5.4 Fracturing Fluid The fluid used for slickwater fracturing is typically comprised of more than 98% fresh water and sand, with chemical additives comprising 2% or less of the fluid.21 The Department has collected compositional information on many of the additives proposed for use in fracturing shale formations in New York directly from chemical suppliers and service companies. This 17 ICF International, 2009. Technical Assistance for the Draft Supplemental Generic EIS: Oil, Gas and Solution Mining Regulatory Program. NYSERDA Agreement No. 9679. pp. 10, 19.
21 GWPC, 2009a. Modern Shale Gas Development in the United States: A Primer, pp. 61-62. DRAFT SGEIS 9/30/2009, Page 5-33 information has been evaluated by the Department’s Air Resources and Water Divisions as well as the Bureaus of Water Supply Protection and Toxic Substances Assessment in the New York State Department of Health. It has also been reviewed by technical consultants contracted by NYSERDA22 to conduct research related to the preparation of this document. Discussion of potential environmental impacts and mitigation measures in Chapters 6 and 7 of this SGEIS reflect analysis and input by all of the foregoing entities. Six service companies23 and twelve chemical suppliers24 have provided additive product compositional information to the Department that includes more complete information than is available on product Material Safety Data Sheets (MSDSs)25. Altogether, some compositional information is on file with the Department for 197 products, with complete compositional information on file for 152 of those products. Within these products are approximately 260 unique chemicals whose CAS Numbers have been disclosed to the Department and an additional 40 compounds which require further disclosure since many are mixtures. Table 5.3 is an alphabetical list of all products for which complete chemical information has been provided to
the Department. Table 5.4 is an alphabetical list of products for which only partial chemical composition information has been provided to the Department. Any product whose name does not appear within Table 5.3 or Table 5.4 was not evaluated in this SGEIS either because no chemical information was submitted to the Department or because the product was not proposed for use in fracturing operations at Marcellus shale wells or other wells targeting other lowpermeability gas reservoirs. MSDSs are on file with the Department for most of the products listed. The Department considers MSDSs to be public information ineligible for exception from disclosure as trade secrets or confidential business information. 22 Alpha Environmental Consultants, Inc., ICF International, URS Corporation
23 BJ Services, Frac Tech Services, Halliburton, Superior Well Services, Universal Well Services, Schlumberger, Superior Well Services
24 Baker Petrolite, CESI/Floteck, Champion Technologies/Special Products, Chem EOR, Cortec, Industrial Compounding, Kemira, Nalco, PfP Technologies, SNF Inc., Weatherford/Clearwater, and WSP Chemicals & Technology
25 MSDSs are designed to provide employees and emergency personnel with proper procedures for handling, working with, and storing a particular substance and are regulated by the Occupational Safety and Health Administration (OSHA)’s Hazard Communication Standard, 29 CFR 1910.1200(g). DRAFT SGEIS 9/30/2009, Page 5-34 Table 5-3 Fracturing Additive Products – Full Composition Disclosure Made to the Department Product Name ABF Acetic Acid 0.1-10% Acid Pensurf / Pensurf Activator W AGA 150 / Super Acid Gell 150 AI-2 Aldacide G Alpha 125 Ammonium Persulfate/OB Breaker APB-1, Ammonium Persulfate Breaker AQF-2 ASP-820 B315 / Friction Reducer B315 B317 / Scale Inhibitor B317 B859 / EZEFLO Surfactant B859 / EZEFLO F103 Surfactant B867 / Breaker B867 / Breaker J218 B868 / EB-CLEAN B868 LT Encapsulated Breaker / EB-Clean J479 LT Encapsulated Breaker
B869 / Corrosion Inhibitor B869 / Corrosion Inhibitor A262 B875 / Borate Crosslinker B875 / Borate Crosslinker J532 B880 / EB-CLEAN B880 Breaker / EB-CLEAN J475 Breaker B890 / EZEFLO Surfactant B890 / EZEFLO F100 Surfactant B900 / EZEFLO Surfactant B900/ EZEFLO F108 Surfactant B910 / Corrosion Inhibitor B910 / Corrosion Inhibitor A264 B916 / Gelling Agent ClearFRAC XT B916 / Gelling Agent ClearFRAC XT J590 BA-2 BA-20 BA-40L BA-40LM BC-140 BC-140 X2 BE-3S DRAFT SGEIS 9/30/2009, Page 5-35 BE-6 BE-7 BE-9 Bentone A-140 BF-1 BF-7 / BF-7L BioClear 1000 / Unicide 1000 Bio-Clear 200 / Unicide 2000 Breaker FR BXL-2, Crosslinker/ Buffer BXL-STD / XL-300MB Carbon Dioxide CL-31 CLA-CHEK LP CLA-STA XP Clay Treat PP Clay Treat TS Clay Treat-3C Clayfix II Clayfix II plus Cronox 245 ES/ CI-14 CS-250 SI CS-650 OS, Oxygen Scavenger CS-Polybreak 210 CS-Polybreak 210 Winterized EB-4L Enzyme G-NE FE-1A FE-2 FE-2A FE-5A Ferchek Ferchek A Ferrotrol 300L Flomax 50
Flomax 70 / VX9173 FLOPAM DR-6000 / DR-6000 FLOPAM DR-7000 / DR-7000 Formic Acid FR-46 FR-48W DRAFT SGEIS 9/30/2009, Page 5-36 FR-56 FRP-121 FRW-14 GasPerm 1000 GBL-8X / LEB-10X / GB-L / En-breaker GBW-20C GBW-30 Breaker Green-Cide 25G / B244 / B244A H015 / Hydrochloric Acid 15% H15 HAI-OS Acid Inhibitor HC-2 High Perm SW-LB HPH Breaker HPH foamer Hydrochloric Acid Hydrochloric Acid (HCl) HYG-3 IC 100L ICA-720 / IC-250 ICA-8 / IC-200 ICI-3240 Inflo-250 InFlo-250W / InFlo-250 Winterized Iron Check / Iron Chek Iron Sta IIC / Iron Sta II Isopropyl Alcohol J313 / Water Friction-Reducing Agen J313 J534 / Urea Ammonium Nitrate Solution J534 J580 / Water Gelling Agent J580 K-34 K-35 KCI L058 / Iron Stabilizer L58 L064 / Temporary Clay Stabilizer L64 LGC-35 CBM LGC-36 UC LGC-VI UC Losurf 300M M003 / Soda Ash M3 MA-844W Methanol DRAFT SGEIS 9/30/2009, Page 5-37 MO-67
Morflo III MSA-II Muriatic Acid 36% Musol A N002 / Nitrogen N2 NCL-100 Nitrogen Para Clear D290 / ParaClean II Paragon 100 E+ PLURADYNE TDA 6 PSA-2L PSI-720 PSI-7208 SAS-2 Scalechek LP-55 Scalechek LP-65 Scalehib 100 / Super Scale Inhibitor / Scale Clear SI-112 SGA II Shale Surf 1000 Shale Surf 1000 Winterized Sodium Citrate SP Breaker STIM-50 / LT-32 Super OW 3 Super Pen 2000 SuperGel 15 U042 / Chelating Agent U42 U066 / Mutual Solvent U66 Unicide 100 / EC6116A Unifoam Unigel 5F UniHibA / SP-43X UnihibG / S-11 Unislik ST 50 / Stim Lube Vicon NF WG-11 WG-17 WG-18 WG-35 DRAFT SGEIS 9/30/2009, Page 5-38 WG-36 WLC-6 XL-1 XL-8 XLW-32 Xylene Table 5-4 Fracturing Additive Products – Partial Composition Disclosure to the Department Product Name 20 Degree Baume Muriatic Acid
