Toxicology of Hydraulic Fracturing NYOEMA Annual Conference October 19, 2012 Michael G. Holland, MD, FAACT, FACMT, FACOEM, FACEP Clinical Associate Professor, SUNY Upstate Medical University Consulting Medical Toxicologist Upstate New York Poison Center, Syracuse, NY Director of Occupational Medicine Center for Occupational Health of Glens Falls Hospital Glens Falls, NY

Background of Fracking n Hydraulic fracturing first performed in 1947 n Has been used on over 1 million producing wells. n Currently, operators now fracture as many as 35,000 wells of all types (vertical and horizontal, oil and natural gas) each year. n Vertical well sections can be 100-1,000’s of feet below the land surface n Lateral sections may extend 1000 to 6000 feet away from the well, often multiple sections and directions

Background n Water is pumped into well at high pressure n Exempt from EPA Clean Water Act n The high pressure fractures or opens up existing fractures in shale. n Water has additives to enhance the process (more detail later) n Proppants (propping agents, usually sand or ceramic) are injected to prop open the new fractures

Background n Water & its additives are withdrawn (flowback), and contained or recycled or disposed of, depending on permit –Regulated by the National Pollutant Discharge Elimination System (NPDES) National Pollutant Discharge Elimination SystemNational Pollutant Discharge Elimination System –Requires flowback to be treated prior to discharge into surface water or underground injection (regulated by either the U.S. Environmental Protection Agency’s (EPA) Underground Injection Control (UIC) program ) n Oil or gas is then extracted

Do not drink this water n n

zEPugpk Hydraulic Fracturing Explained

Areas of Concern n Identification and Toxicology of fracking fluids and additives n Possible groundwater contamination –By the well and the process itself –By storage of contaminated water –NB: Exempt from Safe Drinking Water Act n Radioactive isotopes n Air contamination from VOC produced by well- methane, BTEX n Air/water contamination by industrial equipment & engines used for pumping, extracting, etc. n Traffic, noise, etc in pad area

Horizontal Wells

Continuous Reservoir Weakly Laminated Shale Strongly Laminated Shale (Slatt and others, 2011) Thin section photomicrographs Woodford Shale

Disposal of Fluids from Fracking Water (brine) injection depths are usually deep, in rocks naturally stressed with faults capable of generating earthquakes Fracking well Wastewater well deep injection may trigger earthquakes due to stress relief on faults adapted from geology.com

Induced Seismicity and Enhanced Recovery n Below a few kilometers depth, the Earth’s crust is everywhere stressed. Those natural stresses put faults close to failure. n The injection, which forces fluid along faults and fractures relieves the effective stress, making triggered earthquakes more likely n The formation of new fractures –i.e. the hydrofrac itself, actually doesn’t release much energy compared to the triggered quakes. n But large volumes of fluid are injected during disposal, which flow along fault, and may trigger earthquakes

Drinking Water Aquifers vs Fracture Heights of Marcellus Shale

Chemical Classes Used n Acids- n Biocides n Breakers n Clay Stabilizers n Corrosion Inhibitors n Crosslinker n Friction Reducers n Gelling Agents n Iron Control Agents n Non-Emulsifiers n pH Adjusting Agents n Scale Inhibitors n Surfactants

Fracking Chemicals n Most companies will not divulge exact chemicals since it is protected as “proprietary mixtures” n They are supposed to give info to treating physicians when requested, to treat an exposed patient n While there may be 100’s of chemicals possibly used, each individual site will typically use 10 or less

Acids n Hydrochloric acid (muriatic acid) and Acetic Acid –Dilute acid solutions used during the initial fracturing sequence. –Cleans out cement and debris around the perforations –Facilitates the subsequent slickwater solutions employed in fracturing the formation –Also used to adjust pH when needed

Biocides n Used to prevent the growth of bacteria in the water that may interfere with the fracturing operation- by causing corrosion n Inhibits sulfate-reducing bacteria from forming H 2 S n Typical Biocides- can have irritant/burns on tissue exposure –Glutaraldehyde –Quaternary Ammonium Chloride –Tetrakis Hydroxymethyl-Phosphonium Sulfate –Bromine-based solutions

Biocides- Toxicity n Glutaraldehyde- sterilant for endoscopy equipment n Quaternary Ammonium Chloride- common disinfectant n Tetrakis Hydroxymethyl-Phosphonium Sulfate- also used in flame retardants, fabric treatments n Bromine-based solutions- also used in hot tubs and pools

Breakers n Used to stabilize and prevent breakdown of gel- to keep proppants in suspension –Ammonium Persulfate –Sodium Chloride –Magnesium Peroxide –Magnesium Oxide –Calcium Chloride

