Sunday, September 4, 2011

Chemicals Used in Hydraulic Fracturing

by Diane, M.P.H, M.S.

The following information describes chemicals used in hydraulic fracturing, i.e., hydrofracking, and is included here as an addendum to the article: “The United States Should Do More To Promote Safe Energy Production Which Does Not Threaten Environmental and Public Health”:

Environmental and human health concerns associated with hydraulic fracturing include (3):
  1. Ground water and aquifer contamination
  2. Risks to air quality
  3. Migration of gases and hydraulic fracturing chemicals to the surface
  4. Risk of explosive gases entering private potable water wells, creating “flammable water”
  5. Tremors and earthquakes within surrounding geographic areas
  6. Potential mishandling of waste
  7. Loss of land safe for agricultural production
  8. Loss of land value
  9. Human and animal health risks, including, but not limited to: birth defects, miscarriages, cancers, attention deficit disorder, hyperactivity, learning and other neurological deficits and/or damage. Chemicals currently being used to drill natural gas wells in Pennsylvania have already been associated with neurological problems.
    A 2010 study performed by the Environmental Protection Agency (EPA) found contaminants in drinking water including: arsenic, copper, vanadium, and adamantanes adjacent to drilling operations. The EPA has investigated several sources, including agricultural activity, but noted gas drilling as a potential cause. On June 23, 2011, the EPA announced that it will examine claims of water pollution related to hydraulic fracturing in Texas, North Dakota, Pennsylvania, Colorado and Louisiana (3).

    Chart: States With Drilling Disclosure Rules (8)
    Five states have passed laws or administrative rules requiring drilling companies to reveal some of the chemicals they use when injecting fluids to free natural gas and oil from underground rock formations.

    * Wyoming was the first state to require disclosure of fracking fluids.
    ** Pennsylvania officials did not return calls or emails seeking clarification.
    *** The Texas legislature passed the law in May 2011, but state regulators have until 2013 to complete the actual rules.

    Chemical Constituents in Additives (3)

    About 750 chemicals have been listed as additives for hydraulic fracturing in a report to the US Congress in 2011 (5). The following is a list of the different types of additives that are used in fracturing operations, as indicated by the New York State Department of Environmental Conservation (7).
    Classes of Additives↓Purpose↓Examples↓
    AcidFacilitates entry into rock formationshydrochloric acid
    BiocidesKill bacteria and reduce risk of foulingglutaraldehyde, 2,2 Dibromo-3-nitrilopropionamide
    BreakerFacilitate proppant entryperoxodisulfates
    Clay stabilizerClay stabilizationsalts, ie tetramethylammonium chloride
    Corrosion inhibitorWell maintenancemethanol
    CrosslinkerFacilitate proppant entrypotassium hydroxide
    Friction reducersImprove surface pressuresodium acrylate, polyacrylamide
    Gelling agentsProppant placementguar gum
    Iron controlWell maintenancecitric acid, thioglycolic acid
    Scale inhibitorPrevention of precipitationammonium chloride, ethylene glycol, polyaccrylate
    SurfactantReduction in fluid tensionmethanol, isopropanol

    List of Additives for Hydraulic Fracturing (6)