AcTivator / 78-ACTW AMB-100 B885 / ClearFRAC LT B885 / ClearFRAC LT J551A B892 / EZEFLO B892 / EZEFLO F110 Surfactant CL-22UC Clay Master 5C Corrosion Inhibitor A261 FAW- 5 FDP-S798-05 FDP-S819-05 FE ACID FR-48 FRW-16 FRW-18 FRW-25M GA 8713 GBW-15C GBW-15L GW-3LDF HVG-1, Fast Hydrating Guar Slurry ICA 400 Inflo-102 J134L / Enzyme Breaker J134L KCLS-2, KCL Substitute L065 / Scale Inhibitor L065 LP-65 Magnacide 575 Microbiocide MSA ACID DRAFT SGEIS 9/30/2009, Page 5-39 Multifunctional Surfactant F105 Nitrogen, Refrigerated Liquid OptiKleen-WF Parasperse Cleaner Product 239 S-150 SandWedge WF Scalechek SCP-2 SilkWater FR-A Super Sol 10/20/30 Unislick 30 / Cyanaflo 105L WC-5584 WCS 5177 Corrosion Scale Inhibitor WCW219 Combination Inhibitor WF-12B Foamer WF-12B Salt Inhibitor Stix WF-12B SI Foamer/Salt Inhibitor WF12BH Foamer WFR-C
Information in sections 5.4.1-3 below was compiled primarily by URS Corporation, under contract to NYSERDA. 5.4.1 Properties of Fracturing Fluids Additives are used in hydraulic fracturing operations to elicit certain properties and characteristics that would aide and enhance the operation. The desired properties and characteristics include: • Non-reactive • Non-flammable • Minimal residuals • Minimal potential for scale or corrosion. • Low entrained solids • Neutral pH (pH 6.5 – 7.5) for maximum polymer hydration DRAFT SGEIS 9/30/2009, Page 5-40 • Limited formation damage • Appropriately modify properties of water to carry proppant deep into the shale • Economical to modify fluid properties • Minimal environmental effects 5.4.2 Classes of Additives Table 5.5 lists the types, purposes and examples of additives that have been proposed to date for use in hydraulic fracturing of gas wells in New York State. Table 5-5 - Types and Purposes of Additives Proposed for Use in New York State Additive Type Description of Purpose Examples of Chemicals26 Proppant “Props” open fractures and allows gas / fluids to flow more freely to the well bore. Sand [Sintered bauxite; zirconium oxide; ceramic beads] Acid Cleans up perforation intervals of cement and drilling mud prior to fracturing fluid injection, and provides accessible path to formation. Hydrochloric acid (HCl, 3% to 28%) Breaker Reduces the viscosity of the fluid in order to release proppant into fractures and enhance the recovery of the fracturing fluid. Peroxydisulfates Bactericide / Biocide Inhibits growth of organisms that could produce gases (particularly hydrogen sulfide)
that could contaminate methane gas. Also prevents the growth of bacteria which can reduce the ability of the fluid to carry proppant into the fractures. Gluteraldehyde; 2-Bromo- 2-nitro-1,2-propanediol Clay Stabilizer / Control Prevents swelling and migration of formation clays which could block pore spaces thereby reducing permeability. Salts (e.g., tetramethyl ammonium chloride) [Potassium chloride (KCl)] Corrosion Inhibitor Reduces rust formation on steel tubing, well casings, tools, and tanks (used only in fracturing fluids that contain acid). Methanol Crosslinker The fluid viscosity is increased using phosphate esters combined with metals. The metals are referred to as crosslinking agents. The increased fracturing fluid viscosity allows Potassium hydroxide 26 Chemicals in brackets [ ] have not been proposed for use in the State of New York to date, but are known to be used in other states or shale formations. DRAFT SGEIS 9/30/2009, Page 5-41 Additive Type Description of Purpose Examples of Chemicals26 the fluid to carry more proppant into the fractures. Friction Reducer Allows fracture fluids to be injected at optimum rates and pressures by minimizing friction. Sodium acrylateacrylamide copolymer; polyacrylamide (PAM) Gelling Agent Increases fracturing fluid viscosity, allowing the fluid to carry more proppant into the fractures. Guar gum Iron Control Prevents the precipitation of metal oxides which could plug off the formation. Citric acid; thioglycolic acid Scale Inhibitor Prevents the precipitation of carbonates and sulfates (calcium carbonate, calcium sulfate, barium sulfate) which could plug off the formation. Ammonium chloride; ethylene glycol; polyacrylate Surfactant Reduces fracturing fluid surface tension thereby aiding fluid recovery.
Methanol; isopropanol 5.4.3 Composition of Fracturing Fluids The composition of the fracturing fluid used may vary from one geologic basin or formation to another in order to meet the specific needs of each operation; but the range of additive types available for potential use remains the same. There are a number of different chemical compositions for each additive type; however, only one product of each type is typically utilized in any given gas well. The selection may be driven by the formation and potential interactions between additives. Additionally not all additive types will be utilized in every fracturing job. A sample composition by weight of fracture fluid is provided in Figure 5.3; this composition is based on data from the Fayetteville Shale.27 Based on this data, approximately 90 percent of the fracture fluid is water; another approximately 9 percent is proppant (see Photo 5.17); the remainder, typically less than 0.5 percent consists of chemical additives listed above. 27 Similar to the Marcellus Shale, the Fayetteville Shale is a marine shale rich in unoxidized carbon (i.e. a black shale). The two shales are at similar depths, and vertical and horizontal wells have been drilled/fractured at both shales. DRAFT SGEIS 9/30/2009, Page 5-42 Photo 5.17 - Sand used in hydraulic fracturing operation in Bradford County, PA. Barnett Shale is considered to be the first instance of extensive high-volume hydraulic fracture technology use; the technology has since been applied in other areas such as the Fayetteville Shale and the Haynesville Shale. URS notes that data collected from applications to drill Marcellus Shale wells in New York indicate that the typical fracture fluid composition for operations in the Marcellus Shale is similar to the provided composition in the Fayetteville Shale. Even though no horizontal wells have been drilled in the Marcellus Shale in New York,
