Potassium HydroxideDazomet Prop-2-yn-1-01Diatomaceus Earth Propan-2-01Diesel (use discontinued) Propargyl AlcoholDiethylbenzene Propylene

Hydrofrac Chemicals Continued

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Doclecylbenzene Sulfonic Acid Sodium AshE B Butyl Cellosolve Sodium BicarbonateEthane-1,2-diol Sodium ChlorideEthoxlated Alcohol Sodium HydroxideEthoxylated Alcohol SucroseEthoxylated Octylphenol Tetramethylammonium

ChlorideEthylbenzene Titaniaum OxideEthylene Glycol TolueneEthylhexanol XyleneFerrous Sulfate HeptahydrateFormaldehydeGlutaraldehyde

Hydrofrac Chemicals Continued

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Associated Press Houston, PA Oct 29,2008

Texas Company Pays $208,625 in Settlements for Polluting Creeks in Clearfield County

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Gas well steps:

• Well is drilled• Horizontal boring in vein

• Casings are installed• Hydraulic fracturing• Pressure release• Collection of Blowback water• Disposal of collected material

• Recent procedure• Not all material is collected

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• Casing structure and well depth should allow for minimal contamination

• Reports of casing breeches and surface water exposure reported

• Drill sometimes passes through abandoned mine shafts

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Companies are “Self Reporting”Range ResourcesHalliburton

What is actually reported is not specific

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Product Name Additive Purpose Concentration U.S. MSDS

BE-9™ Biocide Prevents or limits growth of bacteria that can cause formation of hydrogen sulfide and can physically plug flow of oil and gas into the well

0.3 gal/1000 gal

FE-1A™ Acid Additive Prevents precipitation of iron oxides during acid treatment 5 gal/ 1000 gal of HCl acid volume

FR-66™ Friction Reducer Allows fracture fluid to move down the wellbore with the least amount of resistance

0.5 – 1 gal/1000 gal

HAI-OS™ Corrosion Inhibitor / Acid Inhibitor

Prevents acid from causing damage to the wellbore and pumping equipment

0.1-2.0 gal/1000 gal of HCl acid volume

7.5% Hydrochloric Acid (HCl)

Acid / Solvent Removes scale and cleans wellbore prior to fracturing treatment 1000-4000 gal run ahead of frac

LP-65™ Scale Inhibitor Prevents build up of certain materials (i.e. scale) on sides of the well casing and the surface equipment

0.25 – 0.5 gal/1000 gal

Sand – Common White 100 Mesh

Proppant Holds open fracture to allow oil and gas to flow to well 0.5 – 1.0 lbs

Sand – Premium White 40/70 Mesh

Proppant Holds open fracture to allow oil and gas to flow to well 0.75 – 3.0 lbs

Sand – Premium White 30/50 Mesh

Proppant Holds open fracture to allow oil and gas to flow to well 2.0 - 3.0 lbs

Water Base Fluid Base fluid creates fractures and carries proppant, also can be present in some additives

N/A Supplied by Customer

Pennsylvania WaterFrac Formulation - Halliburton

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Pennsylvania WaterFrac Formulation - Halliburton

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Sample PreparationVOC’s

SPMESVOC’s

QuEChERS extractionLiquid/Liquid ABN extractionAutomated sample preparation (J2 Scientific)

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QuEChERSAnastassiades and Lehotay developed the

QuEChERS (“catchers”) method for high aqueous samples (foods)

QuickEasyCheapEffectiveRuggedSafe

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QuEChERSMethodologyProcedure

Sample (matrix)Extract with appropriate solvent (ACN)Phase separation

Salt addition (pre-dispersive)Further matrix clean-up possible

dispersive-Solid Phase Extraction(d-SPE)

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Liquid/Liquid Extraction~500 mL aqueous samples Acid preserved in field3 X 60 mL separatory funnel shakes (2 min

each)Collect extractsAdjust pH to 103 X 60 mL separatory funnel shakes (2 min

each)Collect extracts and combine with aboveReduce solvent volume to 1.0 mL using

Kuderna-Danish concentration

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Analytical Method?GC-MS or GCxGC-MS rather obvious

Time-of-Flight would be preferred mass spectrometerSamples may be quite complexMuch easier deconvolution

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Leco TruTOF HT GC-TOFMS

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Gas Chromatograph ConditionsAgilent 7890Column:

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)

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Leco TruTOF Mass Spec ConditionsTransfer line 250 CSource Temperature 250 C400 sec filament delay45 – 550 amu 10 spectra/sec

ChromaTOF 4.34 used for all instrument control and data processing

NIST 2008 Library for spectral searching

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Data AnalysisSample complexity makes display difficultSurrogate recoveries were biased high in most

samples100-300%

Large number of components Identified400 to 1500 components/sample

No reference standardsAll identifications are tentative, at best

Match of 700 used for searchingS/N of 10:1 used

Likely too low for 500:1 enrichment

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Method Blank

QuEChERS Extract

Liquid/Liquid Extract

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Peak # Name1 Octadecane, 6-methyl-2 4-(5-Bromo-3-tert-butylsalicyl)-2,6-di-tert-butylphenol3 Naphthalene, 1,2,3,4-tetrahydro-1,6-dimethyl-4-(1-methylethyl)-, (1S-cis)-4 5-Ethyldecane5 PCB 18 (surrogate)6 PCB 28 (surrogate)7 PCB 52 (surrogate)8 Triphenylmethane (surrogate)9 tris(1,3-dichloroisopropyl) phosphate (surrogate)10 2-Butanone, 1-(acetyloxy)-

