Transcript Document
Frank L. Dorman, Jessica Westland Penn State University
Frank 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 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
Chemicals Used by Hydraulic Fracturing Companies in Pennsylvania For Surface and Hydraulic Fracturing Activities (PA DEP website)
1,2,4-Trimethylbenzene 1,3,5 Trimethylbenzene 2,2-Dibromo-3-Nitrilopropionamide Glycol Ethers (includes 2BE) Guar gum Hemicellulase Enzyme 2.2-Dibromo-3-Nitrilopropionamide 2-butoxyethanol 2-Ethylhexanol 2-methyl-4-isothiazolin-3-one Hydrochloric Acid Hydrotreated light distillate Hydrotreated Light Distilled Iron Oxide 5-chloro-2-methyl-4-isothiazotin-3-one Isopropanol Acetic Acid Acetic Anhydride Acie Pensurf Alchohol Alphatic Acid Alphatic Alcohol Aluminum Oxide Isopropyl Alcohol Kerosine Magnesium Nitrate Ethoxylated Mesh Sand (Crystalline Silica) Methanol Polyglycol Ether Mineral Spirits Monoethanolamine
Hydrofrac Chemicals Continued Ammonia Bifluoride Ammonia Bisulfite Ammonium chloride Ammonium Salt Ammonia Persulfate Aromatic Hydrocarbon Aromatic Ketones Boric Acid Boric Oxide Butan-1-01 Citric Acid Crystalline Silica: Cristobalite Crystalline Silica: Quartz Dazomet Diatomaceus Earth Diesel (use discontinued) Diethylbenzene Naphthalene Nitrilotriacetamide Oil Mist Petroleum Distallate Blend Petroleum Distillates Petroleum Naphtha Polyethoxylated Alkanol (1) Polyethoxylated Alkanol (2) Polyethylene Glycol Mixture Polysaccharide Potassium Carbonate Potassium Chloride Potassium Hydroxide Prop-2-yn-1-01 Propan-2-01 Propargyl Alcohol Propylene
Hydrofrac Chemicals Continued Doclecylbenzene E B Butyl Cellosolve Ethane-1,2-diol Ethoxlated Alcohol Ethoxylated Alcohol Ethoxylated Octylphenol Ethylbenzene Ethylene Glycol Ethylhexanol Ferrous Sulfate Heptahydrate Formaldehyde Glutaraldehyde Sulfonic Acid Sodium Ash Sodium Bicarbonate Sodium Chloride Sodium Hydroxide Sucrose Tetramethylammonium Chloride Titaniaum Oxide Toluene Xylene
Texas Company Pays $208,625 in Settlements for Polluting Creeks in Clearfield County Associated Press Houston, PA Oct 29,2008
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 Resources Halliburton What is actually reported is not specific
Pennsylvania WaterFrac Formulation - Halliburton Product Name BE-9™ Additive
Biocide
Purpose
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
Concentration
0.3 gal/1000 gal
U.S. MSDS FE-1A™ FR-66™ HAI-OS™ 7.5% Hydrochloric Acid (HCl) LP-65™
Acid Additive Prevents precipitation of iron oxides during acid treatment 5 gal/ 1000 gal of HCl acid volume Friction Reducer Corrosion Inhibitor / Acid Inhibitor Acid / Solvent Scale Inhibitor Proppant Allows fracture fluid to move down the wellbore with the least amount of resistance Prevents acid from causing damage to the wellbore and pumping equipment Removes scale and cleans wellbore prior to fracturing treatment 0.5 – 1 gal/1000 gal 0.1-2.0 gal/1000 gal of HCl acid volume 1000-4000 gal run ahead of frac 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 Holds open fracture to allow oil and gas to flow to well 0.5 – 1.0 lbs
Sand – Common White 100 Mesh Sand – Premium White 40/70 Mesh Sand – Premium White 30/50 Mesh Water
Proppant Proppant Base Fluid Holds open fracture to allow oil and gas to flow to well Holds open fracture to allow oil and gas to flow to well Base fluid creates fractures and carries proppant, also can be present in some additives 0.75 – 3.0 lbs 2.0 - 3.0 lbs N/A Supplied by Customer
Pennsylvania WaterFrac Formulation - Halliburton
Sample Preparation
VOC’s SPME SVOC’s QuEChERS extraction Liquid/Liquid ABN extraction Automated sample preparation (J2 Scientific)
QuEChERS
Anastassiades and Lehotay developed the QuEChERS (“catchers”) method for high aqueous samples (foods)
Quick
Easy
Cheap
Effective
Rugged
Safe
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QuEChERS Methodology