    About 750 chemicals have been listed as additives for hydraulic fracturing in a report to the US Congress in 2011 (5). The following is a partial list of the chemical constituents in additives used in fracturing operations, as indicated by the New York State Department of Environmental Conservation (7).
    CAS Number↓Chemical Constituent↓
    2634-33-51,2-Benzisothiazolin-2-one / 1,2-benzisothiazolin-3-one
    95-63-61,2,4-trimethylbenzene
    123-91-11,4-Dioxane
    3452-07-11-eicosene
    629-73-21-hexadecene
    112-88-91-octadecene
    1120-36-11-tetradecene
    10222-01-22,2 Dibromo-3-nitrilopropionamide, a biocide
    27776-21-22,2′-azobis-{2-(imidazlin-2-yl)propane}-dihydrochloride
    73003-80-22,2-Dibromomalonamide
    15214-89-82-Acrylamido-2-methylpropane sulphonic acid sodium salt polymer
    46830-22-22-acryloyloxyethyl(benzyl)dimethylammonium chloride
    52-51-72-Bromo-2-nitro-1,3-propanediol
    111-76-22-Butoxy ethanol
    1113-55-92-Dibromo-3-Nitriloprionamide (2-Monobromo-3-nitriilopropionamide)
    104-76-72-Ethyl Hexanol
    67-63-02-Propanol / Isopropyl Alcohol / Isopropanol / Propan-2-ol
    26062-79-32-Propen-1-aminium, N,N-dimethyl-N-2-propenyl-chloride, homopolymer
    9003-03-62-propenoic acid, homopolymer, ammonium salt
    25987-30-82-Propenoic acid, polymer with 2 p-propenamide, sodium salt / Copolymer of acrylamide and sodium acrylate
    71050-62-92-Propenoic acid, polymer with sodium phosphinate (1:1)
    66019-18-92-propenoic acid, telomer with sodium hydrogen sulfite
    107-19-72-Propyn-1-ol / Propargyl alcohol
    51229-78-83,5,7-Triaza-1-azoniatricyclo[3.3.1.13,7]decane, 1-(3-chloro-2-propenyl)-chloride,
    115-19-53-methyl-1-butyn-3-ol
    127087-87-04-Nonylphenol Polyethylene Glycol Ether Branched / Nonylphenol ethoxylated / Oxyalkylated Phenol
    64-19-7Acetic acid
    68442-62-6Acetic acid, hydroxy-, reaction products with triethanolamine
    108-24-7Acetic Anhydride
    67-64-1Acetone
    79-06-1Acrylamide
    38193-60-1Acrylamide – sodium 2-acrylamido-2-methylpropane sulfonate copolymer
    25085-02-3Acrylamide – Sodium Acrylate Copolymer or Anionic Polyacrylamide
    69418-26-4Acrylamide polymer with N,N,N-trimethyl-2[1-oxo-2-propenyl]oxy Ethanaminium chloride
    15085-02-3 Acrylamide-sodium acrylate copolymer
    68551-12-2Alcohols, C12-C16, Ethoxylated (a.k.a. Ethoxylated alcohol)
    64742-47-8Aliphatic Hydrocarbon / Hydrotreated light distillate / Petroleum Distillates / Isoparaffinic Solvent / Paraffin Solvent / Napthenic Solvent
    64743-02-8Alkenes
    68439-57-6Alkyl (C14-C16) olefin sulfonate, sodium salt
    9016-45-9Alkylphenol ethoxylate surfactants
    1327-41-9Aluminum chloride
    73138-27-9Amines, C12-14-tert-alkyl, ethoxylated
    71011-04-6Amines, Ditallow alkyl, ethoxylated
    68551-33-7Amines, tallow alkyl, ethoxylated, acetates
    1336-21-6Ammonia
    631-61-8Ammonium acetate
    68037-05-8Ammonium Alcohol Ether Sulfate
    7783-20-2Ammonium bisulfate
    10192-30-0Ammonium bisulfite
    12125-02-9Ammonium chloride
    7632-50-0Ammonium citrate
    37475-88-0Ammonium Cumene Sulfonate
    1341-49-7Ammonium hydrogen-difluoride
    6484-52-2Ammonium nitrate
    7727-54-0Ammonium Persulfate / Diammonium peroxidisulphate
    1762-95-4Ammonium Thiocyanate
    7664-41-7Aqueous ammonia
    121888-68-4Bentonite, benzyl(hydrogenated tallow alkyl) dimethylammonium stearate complex / organophilic clay
    71-43-2Benzene
    119345-04-9Benzene, 1,1′-oxybis, tetratpropylene derivatives, sulfonated, sodium salts
    74153-51-8Benzenemethanaminium, N,N-dimethyl-N-[2-[(1-oxo-2-propenyl)oxy]ethyl]-, chloride, polymer with 2-propenamide
    10043-35-3Boric acid
    1303-86-2Boric oxide / Boric Anhydride
    71-36-3Butan-1-ol
    68002-97-1C10 – C16 Ethoxylated Alcohol
    68131-39-5C12-15 Alcohol, Ethoxylated
    10043-52-4Calcium chloride
    124-38-9Carbon dioxide
    68130-15-4Carboxymethylhydroxypropyl guar
    9012-54-8Cellulase / Hemicellulase Enzyme