Breakers- Toxicity n Ammonium Persulfate- strong oxidizer- caustic (used as catalyst for polyacrylamide) n Sodium Chloride n Magnesium Peroxide- oxygen generator; also used to reduce contaminant levels in groundwater n Magnesium Oxide n Calcium Chloride

Clay Stabilizers n Used to stabilize clay and prevent it from swelling and shifting during drilling operations –Choline Chloride –Tetramethyl ammonium chloride –Sodium Chloride

Clay Stabilizers- Toxicity n Choline Chloride- therapeutic med n Tetramethyl ammonium chloride- n Sodium Chloride- table salt

Corrosion Inhibitors n Used to prevent corrosion of steel well bore –Isopropanol –Methanol –Formic –Acetaldehyde

Corrosion Inhibitors- Toxicity n Isopropanol- rubbing alcohol; bitter taste, metabolized to acetone n Methanol- wood alcohol, poisonous when ingested- metabolic acidosis, retinal, CNS toxicity n Formic Acid- toxic metabolite of methanol, responsible for acidosis and toxicity of methanol n Acetaldehyde- metabolite of ethanol

Cross-linking Agents n Maintains fracking fluid viscosity at high temperatures –Potassium Metaborate –Triethanolamine Zirconate –Sodium Tetraborate –Boric Acid –Zirconium Complex –Borate Salts

Borate Salts- toxicity n Irritants at high concentrations n Oral ingestions cause N/V/D –Stools can be blue-green n Significant ingestions cause erythrodermic rash n Boiled Lobster skin n Desquamation

Cross-linking Agents n Carrier fluids to deliver cross-linkers –Petroleum Distillate –Hydrotreated Light Petroleum Distillate n Crosslink stabilizer –Ethylene Glycol –Methanol

Friction-Reducing Agents n Reduces friction of water as it flows – “slicks” –Polyacrylamide n Carrier fluids to deliver polyacrylamide –Petroleum Distillate –Hydrotreated Light Petroleum Distillate n Crosslink stabilizer & winterizer –Methanol –Ethylene Glycol

Toxicity of Friction-Reducing Agents n Polyacrylamide- –also used in water treatments, grouting –acrylamide monomer is a neurotoxin –Peripheral neuropathy n Carrier fluids –Petroleum Distillate- liquid hydrocarbon –Hydrotreated Light Petroleum Distillate n Crosslink stabilizer & winterizer –Methanol –Ethylene Glycol

Gelling Agents n Thickens water so sand will remain in suspension –Guar Gum- also thickener in ice cream –Polysaccharide Blend- Carboxymethyl Hydroxypropyl Guar n Carrier fluids for guar gum in liquid gels –Petroleum Distillate- liquid hydrocarbon –Hydrotreated Light Petroleum Distillate n Product stabilizer & winterizer –Methanol- metabolic acidosis; retinal and CNS toxin –Ethylene Glycol- metabolic acidosis, nephrotoxin

Toxicity of Gelling Agents n Guar Gum- common food ingredient thickener in ice cream n Polysaccharide Blend- Carboxymethyl Hydroxypropyl Guar

Iron Control Agents- n Prevent precipitation of metallic oxides –Citric Acid- food additive –Acetic Acid- food additive –Sodium Erythorbate- food additive –Thioglycolic Acid- irritant, permanent wave soln

Iron Control Agents- Toxicity n Organic acids- much like Calcium- Lime-Rust (CLR) removing agents –Citric Acid- food additive –Acetic Acid- food additive –Sodium Erythorbate- food additive –Thioglycolic Acid- irritant, permanent wave soln

Emulsifier Reducers n Prevent formation of emulsions of the different components of fluids- –Lauryl Sulfate- surfactant found in shampoos, detergents n Product stabilizer & winterizer –Isopropanol- rubbing alcohol –Ethylene Glycol- metabolic acidosis, nephrotoxin

Emulsifier Reducers- Toxicity n Lauryl Sulfate- surfactant found in numerous consumer products: shampoos, detergents, etc. n Product stabilizer & winterizer –Isopropanol- rubbing alcohol –Ethylene Glycol- metabolic acidosis, nephrotoxin

pH Adjusters n Added to adjust pH of water to enhance properties of crosslinkers –Sodium Hydroxide –Potassium Hydroxide –Acetic Acid –Sodium Carbonate –Potassium Carbonate

pH Adjusters- Toxicity n Sodium Hydroxide- Lye- caustic burns on skin, mucosa when ingested n Potassium Hydroxide- strong alkali caustic burns n Acetic Acid- organic acid- caustic n Sodium Carbonate- aka soda ash- caustic n Potassium Carbonate- aka potash-caustic