applications filed to date indicate that it is realistic to expect that the composition of fracture fluids used in the Marcellus Shale would be similar from one operation to the next. One potential exception is that additional data provided separately to the Department indicates that biocides have comprised up to 0.03% of fracturing fluid instead of 0.001% as noted in Figure 5.3. DRAFT SGEIS 9/30/2009, Page 5-43 Other, 0.44% Scale Inhibitor, 0.04% Surfactant, 0.08% pH Adjusting Agent, 0.01% Acid, 0.11% Breaker, 0.01% Bactericide/Biocide, 0.001% Corrosion Inhibitor, 0.001% Crosslinker, 0.01% Iron Control, 0.004% Gelling Agent, 0.05% Clay Stabilizer/Controler, 0.05% Friction Reducer, 0.08% Water, 90.60% Proppant, 8.96% Figure 5-3 - Sample Fracture Fluid Composition by Weight Each product within the twelve classes of additives may be made up of one or more chemical constituents. Table 5.6 is a list of chemical constituents and their CAS numbers, that have been extracted from complete product chemical compositional information and Material Safety Data Sheets submitted to the NYSDEC for nearly 200 products used or proposed for use in hydraulic fracturing operations in the Marcellus Shale area of New York. It is important to note that several manufacturers and suppliers provide similar chemicals (i.e. chemicals that would serve the same purpose) for any class of additive, and that not all types of additives are used in a single well. Table 5.6 represents constituents of all hydraulic-fracturing-related chemicals submitted to NYSDEC to date for potential use at shale wells in the State, only a handful of which would be utilized in a single well. Data provided to NYSDEC to date indicates similar fracturing fluid compositions for vertically and horizontally drilled wells. DRAFT SGEIS 9/30/2009, Page 5-44
Table 5-6 - Chemical Constituents in Additives/Chemicals28,29 CAS Number30 Chemical Constituent 2634-33-5 1,2 Benzisothiazolin-2-one / 1,2-benzisothiazolin-3-one 95-63-6 1,2,4 trimethylbenzene 123-91-1 1,4 Dioxane 3452-07-1 1-eicosene 629-73-2 1-hexadecene 112-88-9 1-octadecene 1120-36-1 1-tetradecene 10222-01-2 2,2 Dibromo-3-nitrilopropionamide 27776-21-2 2,2'-azobis-{2-(imidazlin-2-yl)propane}-dihydrochloride 73003-80-2 2,2-Dobromomalonamide 15214-89-8 2-Acrylamido-2-methylpropanesulphonic acid sodium salt polymer 46830-22-2 2-acryloyloxyethyl(benzyl)dimethylammonium chloride 52-51-7 2-Bromo-2-nitro-1,3-propanediol 111-76-2 2-Butoxy ethanol 1113-55-9 2-Dibromo-3-Nitriloprionamide (2-Monobromo-3-nitriilopropionamide) 104-76-7 2-Ethyl Hexanol 67-63-0 2-Propanol / Isopropyl Alcohol / Isopropanol / Propan-2-ol 26062-79-3 2-Propen-1-aminium, N,N-dimethyl-N-2-propenyl-chloride, homopolymer 9003-03-6 2-propenoic acid, homopolymer, ammonium salt 25987-30-8 2-Propenoic acid, polymer with 2 p-propenamide, sodium salt / Copolymer of acrylamide and sodium acrylate 71050-62-9 2-Propenoic acid, polymer with sodium phosphinate (1:1) 66019-18-9 2-propenoic acid, telomer with sodium hydrogen sulfite 107-19-7 2-Propyn-1-ol / Progargyl Alcohol 51229-78-8 3,5,7-Triaza-1-azoniatricyclo[3.3.1.13,7]decane, 1-(3-chloro-2-propenyl)- chloride, 115-19-5 3-methyl-1-butyn-3-ol 127087-87-0 4-Nonylphenol Polyethylene Glycol Ether Branched / Nonylphenol ethoxylated / Oxyalkylated Phenol 64-19-7 Acetic acid 68442-62-6 Acetic acid, hydroxy-, reaction products with triethanolamine 108-24-7 Acetic Anhydride 67-64-1 Acetone 79-06-1 Acrylamide
28 Table 5.6 is a list of chemical constituents and their CAS numbers that have been extracted from complete chemical compositions and Material Safety Data Sheets submitted to the NYSDEC.
29 These are the chemical constituents of all chemical additives proposed to be used in New York for hydraulic fracturing operations at shale wells. Only a few chemicals will be used in a single well; the list of chemical constituents used in an individual well will be correspondingly smaller.
30 Chemical Abstracts Service (CAS) is a division of the American Chemical Society. CAS assigns unique numerical identifiers to every chemical described in the literature. The intention is to make database searches more convenient, as chemicals often have many names. Almost all molecule databases today allow searching by CAS number. DRAFT SGEIS 9/30/2009, Page 5-45 CAS Number30 Chemical Constituent
38193-60-1 Acrylamide - sodium 2-acrylamido-2-methylpropane sulfonate copolymer 25085-02-3 Acrylamide - Sodium Acrylate Copolymer or Anionic Polyacrylamide 69418-26-4 Acrylamide polymer with N,N,N-trimethyl-2[1-oxo-2-propenyl]oxy Ethanaminium chloride 15085-02-3 Acrylamide-sodium acrylate copolymer 68551-12-2 Alcohols, C12-C16, Ethoxylated (a.k.a. Ethoxylated alcohol) 64742-47-8 Aliphatic Hydrocarbon / Hydrotreated light distillate / Petroleum Distillates / Isoparaffinic Solvent / Paraffin Solvent / Napthenic Solvent 64743-02-8 Alkenes 68439-57-6 Alkyl (C14-C16) olefin sulfonate, sodium salt 9016-45-9 Alkylphenol ethoxylate surfactants 1327-41-9 Aluminum chloride 73138-27-9 Amines, C12-14-tert-alkyl, ethoxylated 71011-04-6 Amines, Ditallow alkyl, ethoxylated 68551-33-7 Amines, tallow alkyl, ethoxylated, acetates 1336-21-6 Ammonia 631-61-8 Ammonium acetate 68037-05-8 Ammonium Alcohol Ether Sulfate 7783-20-2 Ammonium bisulfate 10192-30-0 Ammonium Bisulphite 12125-02-9 Ammonium Chloride 7632-50-0 Ammonium citrate 37475-88-0 Ammonium Cumene Sulfonate 1341-49-7 Ammonium hydrogen-difluoride 6484-52-2 Ammonium nitrate 7727-54-0 Ammonium Persulfate / Diammonium peroxidisulphate 1762-95-4 Ammonium Thiocyanate 7664-41-7 Aqueous ammonia 121888-68-4 Bentonite, benzyl(hydrogenated tallow alkyl) dimethylammonium stearate complex / organophilic clay 71-43-2 Benzene 119345-04-9 Benzene, 1,1'-oxybis, tetratpropylene derivatives, sulfonated, sodium salts 74153-51-8 Benzenemethanaminium, N,N-dimethyl-N-[2-[(1-oxo-2-propenyl)oxy]ethyl]- , chloride, polymer with 2-propenamide 10043-35-3 Boric acid 1303-86-2 Boric oxide / Boric Anhydride 71-36-3 Butan-1-ol 68002-97-1 C10 - C16 Ethoxylated Alcohol 68131-39-5 C12-15 Alcohol, Ethoxylated 10043-52-4 Calcium chloride 124-38-9 Carbon Dioxide 68130-15-4 Carboxymethylhydroxypropyl guar 9012-54-8 Cellulase / Hemicellulase Enzyme 9004-34-6 Cellulose 10049-04-4 Chlorine Dioxide 77-92-9 Citric Acid DRAFT SGEIS 9/30/2009, Page 5-46 CAS Number30 Chemical Constituent 94266-47-4 Citrus Terpenes 61789-40-0 Cocamidopropyl Betaine