    9004-34-6Cellulose
    10049-04-4Chlorine dioxide
    77-92-9Citric Acid
    94266-47-4Citrus Terpenes
    61789-40-0Cocamidopropyl betaine
    68155-09-9Cocamidopropylamine Oxide
    68424-94-2Coco-betaine
    7758-98-7Copper(II) sulfate
    31726-34-8Crissanol A-55
    14808-60-7Crystalline Silica (Quartz)
    7447-39-4Cupric chloride dihydrate
    1120-24-7Decyldimethyl Amine
    2605-79-0Decyl-dimethyl Amine Oxide
    3252-43-5Dibromoacetonitrile
    25340-17-4Diethylbenzene
    111-46-6Diethylene glycol
    22042-96-2Diethylenetriamine penta (methylenephonic acid) sodium salt
    28757-00-8Diisopropyl naphthalenesulfonic acid
    68607-28-3Dimethylcocoamine, bis(chloroethyl) ether, diquaternary ammonium salt
    7398-69-8Dimethyldiallylammonium chloride
    25265-71-8Dipropylene glycol
    139-33-3Disodium Ethylene Diamine Tetra Acetate
    5989-27-5D-Limonene
    123-01-3Dodecylbenzene
    27176-87-0Dodecylbenzene sulfonic acid
    42504-46-1Dodecylbenzenesulfonate isopropanolamine
    50-70-4D-Sorbitol / Sorbitol
    37288-54-3Endo-1,4-beta-mannanase, or Hemicellulase
    149879-98-1Erucic Amidopropyl Dimethyl Betaine
    89-65-6Erythorbic acid, anhydrous
    54076-97-0Ethanaminium, N,N,N-trimethyl-2-[(1-oxo-2-propenyl)oxy]-, chloride, homopolymer
    107-21-1 Ethane-1,2-diol / Ethylene Glycol
    9002-93-1Ethoxylated 4-tert-octylphenol
    68439-50-9Ethoxylated alcohol
    126950-60-5Ethoxylated alcohol
    67254-71-1Ethoxylated alcohol (C10-12)
    68951-67-7Ethoxylated alcohol (C14-15)
    68439-46-3Ethoxylated alcohol (C9-11)
    66455-15-0Ethoxylated Alcohols
    84133-50-6Ethoxylated Alcohols (C12-14 Secondary)
    68439-51-0Ethoxylated Alcohols (C12-14)
    78330-21-9Ethoxylated branch alcohol
    34398-01-1Ethoxylated C11 alcohol
    61791-12-6Ethoxylated Castor Oil
    61791-29-5Ethoxylated fatty acid, coco
    61791-08-0Ethoxylated fatty acid, coco, reaction product with ethanolamine
    68439-45-2Ethoxylated hexanol
    9036-19-5Ethoxylated octylphenol
    9005-67-8Ethoxylated Sorbitan Monostearate
    9004-70-3Ethoxylated Sorbitan Trioleate
    64-17-5Ethyl alcohol / ethanol
    100-41-4Ethyl Benzene
    97-64-3Ethyl lactate
    9003-11-6Ethylene Glycol-Propylene Glycol Copolymer (Oxirane, methyl-, polymer with oxirane)
    75-21-8Ethylene oxide
    5877-42-9Ethyloctynol
    68526-86-3Exxal 13
    61790-12-3Fatty Acids
    68188-40-9Fatty acids, tall oil reaction products w/ acetophenone, formaldehyde & thiourea
    9043-30-5Fatty alcohol polyglycol ether surfactant
    7705-08-0Ferric chloride
    7782-63-0Ferrous sulfate, heptahydrate
    50-00-0Formaldehyde
    29316-47-0Formaldehyde polymer with 4,1,1-dimethylethyl phenolmethyl oxirane
    153795-76-7Formaldehyde, polymers with branched 4-nonylphenol, ethylene oxide and propylene oxide
    75-12-7Formamide
    64-18-6Formic acid
    110-17-8Fumaric acid
    65997-17-3Glassy calcium magnesium phosphate
    111-30-8Glutaraldehyde
    56-81-5Glycerol / glycerine
    9000-30-0Guar Gum
    64742-94-5Heavy aromatic petroleum naphtha
    9025-56-3Hemicellulase
    7647-01-0Hydrochloric Acid / Hydrogen Chloride / muriatic acid
    7722-84-1Hydrogen peroxide
    79-14-1Hydroxy acetic acid
    35249-89-9Hydroxyacetic acid ammonium salt
    9004-62-0Hydroxyethyl cellulose
    5470-11-1Hydroxylamine hydrochloride
    39421-75-5Hydroxypropyl guar
    35674-56-7Isomeric Aromatic Ammonium Salt
    64742-88-7Isoparaffinic Petroleum Hydrocarbons, Synthetic
    64-63-0Isopropanol
    98-82-8Isopropylbenzene (cumene)
    68909-80-8Isoquinoline, reaction products with benzyl chloride and quinoline
    8008-20-6Kerosene
    64742-81-0Kerosine, hydrodesulfurized
    63-42-3Lactose
    64742-95-6Light aromatic solvent naphtha
    1120-21-4Light Paraffin Oil
    14807-96-6Magnesium Silicate Hydrate (Talc)
    1184-78-7methanamine, N,N-dimethyl-, N-oxide
    67-56-1Methanol
    68891-11-2Methyloxirane polymer with oxirane, mono (nonylphenol) ether, branched