Scale Inhibitors n Prevents scale deposits in pipes –Copolymer of Acrylamide and Sodium Acrylate –Sodium Polycarboxylate –Phosphonic Acid Salt

Scale Inhibitors- Toxicity n Copolymer of Acrylamide and Sodium Acrylate- hygroscopic ingredient of consumer products like cosmetic creams n Sodium Polycarboxylate- common detergent ingredient; HERA safe detergent additive n Phosphonic Acid Salt- HERA safe detergent additive

Surfactants n Used to increase viscosity of fracture fluids n Lauryl Sulfate n Carrier fluid for surfactant ingredients –Petroleum naphtha n Product stabilzers/winterizing agents –Ethanol –Methanol –Isopropyl Alcohol –2-Butoxyethanol

Surfactants- Toxicity – Lauryl Sulfate- common household ingredient: shampoos, soaps n Petroleum naphtha- hydrocarbon liquid n 2-Butoxyethanol- ethylene glycol mono- butyl ether- common cleaning agent n Ethanol n Methanol n Isopropyl Alcohol

BTEX n VOCs commonly produced by oil and natural gas wells n Methane most common n BTEX n Benzene- AML n Toluene- CNS, RTA, leukoenecephalopathy in sniffers n Ethylbenzene- CNS n Xylene- CNS

BTEX “… waters from gas production have higher contents of… BTEX than those from oil operations; … waters discharged from gas/condensate platforms are about 10 times more toxic than from oil platforms. Argonne National Laboratory (pdf) Argonne National Laboratory (pdf)

BTEX – Benzene- AML, aplastic anemia – Toluene- CNS depression, RTA, leukoenecephalopathy in sniffers – Ethylbenzene- CNS depression – Xylene- CNS depression – Methane Simple asphyxiant

Governmental Agencies USEPA Hydraulic Fracturing Website Al things related to hydraulic fracturing, Including EPA’s studies and proposed regulations. Pennsylvania Marcellus Shale Page State regulations, well Permits and locations COGCC Website Comprehensive source of Information regarding hydraulic fracturing in Colorado. Includes regulations, results of Environmental studies, and Informational materials. COGCC HF Information Page Provides many links to informational websites on HFhttp://cogcc.state.co.us/Announcements/Hot_Topics/Hydraulic_Fracturing/Hydra_Frac_topics.html TCEQ Resources for Public Address Provides air quality information Fayetteville Shale Homepage Provides information regarding regulatory standards In the State of Arkansas. Arkansas Well Fracture Information Permits and chemical listings for proposed wells To be fracture stimulated. USGS State of the Science Briefing Contains links to PowerPoint presentations To Congress– general information regarding hydraulic fracturing. US Energy Information Administration General hydraulic fracturing information, economics, production State of New York Environmental Impact Statement The State of New York’s Environmental impact Statement regarding proposed hydraulic fracturing operations WEB-- ‐ BASED RESOURCES FOR INFORMATION REGARDING THE REGULATION AND HEALTH/ENVIRONMENTAL IMPACTS OF HYDRAULIC FRACTURING - Governmental Websites

WEB-- ‐ BASED RESOURCES FOR INFORMATION REGARDING THE REGULATION AND HEALTH/ENVIRONMENTAL IMPACTS OF HYDRAULIC FRACTURING Description Web Address FracFocus All things fracking: General information, chemical registry, well maps, regulations,etc.… SouthwesternEnergy General information regarding each operations area, as well as environmental initiatives Pages/areas.asp x HydraulicFracturing.com Wide-- ‐ ranging Information regarding hydraulic fracturing And regulations m/Pages/infor mation.aspx Halliburton General process information c/projects/pub sdata/hydraulic_fracturing/fracturi ng_101.html API Policy Issues Policy information ‐ and-- ‐ issues/hf.aspx Industry Websites

OrganizationDescritpion Web address Earthworks General information, Groundwater, activism rg/issues/detail/h ydraulic_fracturing_101 National Resources Defense Council (NRDC) Anti--‐fracking blog posts and News stories Sierra Club General information, activism aturalgas/ Greenpeace General information, activism a/en/campaigns/gl obal--‐warming--‐and-- ‐energy/The-- ‐Problem/fracking/ Environmental Working Group General information, activism ‐drilling--‐and--‐fracking WEB-- ‐ BASED RESOURCES FOR INFORMATION REGARDING THE REGULATION AND HEALTH/ENVIRONMENTAL IMPACTS OF HYDRAULIC FRACTURING NGO Websites