Upload
kaveri
View
48
Download
0
Tags:
Embed Size (px)
DESCRIPTION
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
Citation preview
Environmental Forensic Investigation of Hydraulic Fracturing Fluids used in
Shale Gas Wells in the Eastern United States
Frank L. Dorman, Jessica WestlandPenn 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
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
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
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
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
Associated Press Houston, PA Oct 29,2008
Texas Company Pays $208,625 in Settlements for Polluting Creeks in Clearfield County
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
• 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
Companies are “Self Reporting”Range ResourcesHalliburton
What is actually reported is not specific
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
Pennsylvania WaterFrac Formulation - Halliburton
Sample PreparationVOC’s
SPMESVOC’s
QuEChERS extractionLiquid/Liquid ABN extractionAutomated sample preparation (J2 Scientific)
18
QuEChERSAnastassiades and Lehotay developed the
QuEChERS (“catchers”) method for high aqueous samples (foods)
QuickEasyCheapEffectiveRuggedSafe
19
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)
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
Analytical Method?GC-MS or GCxGC-MS rather obvious
Time-of-Flight would be preferred mass spectrometerSamples may be quite complexMuch easier deconvolution
Leco TruTOF HT GC-TOFMS
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)
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
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
Method Blank
QuEChERS Extract
Liquid/Liquid Extract
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
Reynoldsville Quad
Greensburg Quad
Worthington Quad
Kittaning Quad
New Florence Quad
QuEChERS Extracts Method Blank
New Florence Quad
Greensburg Quad
Reynoldsville Quad
Kittaning Quad
Worthington Quad
Liquid/Liquid Extracts
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
Greensburg Quad – 585 peaks
QuEChERS Extract
Liquid/Liquid Extract
Alkoxy OHAlkoxy pyrole
OH’s
Alkoxy OH,Alkanes
Acids, Esters, aliphatics PCB 28
Worthington Quad – 944 peaks
QuEChERS Extract
Liquid/Liquid ExtractAliphatic acidsOH OH OH
Sulfurs, acids, OH’s
PCB 28
Kittaning Quad – 959 peaks
QuEChERS Extract
Liquid/Liquid Extract
Mostly aliphatic
alkaneHexagol, aliphatics, oxy-aliphaticsGlycols, OH’s
Esters and OH’sPCB 28
New Florence Quad – 883 peaks
QuEChERS Extract
Liquid/Liquid ExtractGlycols
AliphaticsAliphatics and OH’s
hydrocarbons
New Florence Quad
QuEChERS Extract
Liquid/Liquid Extract
New Florence Quad
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
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?
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
J2 Scientific PrepLink
New Florence Quad
Greensburg Quad
Reynoldsville Quad
Kittaning Quad
Worthington Quad
Liquid/Liquid Extracts
New Florence Quad
Greensburg Quad
Reynoldsville Quad
Kittaning Quad
Worthington Quad
Liquid/Liquid Extracts – Split Injection
PCB 28S/N = 19:1, 5 pg
Reynoldsville and Kittaning Samples, Sister Wells
UnknownAliphatic Acid
“Unknown”
Early Eluters
Later Eluters
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!
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
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
Thank YouQuestions?
[email protected]@peak-diagnostics.com