Presented at the 2012 Society of Toxicology Meeting in San Francisco, CA

1. EXPOSURE AND TOXICITY OF CHEMICALS RESULTING FROM NATURAL GAS EXTRACTION AND HYDRAULIC FRACTURING Abstract # 2112
Debra A. Kaden, Boston, MA; Angela Harris, Little Rock, AR; John Imse, Denver, CO; Mark Travers, Chicago, IL; Rosalind Schoof, Seattle, OR
INTRODUCTION REGULATORY ACTIVITIES Federal Water Regulations
Study on Impact of Hydraulic Fracturing on Drinking Water Resources (USEPA)
air exposure data summary of groundwater studies
Currently, regulation of industry largely the responsibility of states, sometimes
• Initial study results due end of 2012; additional report based on long-term
What is hydraulic fracturing? regional commissions Study What was measured What was found
study projects in 2014. Pavillion, WY Garfield County, CO LeRoy Township, PA
• Established technology, but more widely used with advances in drilling • Regulations vary from state-to-state
• Researchers examining impacts of: TCEQ Dec 2009 • Up to 84 VOCs over 3 days • All but 1 found non-detectable or below short-term AMVCs • USEPA response to complaints from • Garfield County Board of County • Investigation conducted in 2011 to evaluate
technology (horizontal drilling)
° Direct regulation (Air Pollution Control Act) Due to complaint of odor • Fixed and mobile monitors • p-Diethylbenzene measured above the odor-based AMCV at 1 location, domestic well owners about objectionable Commissioners potential effects of a wellhead valve release on
° large volume water withdrawals from ground- and surface waters
° Over past 6-8 years, use has expanded greatly but not above the health-based AMCV odors and tastes from well water. a well pad to nearby residential wells
° Indirect regulation via permitting • Evaluate surface and groundwater
° surface spills resulting from hydraulic fracturing fluids
° Opens up productivity of unconventional oil and gas • Four phases of investigation conducted vulnerability near gas well developments • Some baseline data available for comparison
resources • Types of regulation March 2009 – April 2011. and other human activities
° injection and fracturing process TCEQ Nov 2010 • 18 carbonyls • All non-detects or below short-term AMCVs
° General permitting • Downwind of possible sources • Formaldehyde concentrations 1-.0 – 5.4 ppbv. • Sampled residential wells, municipal wells, • Four phases of investigation
° surface spills of flowback and produced wastewater treatment and
Why the controversy? • Note, limit of detection of isovaldehyde above AMCV, but characteristic stock wells and monitoring wells
° Project-specific review waste disposal • Baseline groundwater studies have also
odor not detected.
• Expansion in the public awareness regarding those resources and an been conducted in Colorado
intensified regulatory scrutiny of development ° Notification/registration requirements • Results likely to drive regulatory and policy changes—could have significant
impact on the shale gas industry
° Common law – “reasonable use” City of Fort Worth Sept/Oct • ~140 pollutants (> 40 HAPs) measured at 8 • Highest concentrations: Methane, ethane, propane, butane.
• Unconventional resources in areas where oil and gas production has not
been seen on this scale for many years • Several states considering moratoriums on hydraulic fracturing Development of Hydraulic Fracturing Wastewater Standards (USEPA) 2010 (ERG report July 2011) locations • Some pollutants with greater toxicity (e.g., benzene) also found, but at
much lower concentrations.
water exposure data
° Example: Marcellus Shale in Pennsylvania, New York, ° New York has temporary moratorium in place • National standards for wastewater discharges via Clean Water Act (CWA) • High-level activity area site had generally higher concentrations than
and Ohio. effluent guidelines program other sites.
° Vermont considering a three-year moratorium
• Overall increased awareness of environmental issues in society • 2 Medium activity sites (within 350 ft of active well pads) “surprisingly
• Based on best available technologies that are economically achievable Pavillion Garfield County Leroy Township
° Ohio has proposed moratorium on horizontal stimulation until USEPA low “relative to the other sites.”
