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Waste Management of Cuttings, Drilling Fluids, Hydrofrack Water and Produced Water Cuttings and Drilling Fluids/Muds When a well is drilled, the ‘cuttings’ of drilled rock need to be removed from the well bore. The cuttings, the drilling fluid or mud (to lubricate the drill and help remove the cuttings), and water in the bore hole are brought to the surface where the cuttings are then separated from the fluid, which will be reused in the drilling process. The cuttings and remaining fluids are generally stored in a drilling pit. In New York State, there are specifications regarding the construction of these pits, including a requirement that all pits be lined with plastic to avoid polluted water in the pit entering the soil and shallow groundwater. As mentioned in the Runoff section, it appears that the DSGEIS does not require that all drilling waste (including drilling muds, cuttings and flow back waters) be fully contained on site. Rather, drilling waste and possibly flow back waters can apparently be stored in open, lined pits on site except on floodplains and the NYC watershed. It is not clear why full containment should not be required for all sites. “drilling fluids or muds are made up of: a base fluid (water, diesel or mineral oil, or a synthetic compound); weighting agents (most frequently barite is used); bentonite clay chrome lignosulfonates and lignites and various additives that serve specific functions, such as biocides, diesel lubricants and chromate corrosion inhibitors ….Drilling muds that circulate through the well and return to the surface may contain dissolved and suspended contaminants including cadmium, arsenic, and metals such as mercury, copper and lead; hydrocarbons; hydrogen sulfide and natural gas, as well as drilling mud additives, many of which contain potentially harmful chemicals (e.g., chromate, barite).” (http://www.earthworksaction.org/pubs/OGAPMarcellusShaleReport-6-12-08.pdf) Drill cuttings … may be acidic and have the potential to mobilize metals in the cuttings or the soil to which they will be potentially exposed. Additionally, the Marcellus shale contains naturally occurring radioactive materials (NORMs), including radium. Hydrofracking Fluids Hydrofracking fluids are injected into wells under pressure in order to create cracks or fractures in the rock formation. These cracks accelerate gas flow out of the rock and into the well. Hydrofracking fluids are created by adding a proppant (commonly sand) to water. The role of the proppant is to keep the cracks from resealing once the hydrofracking fluid is withdrawn from the well. In addition to the proppant, several types of chemicals are added to the hydrofracking fluid to serve a number of purposes. A friction reducer is added to reduce the friction pressure during pumping operations. A surfactant is used to increase the recovery of injected water into a well. A biocide is used to inhibit the growth of organisms that could produce gases (particularly hydrogen sulfide) that could be dangerous as well as contaminate the methane gas. Scale inhibitors are used to control the precipitation of carbonates and sulfates. There is considerable controversy about the possible effects of the chemicals added to the hydrofracking fluids. Included in the list in the dSGEIS of over 200 chemicals that may be used in hydrofracking are at least two known carcinogens: benzene and formaldehyde. For other compounds, such as xylene and to a lesser extent monoethanolamine, some information suggests carcinogenic activity, but the literature is not in agreement. Table 6-13 of the dSGEIS also lists heavy naptha as a material likely to be used. Heavy naptha is not a unique compound, but rather a mixture of many hydrocarbons, including several that are carcinogenic. Benzene is a high-risk carcinogen and was found in nearly half of all flow back waters (Table 5-9) from Pennsylvania and West Virginia (14/29 samples) at concentrations ranging from 15.7 to 1950 µg/L, with an average of 479.5 µg/L. This average number is nearly 100 times the maximum contaminant level (5 µg/L) established by the EPA. The maximum concentration was nearly 400 times higher. Even if one considers a dilution or attenuation factor, as is done at superfund sites, of as much as 100, it is possible that mishandling of flowback water could contaminate nearby aquifers or groundwater at levels