68155-09-9 Cocamidopropylamine Oxide 68424-94-2 Coco-betaine 7758-98-7 Copper (II) Sulfate 31726-34-8 Crissanol A-55 14808-60-7 Crystalline Silica (Quartz) 7447-39-4 Cupric chloride dihydrate 1120-24-7 Decyldimethyl Amine 2605-79-0 Decyl-dimethyl Amine Oxide 3252-43-5 Dibromoacetonitrile 25340-17-4 Diethylbenzene 111-46-6 Diethylene Glycol 22042-96-2 Diethylenetriamine penta (methylenephonic acid) sodium salt 28757-00-8 Diisopropyl naphthalenesulfonic acid 68607-28-3 Dimethylcocoamine, bis(chloroethyl) ether, diquaternary ammonium salt 7398-69-8 Dimethyldiallylammonium chloride 25265-71-8 Dipropylene glycol 139-33-3 Disodium Ethylene Diamine Tetra Acetate 5989-27-5 D-Limonene 123-01-3 Dodecylbenzene 27176-87-0 Dodecylbenzene sulfonic acid 42504-46-1 Dodecylbenzenesulfonate isopropanolamine 50-70-4 D-Sorbitol / Sorbitol 37288-54-3 Endo-1,4-beta-mannanase, or Hemicellulase 149879-98-1 Erucic Amidopropyl Dimethyl Betaine 89-65-6 Erythorbic acid, anhydrous 54076-97-0 Ethanaminium, N,N,N-trimethyl-2-[(1-oxo-2-propenyl)oxy]-, chloride, homopolymer 107-21-1 Ethane-1,2-diol / Ethylene Glycol 9002-93-1 Ethoxylated 4-tert-octylphenol 68439-50-9 Ethoxylated alcohol 126950-60-5 Ethoxylated alcohol 67254-71-1 Ethoxylated alcohol (C10-12) 68951-67-7 Ethoxylated alcohol (C14-15) 68439-46-3 Ethoxylated alcohol (C9-11) 66455-15-0 Ethoxylated Alcohols 84133-50-6 Ethoxylated Alcohols (C12-14 Secondary) 68439-51-0 Ethoxylated Alcohols (C12-14) 78330-21-9 Ethoxylated branch alcohol 34398-01-1 Ethoxylated C11 alcohol 61791-12-6 Ethoxylated Castor Oil 61791-29-5 Ethoxylated fatty acid, coco 61791-08-0 Ethoxylated fatty acid, coco, reaction product with ethanolamine 68439-45-2 Ethoxylated hexanol DRAFT SGEIS 9/30/2009, Page 5-47 CAS Number30 Chemical Constituent 9036-19-5 Ethoxylated octylphenol 9005-67-8 Ethoxylated Sorbitan Monostearate 9004-70-3 Ethoxylated Sorbitan Trioleate 64-17-5 Ethyl alcohol / ethanol 100-41-4 Ethyl Benzene
97-64-3 Ethyl Lactate 9003-11-6 Ethylene Glycol-Propylene Glycol Copolymer (Oxirane, methyl-, polymer with oxirane) 75-21-8 Ethylene oxide 5877-42-9 Ethyloctynol 68526-86-3 Exxal 13 61790-12-3 Fatty Acids 68188-40-9 Fatty acids, tall oil reaction products w/ acetophenone, formaldehyde & thiourea 9043-30-5 Fatty alcohol polyglycol ether surfactant 7705-08-0 Ferric chloride 7782-63-0 Ferrous sulfate, heptahydrate 50-00-0 Formaldehyde 29316-47-0 Formaldehyde polymer with 4,1,1-dimethylethyl phenolmethyl oxirane 153795-76-7 Formaldehyde, polymers with branched 4-nonylphenol, ethylene oxide and propylene oxide 75-12-7 Formamide 64-18-6 Formic acid 110-17-8 Fumaric acid 65997-17-3 Glassy calcium magnesium phosphate 111-30-8 Glutaraldehyde 56-81-5 Glycerol / glycerine 9000-30-0 Guar Gum 9000-30-01 Guar Gum 64742-94-5 Heavy aromatic petroleum naphtha 9025-56-3 Hemicellulase 7647-01-0 Hydrochloric Acid / Hydrogen Chloride / muriatic acid 7722-84-1 Hydrogen Peroxide 79-14-1 Hydroxy acetic acid 35249-89-9 Hydroxyacetic acid ammonium salt 9004-62-0 Hydroxyethyl cellulose 5470-11-1 Hydroxylamine hydrochloride 39421-75-5 Hydroxypropyl guar 35674-56-7 Isomeric Aromatic Ammonium Salt 64742-88-7 Isoparaffinic Petroleum Hydrocarbons, Synthetic 64-63-0 Isopropanol 98-82-8 Isopropylbenzene (cumene) 68909-80-8 Isoquinoline, reaction products with benzyl chloride and quinoline 8008-20-6 Kerosene 64742-81-0 Kerosine, hydrodesulfurized DRAFT SGEIS 9/30/2009, Page 5-48 CAS Number30 Chemical Constituent 63-42-3 Lactose 64742-95-6 Light aromatic solvent naphtha 1120-21-4 Light Paraffin Oil 14807-96-6 Magnesium Silicate Hydrate (Talc) 1184-78-7 methanamine, N,N-dimethyl-, N-oxide 67-56-1 Methanol 68891-11-2 Methyloxirane polymer with oxirane, mono (nonylphenol) ether, branched 8052-41-3 Mineral spirits / Stoddard Solvent
141-43-5 Monoethanolamine 44992-01-0 N,N,N-trimethyl-2[1-oxo-2-propenyl]oxy Ethanaminium chloride 64742-48-9 Naphtha (petroleum), hydrotreated heavy 91-20-3 Naphthalene 38640-62-9 Naphthalene bis(1-methylethyl) 93-18-5 Naphthalene, 2-ethoxy- 68909-18-2 N-benzyl-alkyl-pyridinium chloride 68139-30-0 N-Cocoamidopropyl-N,N-dimethyl-N-2-hydroxypropylsulfobetaine 7727-37-9 Nitrogen, Liquid form 68412-54-4 Nonylphenol Polyethoxylate 121888-66-2 Organophilic Clays 64742-65-0 Petroleum Base Oil 64741-68-0 Petroleum naphtha 70714-66-8 Phosphonic acid, [[(phosphonomethyl)imino]bis[2,1- ethanediylnitrilobis(methylene)]]tetrakis-, ammonium salt 8000-41-7 Pine Oil 60828-78-6 Poly(oxy-1,2-ethanediyl), a-[3,5-dimethyl-1-(2-methylpropyl)hexyl]-whydroxy- 25322-68-3 Poly(oxy-1,2-ethanediyl), a-hydro-w-hydroxy / Polyethylene Glycol 24938-91-8 Poly(oxy-1,2-ethanediyl), α-tridecyl-ω-hydroxy- 51838-31-4 Polyepichlorohydrin, trimethylamine quaternized 56449-46-8 Polyethlene glycol oleate ester 62649-23-4 Polymer with 2-propenoic acid and sodium 2-propenoate 9005-65-6 Polyoxyethylene Sorbitan Monooleate 61791-26-2 Polyoxylated fatty amine salt 127-08-2 Potassium acetate 12712-38-8 Potassium borate 1332-77-0 Potassium borate 20786-60-1 Potassium Borate 584-08-7 Potassium carbonate 7447-40-7 Potassium chloride 590-29-4 Potassium formate 1310-58-3 Potassium Hydroxide 13709-94-9 Potassium metaborate 24634-61-5 Potassium Sorbate 112926-00-8 Precipitated silica / silica gel 57-55-6 Propane-1,2-diol, or Propylene glycol DRAFT SGEIS 9/30/2009, Page 5-49 CAS Number30 Chemical Constituent 107-98-2 Propylene glycol monomethyl ether 68953-58-2 Quaternary Ammonium Compounds 62763-89-7 Quinoline,2-methyl-, hydrochloride 15619-48-4 Quinolinium, 1-(phenylmethl),chloride 7631-86-9 Silica, Dissolved 5324-84-5 Sodium 1-octanesulfonate 127-09-3 Sodium acetate 95371-16-7 Sodium Alpha-olefin Sulfonate 532-32-1 Sodium Benzoate 144-55-8 Sodium bicarbonate 7631-90-5 Sodium bisulfate 7647-15-6 Sodium Bromide
497-19-8 Sodium carbonate 7647-14-5 Sodium Chloride 7758-19-2 Sodium chlorite 3926-62-3 Sodium Chloroacetate 68-04-2 Sodium citrate 6381-77-7 Sodium erythorbate / isoascorbic acid, sodium salt 2836-32-0 Sodium Glycolate 1310-73-2 Sodium Hydroxide 7681-52-9 Sodium hypochlorite 7775-19-1 Sodium Metaborate .8H2O 10486-00-7 Sodium perborate tetrahydrate 7775-27-1 Sodium persulphate 9003-04-7 Sodium polyacrylate 7757-82-6 Sodium sulfate 1303-96-4 Sodium tetraborate decahydrate 7772-98-7 Sodium Thiosulfate 1338-43-8 Sorbitan Monooleate 57-50-1 Sucrose 5329-14-6 Sulfamic acid 112945-52-5 Syntthetic Amorphous / Pyrogenic Silica / Amorphous Silica 68155-20-4 Tall Oil Fatty Acid Diethanolamine 8052-48-0 Tallow fatty acids sodium salt 72480-70-7 Tar bases, quinoline derivs., benzyl chloride-quaternized 68647-72-3 Terpene and terpenoids 68956-56-9 Terpene hydrocarbon byproducts 533-74-4 Tetrahydro-3,5-dimethyl-2H-1,3,5-thiadiazine-2-thione (a.k.a. Dazomet) 55566-30-8 Tetrakis(hydroxymethyl)phosphonium sulfate (THPS) 75-57-0 Tetramethyl ammonium chloride 64-02-8 Tetrasodium Ethylenediaminetetraacetate 68-11-1 Thioglycolic acid 62-56-6 Thiourea 68527-49-1 Thiourea, polymer with formaldehyde and 1-phenylethanone 108-88-3 Toluene DRAFT SGEIS 9/30/2009, Page 5-50 CAS Number30 Chemical Constituent 81741-28-8 Tributyl tetradecyl phosphonium chloride 68299-02-5 Triethanolamine hydroxyacetate 112-27-6 Triethylene Glycol 52624-57-4 Trimethylolpropane, Ethoxylated, Propoxylated 150-38-9 Trisodium Ethylenediaminetetraacetate 5064-31-3 Trisodium Nitrilotriacetate 7601-54-9 Trisodium ortho phosphate 57-13-6 Urea 25038-72-6 Vinylidene Chloride/Methylacrylate Copolymer 7732-18-5 Water 1330-20-7 Xylene Chemical Constituent Aliphatic acids Aliphatic alcohol glycol ether Alkyl Aryl Polyethoxy Ethanol