Method Blank Compound ID’s

Peak # Name1 Ethanol, 2-chloro-, acetate2 Ethanol, 2-chloro-, acetate3 PCB 18 (surrogate)4 PCB 28 (surrogate)5 PCB 52 (surrogate)6 Triphenylmethane (surrogate)7 tris(1,3-dichloroisopropyl) phosphate (surrogate)8 Cyclotrisiloxane, hexamethyl-9 6-Amino-5-cyano-4-(3-iodo-phenyl)-2-methyl-4H-pyran-3-carb.acid

ethyl ester10 1H-Benzo[4,5]furo[3,2-f]indole10 Several small siloxane-related compounds late in the

chromatogram

QuEChERS Extract

Liquid/Liquid Extract

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Reynoldsville Quad

Greensburg Quad

Worthington Quad

Kittaning Quad

New Florence Quad

QuEChERS Extracts Method Blank

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New Florence Quad

Greensburg Quad

Reynoldsville Quad

Kittaning Quad

Worthington Quad

Liquid/Liquid Extracts

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Reynoldsville Quad - 1093 peaks

Liquid/Liquid Extract

QuEChERS Extract

Heavier OH’s

Mid OH’s Sulfur

Aliphatics, OH’s, esters, COOH’s, etc…

Sulfur’sFew OH’s

PCB 28

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Greensburg Quad – 585 peaks

QuEChERS Extract

Liquid/Liquid Extract

Alkoxy OHAlkoxy pyrole

OH’s

Alkoxy OH,Alkanes

Acids, Esters, aliphatics PCB 28

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Worthington Quad – 944 peaks

QuEChERS Extract

Liquid/Liquid ExtractAliphatic acidsOH OH OH

Sulfurs, acids, OH’s

PCB 28

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Kittaning Quad – 959 peaks

QuEChERS Extract

Liquid/Liquid Extract

Mostly aliphatic

alkaneHexagol, aliphatics, oxy-aliphaticsGlycols, OH’s

Esters and OH’sPCB 28

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New Florence Quad – 883 peaks

QuEChERS Extract

Liquid/Liquid ExtractGlycols

AliphaticsAliphatics and OH’s

hydrocarbons

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New Florence Quad

QuEChERS Extract

Liquid/Liquid Extract

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New Florence Quad

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Peak # Name R.T. (s)Similarity405 Cyclohexane, 1,2,3-trimethyl-, (1à,2à,3à)- 1193.8787406 Undecane, 2,6-dimethyl- 1194.4805407 Fumaric acid, decyl pent-4-enyl ester 1194.9783408 Adipic acid, 2-ethylcyclohexyl isohexyl ester 1196.3881409 Octadecanamide 1196.7919410 Sulfurous acid, butyl 2-ethylhexyl ester 1197.9 737411 Fumaric acid, eicosyl trans-hex-3-enyl ester 1199.2939412 Dichloroacetic acid, 1-cyclopentylethyl ester 1199.6785413 1,5,9,13-Tetradecatetraene 1200728414 7,9-Dimethyl-8-nitrobicyclo[4.3.1]decan-10-one1200.4 822415 Tridecane, 2,5-dimethyl- 1201.7973

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Mid-point Summary:Analytical methodology is acceptable, but

generally results in chromatographic overloadSample preparation seems to require liquid/liquid

extraction, but this is time-consumingSamples all appear different, but many, many

more samples need to be evaluatedPreparation technique must be adapted

Automated Sample preparation, coupled with split injection?

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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 10Each Fraction extracted using C18/DVB Dichloromethane elution (20 mL) each

Point of further method developementCollect extracts and combine GPC cleanup (sulfur removal)Reduce solvent volume to 1.0 mL AccuVap module

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J2 Scientific PrepLink

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New Florence Quad

Greensburg Quad

Reynoldsville Quad

Kittaning Quad

Worthington Quad

Liquid/Liquid Extracts

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New Florence Quad

Greensburg Quad

Reynoldsville Quad

Kittaning Quad

Worthington Quad

Liquid/Liquid Extracts – Split Injection

PCB 28S/N = 19:1, 5 pg

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Reynoldsville and Kittaning Samples, Sister Wells

UnknownAliphatic Acid

“Unknown”

Early Eluters

Later Eluters

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ConclusionsQuEChERS extraction was mildly

successful in determination of very large differencesDid not work well on high MW polar compoundsDid provide some complimentary information

Liquid/Liquid extraction produces extracts of high quality to allow for characterizationPrepLink (J2 Scientific) will become method of

choiceSamples are relatively complex, but each

shows differencesLower sample volumes, split injection

Several of the cited compounds were found, along with many, many others

GC-TOFMS worked well for sample characterizationQuantification ongoing, requires standards!

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Continued WorkMore samples need to be characterizedAdditional sources of blowback water will be

investigatedPost wastewater treatment samples under

investigationVOC portion will be addedAutomated sample preparation under developmentPossible collaboration with the gas-drilling industry

being soughtGCxGC-TOFMS being explored

Samples already analyzed

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Acknowledgements:LECO Corporation

Nick Hall, Joe Binkley, Mark Merrick, R.J. Warren

Todd Barton, Ray CliffordJ2 Scientific

Jeff Wiseman, Tom DobbsRestek Corporation

Jack Cochran, Gary StidsenPenn State University

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Thank YouQuestions?

[email protected]@peak-diagnostics.com