that could exceed a Maximum Contaminant Level (MCL) established by the EPA. Other compounds of concern in fracking fluids are nonylphenol and octylphenol ethoxylate surfactants Flowback After hydrofracking, the hydrofracking fluid is withdrawn from the well, and to the extent possible, from the formation. Currently in Pennsylvania, about 15% of the hydrofracking fluid returns to the surface within 2 to 8 weeks (http://www.srbc.net/programs/docs/ProjectReviewMarcellusShale(NEW)(1_2010).pdf); this is referred to as flowback water. The flowback water can be reused in hydrofracking other wells or disposed of as waste water…. This waste water will likely contain high levels of total dissolved solids (mostly salt or sodium chloride) and NORMS, as well as added chemicals and/or their degradation products. There are three ways this water, now considered industrial waste water can be disposed: 1) underground injection, 2) municipal sewage treatment facilities (POTWs) that have an approved pretreatment program for industrial waste, and 3) private industrial waste treatment facilities. The sites available for underground injection of waste water are limited, and there are concerns that in certain locations underground injection may induce seismicity. POTWs must pretreat the waste water to the extent that the waste stream does not damage the sewage treatment system and does not exceed its permitted capacity to release pollutants to receiving waters. POTWs are generally not effective in removing salts from waste water, so there is concern that individual and cumulative releases to surface waters from treated, yet salt enriched, waste water could, from individual or cumulative releases, disrupt freshwater ecosystems. Currently, there are no private industrial waste treatment facilities for handling Marcellus shale flowback water in New York State. The issue of NORMS, primarily radium, in the flowback water needs to be considered as well. Radium in flowback water may be reduced during treatment to acceptable levels to discharge into surface waters through being retained in the solid waste. This raises the issue of where to dispose of the radium enriched solid waste from pre-treatment of flowback water or flowback water treated in private facilities. IMPORTANT DEFINITIONS: Toxicity: Poisonous substance that does injury or death to a living system (human, animal or plant) Persistance: chemical that does NOT biodegrade, stays forever in whatever it contacts (soil, human, animal, plant) Bioaccumulate: means an increase in the concentration of a chemical in a biological organism over time Heavy Metals Introduction The term heavy metal refers to any metallic chemical element that has a relatively high density and is toxic or poisonous at low concentrations. Examples of heavy metals include mercury (Hg), cadmium (Cd), arsenic (As), chromium (Cr), thallium (Tl), and lead (Pb). Heavy metals are natural components of the Earth's crust. They cannot be degraded or destroyed. However, at higher concentrations they can lead to poisoning. Heavy metal poisoning could result, for instance, from drinking-water contamination, high ambient air concentrations near emission sources, or intake via the food chain. Heavy metals are dangerous because they tend to bioaccumulate. Bioaccumulation means an increase in the concentration of a chemical in a biological organism over time, compared to the chemical's concentration in the environment. Compounds accumulate in living things any time they are taken up and stored faster than they are broken down (metabolized) or excreted. Heavy metals can enter a water supply by industrial and consumer waste, and releasing heavy metals into streams, lakes, rivers, and groundwater. Chemicals Used by Hydraulic Fracturing Companies in Pennsylvania For Surface and Hydraulic Fracturing Activities Prepared by the Department of Environmental Protection Bureau of Oil and Gas Management Compiled from Material Safety Data Sheets obtained from Industry 1,2,4-Trimethylbenzene Glycol Ethers (includes 2BE) 1,3,5 Trimethylbenzene Guar gum 2,2-Dibromo-3-Nitrilopropionamide Hemicellulase Enzyme 2.2-Dibromo-3-Nitrilopropionamide Hydrochloric Acid 2-butoxyethanol Hydrotreated light distillate 2-Ethylhexanol Hydrotreated Light Distilled 2-methyl-4-isothiazolin-3-one Iron Oxide 5-chloro-2-methyl-4-isothiazotin-3-one Isopropanol Acetic Acid Isopropyl Alcohol Acetic Anhydride Kerosine Acie Pensurf