Alkylaryl Sulfonate Aromatic hydrocarbons Aromatic ketones Oxyalkylated alkylphenol Petroleum distillate blend Polyethoxylated alkanol Polymeric Hydrocarbons Salt of amine-carbonyl condensate Salt of fatty acid/polyamine reaction product Sugar Surfactant blend Chemical constituents are not linked to product names in Table 5.6 because a significant number of product composition and formulas have been justified as trade secrets as defined and provided by Public Officers Law §87.2(d) and the Department’s implementing regulation, 6 NYCRR 616.7. 5.4.3.1 Chemical Categories and Health Information DEC requested assistance from NYSDOH in identifying potential exposure pathways and constituents of concern associated with high-volume hydraulic fracturing for low-permeability gas reservoir development. DEC provided DOH with fracturing additive product constituents based on Material Safety Data Sheets (MSDSs) and product-composition disclosures for hydraulic fracturing additive products that were provided by well-service companies and the chemical supply companies that manufacture the products. DRAFT SGEIS 9/30/2009, Page 5-51 Compound-specific toxicity data are very limited for many chemical additives to fracturing fluids, so chemicals potentially present in fracturing fluids were grouped together into categories according to their chemical structure (or function in the case of microbiocides) in Table 5.7, compiled by NYSDOH. As explained above, any given individual fracturing job will only involve a handful of chemicals and may not include every category of chemicals. Table 5-7 - Categories based on chemical structure of potential fracturing fluid constituents. Chemicals are grouped in order of ascending CAS Number by category.
Chemical CAS Number Amides Formamide 75-12-7 acrylamide 79-06-1 Amines urea 57-13-6 thiourea 62-56-6 tetramethyl ammonium chloride 75-57-0 monoethanolamine 141-43-5 Decyldimethyl Amine 1120-24-7 methanamine, N,N-dimethyl-, N-oxide 1184-78-7 Decyl-dimethyl Amine Oxide 2605-79-0 dimethyldiallylammonium chloride 7398-69-8 polydimethyl dially ammonium chloride 26062-79-3 dodecylbenzenesulfonate isopropanolamine 42504-46-1 N,N,N-trimethyl-2[1-oxo-2-propenyl]oxy ethanaminium chloride 44992-01-0 2-acryloyloxyethyl(benzyl)dimethylammonium chloride 46830-22-2 ethanaminium, N,N,N-trimethyl-2-[(1-oxo-2-propenyl)oxy]-, chloride, homopolymer 54076-97-0 Cocamidopropyl Betaine 61789-40-0 polyoxylated fatty amine salt 61791-26-2 quinoline, 2-methyl, hydrochloride 62763-89-7 N-cocoamidopropyl-N,N-dimethyl-N-2-hydroxypropylsulfobetaine 68139-30-0 tall oil fatty acid diethanolamine 68155-20-4 N-cocoamidopropyl-N,N-dimethyl-N-2-hydroxypropylsulfobetaine 68424-94-2 amines, tallow alkyl, ethoxylated, acetates 68551-33-7 DRAFT SGEIS 9/30/2009, Page 5-52 Chemical CAS Number quaternary ammonium compounds, bis(hydrogenated tallow alkyl) dimethyl, salts with bentonite 68953-58-2 amines, ditallow alkyl, ethoxylated 71011-04-6 amines, C-12-14-tert-alkyl, ethoxylated 73138-27-9 benzenemethanaminium, N,N-dimethyl-N-[2-[(1-oxo-2-propenyl)oxy]ethyl]-, chloride, polymer with 2-propenamide 74153-51-8 Erucic Amidopropyl Dimethyl Betaine 149879-98-1 Petroleum Distillates light paraffin oil 1120-21-4 kerosene 8008-20-6 stoddard solvent 8052-41-3 petroleum naphtha 64741-68-0 Multiple names listed under same CAS#: LVP aliphatic hydrocarbon, hydrotreated light distillate, low odor paraffin solvent, paraffin solvent, paraffinic napthenic solvent, isoparaffinic solvent, distillates (petroleum) hydrotreated light, petroleum light distillate, aliphatic hydrocarbon, petroleum distillates
64742-47-8 naphtha, hydrotreated heavy 64742-48-9 petroleum base oil 64742-65-0 kerosine (petroleum, hydrodesulfurized) 64742-81-0 kerosine (petroleum, hydrodesulfurized) 64742-88-7 Multiple names listed under same CAS#: heavy aromatic petroleum naphtha, light aromatic solvent naphtha 64742-94-5 light aromatic solvent naphtha 64742-95-6 alkenes, C> 10 α- 64743-02-8 Aromatic Hydrocarbons benzene 71-43-2 naphthalene 91-20-3 naphthalene, 2-ethoxy 93-18-5 1,2,4-trimethylbenzene 95-63-6 cumene 98-82-8 ethyl benzene 100-41-4 toluene 108-88-3 dodecylbenzene 123-01-3 xylene 1330-20-7 DRAFT SGEIS 9/30/2009, Page 5-53 Chemical CAS Number diethylbenzene 25340-17-4 naphthalene bis(1-methylethyl) 38640-62-9 Alcohols sorbitol (or) D-sorbitol 50-70-4 Glycerol 56-81-5 propylene glycol 57-55-6 ethanol 64-17-5 isopropyl alcohol 67-63-0 methanol 67-56-1 isopropyl alcohol 67-63-0 butanol 71-36-3 2-ethyl-1-hexanol 104-76-7 propargyl alcohol 107-19-7 ethylene glycol 107-21-1 Diethylene Glycol 111-46-6 3-methyl-1-butyn-3-ol 115-19-5 Ethyloctynol 5877-42-9 Glycol Ethers & Ethoxylated Alcohols propylene glycol monomethyl ether 107-98-2 ethylene glycol monobutyl ether 111-76-2 triethylene glycol 112-27-6 oxylated 4-tert-octylphenol 9002-93-1 ethoxylated sorbitan trioleate 9005-70-3 Polysorbate 80 9005-65-6 ethoxylated sorbitan monostearate 9005-67-8 Polyethylene glycol-(phenol) ethers 9016-45-9 Polyethylene glycol-(phenol) ethers 9036-19-5