    8052-41-3Mineral spirits / Stoddard Solvent
    141-43-5Monoethanolamine
    44992-01-0N,N,N-trimethyl-2[1-oxo-2-propenyl]oxy Ethanaminium chloride
    64742-48-9Naphtha (petroleum), hydrotreated heavy
    91-20-3Naphthalene
    38640-62-9Naphthalene bis(1-methylethyl)
    93-18-5Naphthalene, 2-ethoxy-
    68909-18-2N-benzyl-alkyl-pyridinium chloride
    68139-30-0N-Cocoamidopropyl-N,N-dimethyl-N-2-hydroxypropylsulfobetaine
    7727-37-9Nitrogen, Liquid form
    68412-54-4Nonylphenol Polyethoxylate
    121888-66-2Organophilic Clays
    64742-65-0Petroleum Base Oil
    64741-68-0Petroleum naphtha
    70714-66-8Phosphonic acid, [[(phosphonomethyl)imino]bis[2,1-ethanediylnitrilobis(methylene)]]tetrakis-, ammonium salt
    8000-41-7Pine Oil
    60828-78-6Poly(oxy-1,2-ethanediyl), a-[3,5-dimethyl-1-(2-methylpropyl)hexyl]-w-hydroxy-
    25322-68-3Poly(oxy-1,2-ethanediyl), a-hydro-w-hydroxy / Polyethylene Glycol
    24938-91-8Poly(oxy-1,2-ethanediyl), α-tridecyl-ω-hydroxy-
    51838-31-4Polyepichlorohydrin, trimethylamine quaternized
    56449-46-8Polyethlene glycol oleate ester
    62649-23-4Polymer with 2-propenoic acid and sodium 2-propenoate
    9005-65-6Polyoxyethylene Sorbitan Monooleate
    61791-26-2Polyoxylated fatty amine salt
    127-08-2Potassium acetate
    12712-38-8Potassium borate
    1332-77-0Potassium borate
    20786-60-1Potassium Borate
    584-08-7Potassium carbonate
    7447-40-7Potassium chloride
    590-29-4Potassium formate
    1310-58-3Potassium Hydroxide
    13709-94-9Potassium metaborate
    24634-61-5Potassium sorbate
    112926-00-8Precipitated silica / silica gel
    57-55-6Propane-1,2-diol, or Propylene glycol
    107-98-2Propylene glycol monomethyl ether
    68953-58-2Quaternary Ammonium Compounds
    62763-89-7Quinoline,2-methyl-, hydrochloride
    15619-48-4Quinolinium, 1-(phenylmethl),chloride
    7631-86-9Silica, Dissolved
    5324-84-5Sodium 1-octanesulfonate
    127-09-3Sodium acetate
    95371-16-7Sodium Alpha-olefin Sulfonate
    532-32-1Sodium benzoate
    144-55-8Sodium bicarbonate
    7631-90-5Sodium bisulfate
    7647-15-6Sodium bromide
    497-19-8Sodium carbonate
    7647-14-5Sodium Chloride
    7758-19-2Sodium chlorite
    3926-62-3Sodium chloroacetate
    68-04-2Sodium citrate
    6381-77-7Sodium erythorbate / isoascorbic acid, sodium salt
    2836-32-0Sodium Glycolate
    1310-73-2Sodium Hydroxide
    7681-52-9Sodium hypochlorite
    7775-19-1Sodium Metaborate .8H2O
    10486-00-7Sodium perborate tetrahydrate
    7775-27-1Sodium persulfate
    9003-04-7Sodium polyacrylate
    7757-82-6Sodium sulfate
    1303-96-4Sodium tetraborate decahydrate
    7772-98-7Sodium thiosulfate
    1338-43-8Sorbitan Monooleate
    57-50-1Sucrose
    5329-14-6Sulfamic acid
    112945-52-5Synthetic Amorphous / Pyrogenic Silica / Amorphous Silica
    68155-20-4Tall Oil Fatty Acid Diethanolamine
    8052-48-0Tallow fatty acids sodium salt
    72480-70-7Tar bases, quinoline derivs., benzyl chloride-quaternized
    68647-72-3Terpene and terpenoids
    68956-56-9Terpene hydrocarbon byproducts
    533-74-4Tetrahydro-3,5-dimethyl-2H-1,3,5-thiadiazine-2-thione (a.k.a. Dazomet)
    55566-30-8Tetrakis(hydroxymethyl)phosphonium sulfate (THPS)
    75-57-0Tetramethyl ammonium chloride
    64-02-8Tetrasodium Ethylenediaminetetraacetate
    68-11-1Thioglycolic acid
    62-56-6Thiourea
    68527-49-1Thiourea, polymer with formaldehyde and 1-phenylethanone
    108-88-3Toluene
    81741-28-8Tributyl tetradecyl phosphonium chloride
    68299-02-5Triethanolamine hydroxyacetate
    112-27-6Triethylene glycol
    52624-57-4Trimethylolpropane, Ethoxylated, Propoxylated
    150-38-9Trisodium Ethylenediaminetetraacetate
    5064-31-3Trisodium Nitrilotriacetate
    7601-54-9Trisodium orthophosphate
    57-13-6Urea
    25038-72-6Vinylidene Chloride/Methylacrylate Copolymer
    7732-18-5Water
    1330-20-7Xylene
    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