Magnesium Nitrate Alchohol Ethoxylated Mesh Sand (Crystalline Silica) Alphatic Acid Methanol Alphatic Alcohol Polyglycol Ether Mineral Spirits Aluminum Oxide Monoethanolamine Ammonia Bifluoride Naphthalene Ammonia Bisulfite Nitrilotriacetamide Ammonium chloride Oil Mist Ammonium Salt Petroleum Distallate Blend Ammonia Persulfate Petroleum Distillates Aromatic Hydrocarbon Petroleum Naphtha Aromatic Ketones Polyethoxylated Alkanol (1) Boric Acid Polyethoxylated Alkanol (2) Boric Oxide Polyethylene Glycol Mixture Butan-1-01 Polysaccharide Citric Acid Potassium Carbonate Crystalline Silica: Cristobalite Potassium Chloride Crystalline Silica: Quartz Potassium Hydroxide Dazomet Prop-2-yn-1-01 Diatomaceus Earth Propan-2-01 Diesel (use discontinued) Propargyl Alcohol OTHER KNOWN CHEMICALS USED IN THE HYDRO FRACKING PROCESS: Agency for Toxic Substances & Disease Registry BTEX Affected Organ Systems: Hematological (Blood Forming), Immunological (Immune System), Neurological (Nervous System) Cancer Effects: Known to be a Human Carcinogen Chemical Classification: Volatile organic compounds Definitions BTEX - is an acronym that stands for benzene, toluene, ethylbenzene, and xylenes.[1] These compounds are some of the volatile organic compounds (VOCs) found in petroleum derivatives such as petrol (gasoline). Toluene, ethylbenzene, and xylenes have harmful effects on the central nervous system. BTEX compounds are notorious due to the contamination of soil and groundwater with these compounds. Naphthalene may also be included in Total BTEX analysis yielding results referred to as BTEXN. In the same way, styrene is sometimes added, making it BTEXS. Toluene To help public health professionals and others address the needs of persons living or working near hazardous waste sites, the information in this section is organized first by route of exposure (inhalation, oral, and dermal) and then by health effect (death, systemic, immunological, neurological, reproductive, developmental, genotoxic, and carcinogenic effects). These data are discussed in terms of three exposure periods: acute (14 days or less), intermediate (15–364 days), and chronic (365 days or more). Toluene dissolved in well water does not break down quickly while the water is under the ground because there are few microorganisms in underground water. A serious health concern is that toluene may have an effect on your brain. Toluene can cause headaches and sleepiness, and can impair your ability to think clearly. Toluene causes death by interfering with the way you breathe and the way your heart beats. Repeated exposure You may also experience problems with your speech, vision, or hearing, have loss of muscle control, loss of memory, poor balance, and decreased mental ability. Some of these changes may be permanent. Combinations of toluene and some common medicines like aspirin and acetaminophen may increase the effects of toluene on your hearing. Some studies in people have shown reproductive effects, such as an increased risk of spontaneous abortions, from exposure to toluene main effect of toluene is on the brain and nervous system. Toxicological Profile for Xylene meta-xylene, ortho-xylene, and para-xylene (m-, o-, and p-xylene). These different forms are referred to as isomers. Xylene is a liquid, and it can leak into soil, surface water (creeks, streams, rivers), or groundwater. Xylene below the soil surface may travel down through the soil and enter underground water (groundwater). Xylene may remain in groundwater for several months before it is finally broken down by small organisms. If a large amount of xylene enters soil from an accidental spill, a hazardous waste site, or a landfill, it may travel through the soil and contaminate drinking water wells. Chromium CAS ID #: 7440-47-3 Affected Organ Systems: Immunological (Immune System), Renal (Urinary System or Kidneys), Respiratory (From the Nose to the Lungs) Cancer Effects: Known to be a Human Carcinogen Chemical Classification: Inorganic substances Summary: Chromium is a naturally occurring element found in rocks, animals, plants, soil, and in volcanic dust and gases. Chromium is present in the environment in several different forms. The most common forms are chromium(0), chromium(III), and chromium(VI). No taste or odor is associated with chromium compounds. Chromium(III) occurs naturally in the environment and is an essential nutrient. Chromium(VI) and chromium(0) are generally produced by industrial processes. Long-term exposure can cause kidney and liver damage, and damage too circulatory and nerve tissue. Chromium often accumulates in aquatic life, adding to the danger of eating fish that may have been exposed to high levels of chromium. 