fatty alcohol polyglycol ether surfactant 9043-30-5 Poly(oxy-1,2-ethanediyl), α-tridecyl-ω-hydroxy- 24938-91-8 Dipropylene glycol 25265-71-8 Nonylphenol Ethoxylate 26027-38-3 crissanol A-55 31726-34-8 Polyethylene glycol-(alcohol) ethers 34398-01-1 Trimethylolpropane, Ethoxylated, Propoxylated 52624-57-4 Polyethylene glycol-(alcohol) ethers 60828-78-6 Ethoxylated castor oil [PEG-10 Castor oil] 61791-12-6 DRAFT SGEIS 9/30/2009, Page 5-54 Chemical CAS Number ethoxylated alcohols 66455-15-0 ethoxylated alcohol 67254-71-1 Ethoxylated alcohols (9 – 16 carbon atoms) 68002-97-1 ammonium alcohol ether sulfate 68037-05-8 Polyethylene glycol-(alcohol) ethers 68131-39-5 Polyethylene glycol-(phenol) ethers 68412-54-4 ethoxylated hexanol 68439-45-2 Polyethylene glycol-(alcohol) ethers 68439-46-3 Ethoxylated alcohols (9 – 16 carbon atoms) 68439-50-9 C12-C14 ethoxylated alcohols 68439-51-0 Exxal 13 68526-86-3 Ethoxylated alcohols (9 – 16 carbon atoms) 68551-12-2 alcohols, C-14-15, ethoxylated 68951-67-7 Ethoxylated Branched C11-14, C-13-rich Alcohols 78330-21-9 Ethoxylated alcohols (9 – 16 carbon atoms) 84133-5-6 alcohol ethoxylated 126950-60-5 Polyethylene glycol-(phenol) ethers 127087-87-0 Microbiocides bronopol 52-51-7 glutaraldehyde 111-30-8 2-monobromo-3-nitrilopropionamide 1113-55-9 1,2-benzisothiazolin-3-one 2634-33-5 dibromoacetonitrile 3252-43-5 dazomet 533-74-4 Hydrogen Peroxide 7722-84-1 2,2-dibromo-3-nitrilopropionamide 10222-01-2 tetrakis 55566-30-8 2,2-dibromo-malonamide 73003-80-2 Organic Acids and Related Chemicals tetrasodium EDTA 64-02-8 formic acid 64-18-6 acetic acid 64-19-7 sodium citrate 68-04-2 thioglycolic acid 68-11-1 hydroxyacetic acid 79-14-1 erythorbic acid, anhydrous 89-65-6 DRAFT SGEIS 9/30/2009, Page 5-55 Chemical CAS Number ethyl lactate 97-64-3
acetic anhydride 108-24-7 fumaric acid 110-17-8 potassium acetate 127-08-2 sodium acetate 127-09-3 Disodium Ethylene Diamine Tetra Acetate 139-33-3 Trisodium Ethylenediamine tetraacetate 150-38-9 sodium benzoate 532-32-1 potassium formate 590-29-4 ammonium acetate 631-61-8 Sodium Glycolate 2836-32-0 Sodium Chloroacetate 3926-62-3 trisodium nitrilotriacetate 5064-31-3 sodium 1-octanesulfonate 5324-84-5 Sodium Erythorbate 6381-77-7 ammonium citrate 7632-50-0 tallow fatty acids sodium salt 8052-48-0 quinolinium, 1-(phenylmethyl), chloride 15619-48-4 diethylenetriamine penta (methylenephonic acid) sodium salt 22042-96-2 potassium sorbate 24634-61-5 dodecylbenzene sulfonic acid 27176-87-0 diisopropyl naphthalenesulfonic acid 28757-00-8 hydroxyacetic acid ammonium salt 35249-89-9 isomeric aromatic ammonium salt 35674-56-7 ammonium cumene sulfonate 37475-88-0 Fatty Acids 61790-12-3 fatty acid, coco, ethoxylated 61791-29-5 2-propenoic acid, telomer with sodium hydrogen sulfite 66019-18-9 carboxymethylhydroxypropyl guar 68130-15-4 fatty acids, tall oil reaction products w/ acetophenone, formaldehyde & thiourea 68188-40-9 triethanolamine hydroxyacetate 68299-02-5 alkyl (C14-C16) olefin sulfonate, sodium salt 68439-57-6 triethanolamine hydroxyacetate 68442-62-6 N-benzyl-alkyl-pyridinium chloride 68909-18-2 phosphonic acid, [[(phosphonomethyl)imino]bis[2,1-ethanediylnitrilobis (methylene)]]tetrakisammonium salt 70714-66-8 tributyl tetradecyl phosphonium chloride 81741-28-8 sodium alpha-olefin sulfonate 95371-16-7 DRAFT SGEIS 9/30/2009, Page 5-56 Chemical CAS Number benzene, 1,1'-oxybis, tetratpropylene derivatives, sulfonated, sodium salts 119345-04-9 Polymers guar gum 9000-30-0 guar gum 9000-30-01 2-propenoic acid, homopolymer, ammonium salt 9003-03-6 low mol wt polyacrylate 9003-04-7 Low Mol. Wt. Polyacrylate 9003-04-7 Multiple names listed under same CAS#: oxirane, methyl-, polymer with oxirane, Ethylene Glycol-Propylene Glycol Copolymer
9003-11-6 cellulose 9004-34-6 hydroxyethyl cellulose 9004-62-0 cellulase/hemicellulase enzyme 9012-54-8 hemicellulase 9025-56-3 acrylamide-sodium acrylate copolymer 25085-02-3 Vinylidene Chloride/Methylacrylate Copolymer 25038-72-6 polyethylene glycol 25322-68-3 copolymer of acrylamide and sodium acrylate 25987-30-8 formaldehyde polymer with 4,1,1-dimethylethyl phenolmethyl oxirane 29316-47-0 hemicellulase 37288-54-3 acrylamide - sodium 2-acrylamido-2-methylpropane sulfonate copolymer 38193-60-1 oxiranemthanaminium, N,N,N-trimethyl-, chloride, homopolymer (aka: polyepichlorohydrin, trimethylamine quaternized) 51838-31-4 polyethlene glycol oleate ester 56449-46-8 polymer with 2-propenoic acid and sodium 2-propenoate 62649-23-4 modified thiourea polymer 68527-49-1 methyloxirane polymer with oxirane, mono (nonylphenol) ether, branched 68891-11-2 acrylamide polymer with N,N,N-trimethyl-2[1-oxo-2-propenyl]oxy ethanaminium chloride 69418- 26-4 2-propenoic acid, polymer with sodium phosphinate (1:1) 71050-62-9 formaldehyde, polymers with branched 4-nonylphenol, ethylene oxide and propylene oxide 153795-76-7 Minerals, Metals and other Inorganics carbon dioxide 124-38-9 sodium bicarbonate 144-55-8 Sodium Carbonate 497-19-8 Potassium Carbonate 584-08-7 Boric Anhydride (a.k.a. Boric Oxide) 1303-86-2 sodium tetraborate decahydrate 1303-96-4 Potassium Hydroxide 1310-58-3 DRAFT SGEIS 9/30/2009, Page 5-57 Chemical CAS Number sodium hydroxide 1310-73-2 aluminum chloride, basic 1327-41-9 sodium tetraborate decahydrate 1332-77-0 aqua ammonia 29.4% 1336-21-6 ammonium hydrogen-difluoride 1341-49-7 ammonium thiocyanate 1762-95-4 sulfamic acid 5329-14-6 hydroxylamine hydrochloride 5470-11-1 ammonium nitrate 6484-52-2 cupric chloride dihydrate 7447-39-4 potassium chloride 7447-40-7 Trisodium ortho phosphate 7601-54-9 Non-Crystaline Silica 7631-86-9 sodium bisulfate 7631-90-5 hydrochloric acid 7647-01-0 sodium chloride 7647-14-5 sodium bromide 7647-15-6
aqueous ammonia 7664-41-7 sodium hypochlorite 7681-52-9 ferric chloride 7705-08-0 nitrogen 7727-37-9 ammonium persulfate 7727-54-0 water 7732-18-5 sodium sulfate 7757-82-6 sodium chlorite 7758-19-2 sodium thousulfate 7772-98-7 Sodium Metaborate.8H2O 7775-19-01 Sodium Persulphate 7775-27-1 ferrous sulfate, heptahydrate 7782-63-0 ammonium bisulfate 7783-20-2 boric acid 10043-35-3 Calcium Chloride 10043-52-4 Chlorine Dioxide 10049-04-4 ammonium bisulphite 10192-30-0 sodium perborate tetrahydrate 10486-00-7 ammonium chloride 12125-02-9 potassium borate 12714-38-8 potassium metaborate 13709-94-9 DRAFT SGEIS 9/30/2009, Page 5-58 Chemical CAS Number Magnesium Silicate Hydrate (Talc) 14807-96-6 crystalline silica (quartz) 14808-60-7 glassy calcium magnesium phosphate 65997-17-3 silica gel 112926-00-8 synthetic amorphous, pyrogenic silica 112945-52-5 synthetic amorphous, pyrogenic silica 121888-66-2 Miscellaneous formaldehyde 50-00-0 Sucrose 57-50-1 lactose 63-42-3 acetone 67-64-1 ethylene oxide 75-21-8 1-octadecene 112-88-9 1,4-dioxane 123-91-1 1-hexadecene 629-73-2 1-tetradecene 1120-36-1 sorbitan monooleate 1338-43-8 1-eicosene 3452-07-1 D-Limonene 5989-27-5 Pine Oil 8000-41-7 2,2'-azobis-{2-(imidazlin-2-yl)propane}-dihydrochloride 27776-21-2 3,5,7-triaza-1-azoniatricyclo[3.3.1.13,7]decane, 1-(3-chloro-2-propenyl)-chloride 51229-78-8 alkenes 64743-02-8 Cocamidopropyl Oxide 68155-09-9 terpene and terpenoids 68647-72-3 terpene hydrocarbon byproducts 68956-56-9 tar bases, quinoline derivs., benzyl chloride-quaternized 72780-70-7