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)
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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
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
Leco TruTOF HT GC-TOFMS
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)
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
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
Method Blank
QuEChERS Extract Liquid/Liquid Extract
7 8 9 10 10 3 4 5 6 1 Peak # 2 7 8 9 10 1 Peak # 2 3 4 5 6 Name
Method Blank Compound ID’s
QuEChERS Extract Octadecane, 6-methyl 4-(5-Bromo-3-tert-butylsalicyl)-2,6-di-tert-butylphenol Naphthalene, 1,2,3,4-tetrahydro-1,6-dimethyl-4-(1-methylethyl)-, (1S-cis) 5-Ethyldecane PCB 18 (surrogate) PCB 28 (surrogate) PCB 52 (surrogate) Triphenylmethane (surrogate) tris(1,3-dichloroisopropyl) phosphate (surrogate) 2-Butanone, 1-(acetyloxy) Name Ethanol, 2-chloro-, acetate Ethanol, 2-chloro-, acetate PCB 18 (surrogate) PCB 28 (surrogate) PCB 52 (surrogate) Triphenylmethane (surrogate) Liquid/Liquid Extract tris(1,3-dichloroisopropyl) phosphate (surrogate) Cyclotrisiloxane, hexamethyl 6-Amino-5-cyano-4-(3-iodo-phenyl)-2-methyl-4H-pyran-3-carb.acid ethyl ester 1H-Benzo[4,5]furo[3,2-f]indole Several small siloxane-related compounds late in the chromatogram
QuEChERS Extracts Method Blank Reynoldsville Quad Greensburg Quad Worthington Quad Kittaning Quad New Florence Quad
Liquid/Liquid Extracts
Worthington Quad Kittaning Quad Reynoldsville Quad Greensburg Quad New Florence Quad
Reynoldsville Quad - 1093 peaks Few OH’s QuEChERS Extract Sulfur’s Aliphatics, OH’s, esters, COOH’s, etc… Mid OH’s Sulfur Liquid/Liquid Extract Heavier OH’s PCB 28
Greensburg Quad – 585 peaks Alkoxy OH Alkoxy pyrole QuEChERS Extract OH’s Alkoxy OH, Alkanes Acids, Esters, aliphatics Liquid/Liquid Extract PCB 28
Worthington Quad – 944 peaks Sulfurs, acids, OH’s QuEChERS Extract OH Aliphatic acids OH OH Liquid/Liquid Extract PCB 28
Kittaning Quad – 959 peaks Mostly aliphatic QuEChERS Extract alkane Hexagol, aliphatics, oxy-aliphatics Glycols, OH’s Liquid/Liquid Extract PCB 28 Esters and OH’s
New Florence Quad – 883 peaks
hydrocarbons QuEChERS Extract Aliphatics Aliphatics and OH’s Glycols Liquid/Liquid Extract
New Florence Quad
QuEChERS Extract Liquid/Liquid Extract
New Florence Quad
Peak # 405 406 407 408 409 410 411 412 413 414 415 Name Cyclohexane, 1,2,3-trimethyl-, (1à,2à,3à) Undecane, 2,6-dimethyl Fumaric acid, decyl pent-4-enyl ester Adipic acid, 2-ethylcyclohexyl isohexyl ester Octadecanamide Sulfurous acid, butyl 2-ethylhexyl ester Fumaric acid, eicosyl trans-hex-3-enyl ester Dichloroacetic acid, 1-cyclopentylethyl ester 1,5,9,13-Tetradecatetraene 7,9-Dimethyl-8-nitrobicyclo[4.3.1]decan-10-one Tridecane, 2,5-dimethyl R.T. (s) Similarity 1193.8
1194.4
787 805 1194.9
1196.3
1196.7
1197.9
1199.2
783 881 919 737 939 1199.6
1200 1200.4
1201.7
785 728 822 973
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?
Automated Liquid/Liquid Extraction J
2
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
J
2
Scientific PrepLink
Liquid/Liquid Extracts
Worthington Quad Kittaning Quad Reynoldsville Quad Greensburg Quad New Florence Quad
Liquid/Liquid Extracts – Split Injection
Worthington Quad Kittaning Quad PCB 28 S/N = 19:1, 5 pg Reynoldsville Quad Greensburg Quad New Florence Quad
Reynoldsville and Kittaning Samples, Sister Wells Early Eluters Unknown Aliphatic Acid Later Eluters “Unknown”
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 (J 2 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!
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
Acknowledgements:
LECO Corporation
Nick Hall, Joe Binkley, Mark Merrick, R.J. Warren Todd Barton, Ray Clifford J 2 Scientific Jeff Wiseman, Tom Dobbs Restek Corporation Jack Cochran, Gary Stidsen Penn State University
Thank You
Questions?