    References:

    1. Burkey, Brent M. “See the State’s List of Chemicals Used in Hydrofracking.” July 19, 2010. ( www.yorkblog.com/…/see-the-states-list-of-chemicals-used-in-hydr…)
    2. Hydrofracking Can Leach Toxic Chemicals. Are You Safe? (www.nrdc.org)
    3. “Hydraulic Fracturing.” Wikipedia: The Free Encyclopedia. July 21, 2011. (en.wikipedia.org/wiki/Hydraulic_fracturing)
    4. Kuznetz, Nicholas. “Critics Find Gaps in State Laws to Disclose Hydrofracking Chemicals.” ProPublica. June 20, 2011.(www.propublica.org/article/…hydrofracking chemicals-single)
    5. Kusnetz, Nicholas. ”Fracking Chemicals Cited in Congressional Report Stay Underground”. ProPublica. Published April 8, 2011. Retrieved July 11, 2011.
    6. “List of Additives for Hydraulic Fracturing.” Wikipedia: The Free Encyclopedia. July 27, 2011. (en.wikipedia.org/wiki/List-of-additives-for-hydraulic -fracturing)
    7. “Natural Gas Development Activities and High-Volume Hydraulic Fracturing”. New York State Department of Environmental Conservation. September 30, 2009. pp. 45–51.
    8. “States With Drilling Disclosure Rules”. WTFrack.org: Chart: States With Drilling Disclosure Rules”. June 24, 2011. <strong>Source:</strong> <em>Reporting by Nicholas Kusnetz/ProPublica</em> (wtfrackorg.blogspot.com/…/chart-states-with-drilling-disclosure.html)
    9. http://anga.us/media/136662/cogis%20complaint%20report%205-23-08.pdf
    10. “EPA: Natural Gas Drilling May Contaminate Drinking Water – Science News”. redOrbit. 2011-06-25. Retrieved 2011-07-13.

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