citrus terpenes 94266-47-4 organophilic clays 121888-68-4 Listed without CAS Number31 belongs with amines proprietary quaternary ammonium compounds NA quaternary ammonium compound NA
31 Constituents listed without CAS #’s were tentatively placed in chemical categories based on the name listed on the MSDS or within confidential product composition disclosures. Many of the constituents reported without CAS #s, are mixtures which require further disclosure to DEC. DRAFT SGEIS 9/30/2009, Page 5-59 Chemical CAS Number triethanolamine (tea) 85%, drum NA Quaternary amine NA Fatty amidoalkyl betaine NA belongs with petroleum distillates petroleum distillate blend NA belongs with aromatic hydrocarbons aromatic hydrocarbon NA aromatic ketones NA belongs with glycol ethers and ethoxylated alcohols Acetylenic Alcohol NA Aliphatic Alcohols, ethoxylated NA Aliphatic Alcohol glycol ether NA Ethoxylated alcohol linear NA Ethoxylated alcohols NA aliphatic alcohol polyglycol ether NA alkyl aryl polyethoxy ethanol NA misture of ethoxylated alcohols NA nonylphenol ethoxylate NA oxyalkylated alkylphenol NA polyethoxylated alkanol NA Oxyalkylated alcohol NA belongs with organic acids Aliphatic acids derivative NA Aliphatic Acids NA hydroxy acetic acid NA citric acid 50%, base formula NA Alkylaryl Sulfonate NA belongs with polymers hydroxypropyl guar NA 2-acrylamido-2-methylpropanesulphonic acid sodium salt polymer NA belongs with minerals, metals and other inorganics precipitated silica NA sodium hydroxide NA belongs with miscellaneous epa inert ingredient NA non-hazardous ingredients NA proprietary surfactant NA salt of fatty acid/polyamine reaction product NA
DRAFT SGEIS 9/30/2009, Page 5-60 Chemical CAS Number salt of amine-carbonyl condensate NA surfactant blend NA sugar NA polymeric hydrocarbon mixture NA Although exposure to fracturing additives would require a failure of operational controls such as an accident, a spill or other non-routine incident, the health concerns noted by NYSDOH for each chemical category are discussed below. The discussion is based on available qualitative hazard information for chemicals from each category. Qualitative descriptions of potential health concerns discussed below generally apply to all exposure routes (i.e., ingestion, inhalation or skin contact) unless a specific exposure route is mentioned. For most chemical categories, health information is available for only some of the chemicals in the category. More specific assessment of health risks associated with a contamination event would entail an analysis based on the specific additives being used and site-specific information about exposure pathways and environmental contaminant levels. Potential human health risks of a specific event would be assessed by comparison of case-specific exposure data with existing drinking standards or ambient air guidelines.32 If needed, other chemical-specific health comparison values would be developed, based on a case-specific review of toxicity literature for the chemicals involved. A case-specific assessment would include information on how potential health effects might differ (both qualitatively and quantitatively) depending on the route of exposure. Petroleum Distillate Products Petroleum-based constituents are included in some fracturing fluid additive products. They are listed in MSDSs as various petroleum distillate fractions including kerosene, petroleum naphtha, aliphatic hydrocarbon, petroleum base oil, heavy aromatic petroleum naphtha, mineral spirits,
hydrotreated light petroleum distillates, stoddard solvent or aromatic hydrocarbon. These can be found in a variety of additive products including corrosion inhibitors, friction reducers and solvents. Petroleum distillate products are mixtures that vary in their composition, but they have similar adverse health effects. Accidental ingestion that results in exposure to large amounts of 32 10 NYCRR Part 5: Drinking Water Supplies; Subpart 5-1: Public Water Systems, Maximum Contaminant Levels; NYS DEC Policy DAR-1: Guidelines for the Control of Toxic Ambient Air Contaminants DRAFT SGEIS 9/30/2009, Page 5-61 petroleum distillates is associated with adverse effects on the gastrointestinal system and central nervous system. Skin contact with kerosene for short periods can cause skin irritation, blistering or peeling. Breathing petroleum distillate vapors can adversely affect the central nervous system. Aromatic Hydrocarbons Some fracturing additive products contain specific aromatic hydrocarbon compounds that can also occur in petroleum distillates (benzene, toluene, ethylbenzene and xylene or BTEX; naphthalene and related derivatives, trimethylbenzene, diethylbenzene, dodecylbenzene, cumene). BTEX compounds are associated with adverse effects on the nervous system, liver, kidneys and blood-cell-forming tissues. Benzene has been associated with an increased risk of leukemia in industrial workers who breathed elevated levels of the chemical over long periods of time in workplace air. Exposure to high levels of xylene has damaged the unborn offspring of laboratory animals exposed during pregnancy. Naphthalene is associated with adverse effects on red blood cells when people consumed naphthalene mothballs or when infants wore cloth diapers stored in mothballs. Laboratory animals breathing naphthalene vapors for their lifetimes had damage to their respiratory tracts and increased risk of nasal and lung tumors. Glycols