1,2,4-Trimethylbenzene - irritation eyes, skin, nose, throat, respiratory system; bronchitis; hypochromic anemia; headache, drowsiness, lassitude (weakness, exhaustion), dizziness, nausea, incoordination; vomiting, confusion; chemical pneumonitis (aspiration liquid) Target Organs Eyes, skin, respiratory system, central nervous system, blood Breathing: Respiratory support Swallow: Medical attention immediately 1,3,5-Trimethylbenzene Exposure Routes inhalation, ingestion, skin and/or eye contact Symptoms irritation eyes, skin, nose, throat, respiratory system; bronchitis; hypochromic anemia; headache, drowsiness, lassitude (weakness, exhaustion), dizziness, nausea, incoordination; vomiting, confusion; chemical pneumonitis (aspiration liquid) Target Organs Eyes, skin, respiratory system, central nervous system, blood Breathing: Respiratory support Swallow: Medical attention immediately COMPARE THE LIST OF CHEMICALS TO SEE HOW MANY WAYS THEY AFFECT THE HUMAN BODY Hematological (Blood Forming) The blood cells (erythrocytes, granulocytes, and platelets) and the tissues that form them ((bone marrow, spleen, and lymph nodes) make up the hematological system. Blood carries oxygen, nutrients, and hormones to cells throughout the body. Also, it keeps the blood vessels open, helps the immunological system function (see immunological below), and removes waste and carbon dioxide from body cells. Substances Listing 1,2-Dichloroethene 1,2-Dichloropropane 1,3 Dinitrobenzene & 1,3,5 Trinitrobenzene 2,4,6-Trinitrotoluene (TNT) 2,4- & 2,6-Dinitrotoluene 2-Butoxyethanol Acetone Acrolein Acrylonitrile Benzene Cobalt Copper Diisopropyl Methylphosphonate (DIMP) Dinitrophenols Lead Methyl Mercaptan Methyl Parathion Naphthalene, 1-Methylnapthalene, 2-Methylnapthalen Nitrobenzene Nitrophenols Otto Fuel II and its Components Pentachlorophenol Phenol Radium Thorium Tin and Compounds Total Petroleum Hydrocarbons (TPH) Used Mineral-based Crankcase Oil Zinc Cardiovascular (Heart and Blood Vessels) The heart and blood vessels (arteries, capillaries, and veins) are called the cardiovascular system. The cardiovascular system carries blood throughout the body. The heart pumps blood through blood vessels called “arteries” and then through smaller blood vessels called “capillaries” to each organ and tissue in the body. The blood feeds each organ and tissue. Blood adds or removes gases, nutrients, hormones, and wastes as it passes through each organ to carry out metabolic processes (to keep the body alive). The capillaries then drain used blood into veins that flow back to the heart to be recirculated. Substances Listing 1,1,1-Trichloroethane 1,1-Dichloroethane 1,1-Dichloroethene 1,2-Dichloroethene 2,4- & 2,6-Dinitrotoluene Acrolein Antimony Barium Boron Bromomethane Cadmium Carbon Disulfide Carbon Monoxide Carbon Tetrachloride Chloroethane Chloroform Chloromethane Cobalt Lead Manganese Methylene Chloride Nickel Toluene Vanadium and Compounds Vinyl Chloride Hepatic (Liver) The hepatic system includes the liver and biliary tract . The liver maintains stable conditions throughout the body. It plays an important role in digesting food (through the secretion of bile), in synthesizing proteins (albumin, carrier proteins, coagulation factors, and many hormonal and growth factors), and in detoxifying harmful substances. Substances Listing 1,1,2,2-Tetrachloroethane 1,1,2-Trichloroethane 1,1-Dichloroethene 1,2,3 Trichloropropane 1,2-Dibromoethane 1,2-Dichloroethane 1,2-Dichloroethene 1,2-Dichloropropane 1,2-Diphenylhydrazine 1,4-Dioxane 2,3-Benzofuran 2-Butoxyethanol 4,4'-Methylenebis(2-Chloroaniline)(MBOCA) 4,4'-Methylenedianiline Aldrin/Dieldrin Arsenic Bromodichloromethane Bromoform & Dibromochloromethane Bromoform & Dibromochloromethane Carbon Disulfide Carbon Tetrachloride Chlordane Chlorobenzene Chlorodibenzofurans (CDFs) Chloroform Chloromethane Chlorophenols Copper Creosote DDT, DDE, DDD Di-n-octylphthalate (DNOP) Dichlorobenzenes Diethyl phthalate Endosulfan Fuel Oils / Kerosene Fuel Oils / Kerosene Heptachlor/Heptachlor Epoxide Hexachlorobenzene Hexachlorocyclohexane (HCH) Hexachloroethane HMX (Octogen) Hydrazines Isophorone