Glycols occur in several fracturing fluid additives including crosslinkers, breakers, clay and iron controllers, friction reducers and scale inhibitors. Propylene glycol has low inherent toxicity and is used as an additive in food, cosmetic and drug products. High exposure levels of ethylene glycol adversely affect the kidneys and reproduction in laboratory animals. Glycol Ethers Glycol ethers and related ethoxylated alcohols and phenols are present in fracturing fluid additives, including corrosion inhibitors, surfactants and friction reducers. Some glycol ethers (e.g., monomethoxyethanol, monoethoxyethanol, propylene glycol monomethyl ether, ethylene glycol monobutyl ether) can affect the male reproductive system and red blood cell formation in laboratory animals at high exposure levels. DRAFT SGEIS 9/30/2009, Page 5-62 Alcohols Alcohols are present in some fracturing fluid additive products, including corrosion inhibitors, foaming agents, iron and scale inhibitors and surfactants. Exposure to high levels of some alcohols (e.g., ethanol, methanol) affect the central nervous system. Amides Acrylamide is used in some fracturing fluid additives to create polymers during the stimulation process. These polymers are part of some friction reducers and scale inhibitors. Although the reacted polymers that form during fracturing are of low inherent toxicity, unreacted acrylamide may be present in the fracturing fluid, or breakdown of the polymers could release acrylamide back into the flowback water. High levels of acrylamide damage the nervous system and reproductive system in laboratory animals and also cause cancer in laboratory animals. Formamide may be used in some corrosion inhibitors products. Ingesting high levels of formamide adversely affects the female reproductive system in laboratory animals. Amines
Amines are constituents of fracturing fluid products including corrosion inhibitors, cross-linkers, friction reducers, iron and clay controllers and surfactants. Chronic ingestion of mono-, di- or tri-ethanolamine adversely affects the liver and kidneys of laboratory animals. Some quaternary ammonium compounds, such as dimethyldiallyl ammonium chloride, can react with chemicals used in some systems for drinking water disinfection to form nitrosamines. Nitrosamines cause genetic damage and cancer when ingested by laboratory animals. Organic Acids, Salts and Related Chemicals Organic acids and related chemicals are constituents of fracturing fluid products including acids, buffers, corrosion and scale inhibitors, friction reducers, iron and clay controllers, solvents and surfactants. Some short-chain organic acids such as formic, acetic and citric acids can be corrosive or irritating to skin and mucous membranes at high concentrations. However, acetic and citric acids are regularly consumed in foods (such as vinegar and citrus fruits) where they occur naturally at lower levels that are not harmful. DRAFT SGEIS 9/30/2009, Page 5-63 Some foaming agents and surfactant products contain organic chemicals included in this category that contain a sulfonic acid group (sulfonates). Exposure to elevated levels of sulfonates is irritating to the skin and mucous membranes. Microbiocides Microbiocides are antimicrobial pesticide products intended to inhibit the growth of various types of bacteria in the well. A variety of different chemicals are used in different microbiocide products that are proposed for Marcellus wells. Toxicity information is limited for several of the microbiocide chemicals. However, for some, high exposure has caused effects in the respiratory and gastrointestinal tracts, the kidneys, the liver and the nervous system in laboratory animals. Other Constituents
The remaining chemicals listed in MSDSs and confidential product composition disclosures provided to DEC are included in Table 5.7 under the following categories: polymers, miscellaneous chemicals that did not fit another chemical category and product constituents that were not identified by a Chemical Abstract Service (CAS) number. Readily available health effects information is lacking for many of these constituents, but two that are relatively well studied are discussed here. In the event of environmental contamination involving chemicals lacking readily available health effects information, the toxicology literature would have to be researched for chemical-specific toxicity data. Formaldehyde is listed as a constituent in some corrosion inhibitors, scale inhibitors and surfactants. In most cases, the concentration listed in the product is relatively low (< 1%) and is listed alongside a formaldehyde-based polymer constituent. Formaldehyde is irritating to tissues when it comes into direct contact with them. The most common symptoms include irritation of the skin, eyes, nose, and throat, along with increased tearing. Severe pain, vomiting, coma, and possible death can occur after drinking large amounts of formaldehyde. Several studies of laboratory rats exposed for life to high amounts of formaldehyde in air found that the rats developed nose cancer. Some studies of humans exposed to lower amounts of formaldehyde in workplace air found more cases of cancer of the nose and throat (nasopharyngeal cancer) than expected, but other studies have not found nasopharyngeal cancer in other groups of workers exposed to formaldehyde in air. DRAFT SGEIS 9/30/2009, Page 5-64 1,4-dioxane may be used in some surfactant products. 1,4-Dioxane is irritating to the eyes and nose when vapors are breathed. Exposure to very high levels may cause severe kidney and liver
effects and possibly death. Studies in animals have shown that breathing vapors of 1,4-dioxane, swallowing liquid 1,4-dioxane or contaminated drinking water, or having skin contact with liquid 1,4-dioxane affects mainly the liver and kidneys. Laboratory rats and mice that drank water containing 1,4-dioxane during most of their lives developed liver cancer; the rats also developed cancer inside the nose. Conclusions The hydraulic fracturing product additives proposed for use in NYS and used for fracturing horizontal Marcellus shale wells in other states contain similar types of chemical constituents as the products that have been used for many years for hydraulic fracturing of traditional vertical wells in NYS. Some of the same products are used in both well types. The total amount of fracturing additives and water used in hydraulic fracturing of horizontal wells is considerably larger than for traditional vertical wells. This suggests the potential environmental consequences of an upset condition could be proportionally larger for horizontal well drilling and fracturing operations. As mentioned earlier, the 1992 GEIS addressed hydraulic fracturing in Chapter 9, and NYSDOH’s review did not identify any potential exposure situations associated with horizontal drilling and high-volume hydraulic fracturing that are qualitatively different from those addressed in the GEIS.
Name der Studie Titel der abgelaufenden klinischen Studien Stand der Studie A Phase 3 Randomized, Double-blind, Parallel-group, Multi-center Study of the Safety and Efficacy of Apixaban for Prophylaxis of Venous Thromboembolism in Acutely III Medical Subjects During and Following HospitalizationA Safety and Efficacy Trial Evaluating the Use of Apixaban for the extended Treatment of Deep