Jet Fuels JP-4 and JP-7 Jet Fuels JP-5 and JP-8 Manganese Methyl tert-Butyl Ether (MTBE) Methylene Chloride n-Nitrosodi-n-propylamine Naphthalene, 1-Methylnapthalene, 2-Methylnapthalen Perfluoroalkyls Phosphate Ester Flame Retardants Plutonium Polybrominated Biphenyls (PBBs) Polychlorinated Biphenyls (PCBs) Polycyclic Aromatic Hydrocarbons (PAHs) Pyridine Styrene Thallium Thorium Total Petroleum Hydrocarbons (TPH) Toxaphene Vinyl Chloride Xylenes Neurological (Nervous System) The nervous system receives and sends signals throughout the body to control bodily functions. The nervous system consists of the central nervous system (brain and spinal cord) and peripheral nervous system (nerve fibers that attach to and lie outside the brain and spinal cord). The nervous system has two components, motor (efferent) and sensory (afferent), that carry information from and to, respectively, the central nervous system. The brain is the organ of thought, emotion, and processing of the various senses and communicates with and controls various other systems and functions. The nervous system also provides special senses such as sight, hearing, taste, feel, and smell. It uses the eyes, ears, tongue, skin, and nose to gather information about the body's environment. Substances Listing 1,1,1-Trichloroethane 1,1,2-Trichloroethane 1,1-Dichloroethene 1,2-Dichloropropane 1,3-Butadiene 2,4- & 2,6-Dinitrotoluene 2-Hexanone Acetone Acrylamide Acrylonitrile Aldrin/Dieldrin Aluminum Americium Arsenic Benzene Bis(chloromethyl) Ether Bromoform & Dibromochloromethane Bromomethane Cadmium Carbon Disulfide Carbon Monoxide Carbon Tetrachloride Chlordane Chlordecone Chlorfenvinphos Chlorine Dioxide & Chlorite Chlorobenzene Chloroform Chloromethane Chlorpyrifos Cresols Cyanide DDT, DDE, DDD Diazinon Dichlorvos Dinitrocresols Disulfoton Endosulfan Endrin/Endrin aldehyde Ethion Ethylbenzene Ethylene Oxide Fuel Oils / Kerosene Gasoline, Automotive Heptachlor/Heptachlor Epoxide Hexachlorocyclohexane (HCH) Hexachloroethane HMX (Octogen) Hydraulic Fluids Hydrogen Sulfide Ionizing Radiation Jet Fuels JP-4 and JP-7 Jet Fuels JP-5 and JP-8 Lead Malathion Manganese Mercury Metallic Mercury Methoxychlor Methyl Mercaptan Methyl Parathion Methyl tert-Butyl Ether (MTBE) Methylene Chloride Naphthalene, 1-Methylnapthalene, 2-Methylnapthalen Otto Fuel II and its Components Polychlorinated Biphenyls (PCBs) Pyrethrins-and-Pyrethroids Pyridine RDX (Cyclonite) Stoddard Solvent Styrene Tetrachloroethylene (PERC) Tetryl Thallium Tin and Compounds Toluene Trichloroethylene (TCE) Used Mineral-based Crankcase Oil Xylenes Endocrine (Glands and Hormones) The endocrine system consists of specialized groups of cells called glands that make, store, and release regulating chemicals called hormones directly into the bloodstream to regulate how the body functions. Some of these endocrine glands include the adrenals, chemoreceptor organs, gonads (testis and ovary), hypothalamus, pancreatic islets, parathyroid, pineal, pituitary, and thyroid. These glands secrete hormones that travel through the circulatory system to regulate the various body systems. A few of these hormones include steroids, growth hormones, and thyroxine. Substances Listing Aldrin/Dieldrin Atrazine DDT, DDE, DDD Endosulfan Iodine Malathion Methoxychlor Pentachlorophenol Polybrominated Biphenyls (PBBs) Polybrominated Diphenyl Ethers (PBDEs) Polychlorinated Biphenyls (PCBs) Toxaphene Renal (Urinary System or Kidneys) The urinary system consists of the kidneys, ureters, bladder, and urethra. The kidneys play a major role in balancing fluids and electrolytes, regulating blood pressure, producing erythropoietin (which increases erythrocyte formation), and eliminating waste products through the urine . The urine is formed in the kidney, stored in the urinary bladder, and voided via the urethra. Substances Listing 1,1-Dichloroethene 1,2-Dibromoethane 1,2-Dichloroethane 1,4-Dioxane 2,3-Benzofuran Bromodichloromethane Bromoform & Dibromochloromethane Cadmium Chlordecone Chlorobenzene Chloroform Chromium Dichlorobenzenes Ethylene Glycol Ethylene Oxide Hexachlorobutadiene Hexachlorocyclopentadiene (HCCPD) Ionizing Radiation Jet Fuels JP-5 and JP-8 Lead Mercury Methyl tert-Butyl Ether (MTBE) n-Nitrosodiphenylamine Perfluoroalkyls Phosphate Ester Flame Retardants Propylene Glycol Silver Thallium Total Petroleum Hydrocarbons (TPH) Uranium and Compounds Vanadium and Compounds Xylenes