• Vast array of readily available and accessible information resources water study complete • Prohibit on-site direct discharge of wastewater from shale gas extraction into Analyte
(mg/L) Deep Shallow
US waters Residential
° Michigan has proposed two-year moratorium on new permits until (Monitoring (Residential Baseline Studies Groundwater Baseline
Zielinska et al 2010 • Non-methane volatile organic compounds >90% ethane, propane, n-butane, iso-butane, iso-pentane, and n-pentane Well1
USEPA water study complete • Currently, disposal of wastewater regulated by the states. In some states, Wells) Wells)
(NM VOC) examined near gas well sources
wastewater injected into deep underground shafts; in others, wastewater ~10% of VOC were mostly C6-C8 n-alkanes, branched- and cyclo-alkanes.
° USEPA assured states it will not issue a moratorium on hydraulic
WHAT ARE THE POTENTIAL fracturing
sent to sewage treatment plants ~0.1 – 0.2% benzene, toluene, and xylenes (part of BTEX) pH 11.2 – 12.0 6.9 – 10.0 7.82 7.42 8.42 7.3 – 8.6
• USEPA gathering data, consulting with stakeholders, soliciting public
EXPOSURE PATHWAYS? • Existing or possible new state and local regulations and practices can serve 4-week average individual VOC concentrations were low, generally <1 ppb
comment on proposed rule for wastewater discharges Comparable or slightly higher than TCEQ sites (same time period)
to manage groundwater impacts
Monitoring at a nearby residential community found average speciated Methane 16.0 – 19.0 ND - .808 ND – 36.73 ND - 11 0.76 .76 - 12
° Proposed rule for coalbed methane in 2012
° Regulations for construction, maintenance and closure of both gas wells VOC concentrations generally <1 ppb.
Inhalation and water wells ° Proposed rule for shale gas in 2014
Cl 23.1 - 466 0.6– 80.3 147.52 1.0 - 2300 116 1750
• Exploratory drilling ° Baseline and ongoing groundwater well water quality monitoring University of Colorado Air • Measured VOC, carbonyls, ozone From PCA results, mobile source exhaust, natural gas condensate emissions,
Permitting Guidance on Underground Injection Control for Facilities that Use Anions
• Methane fugitive emissions Toxics Study (2007-2008) • Source apportionment to tie back to sources and meteorology are significant pollution source
CHEMICALS ASSOCIATED WITH HYDRAULIC FRACTURING ° Public disclosure of chemicals used Diesel Fuels in Injection Fluids (USEPA)
Collaboration between BCPH, U K 24.7 – 54.9 0.3 – 11.4 3.02 0.4 – 14.2 1.78 0.38 - 6.7
• Vapor intrusion • Safe Drinking Water Act’s (SDWA) Underground Injection Control (UIC) Colorado, EPA Region 8
• Air toxic emission Pollutant Emissions (tpy) Health concerns Increased Federal Activities in Recent Years program has requirements for proper well siting, construction, operation to
minimize risks to underground sources of drinking water DRO 0.63 – 4.0 ND - .10 NA NA
• Hydrogen sulfide • USEPA: New rules under Clean Air Act expected by April 3, 2012
Garfield County 2008 • 4 Locations within 1.5 miles of oil & gas • Used conservative assumptions (95% upper confidence level of mean
VOCs 2.2 million VOCs react in the air to form ozone and PM2.5. • Energy Policy Act of 2005 excluded hydraulic fracturing for oil and gas Monitoring development activities: values for chronic/ maximum values for acute; assumes 24/7, 30 years) TPH NR NR
• Particulates ° Includes review of four rules for the oil and natural gas industry
Ethane Isopentane production from permitting but exclusion did not include fracturing using CO Department of Public Health ° 2 urban, near I 70 • Cancer risk found within EPA acceptable range
Ozone (regulated as a criteria pollutant) can cause asthma attacks, hospital and emergency GRO 0.39 – 3.7 ND – 0.48 NA NA
Propane Isobutane ° New source performance standard for VOCs diesel fuel & Environment with review by ° 2 rural, close to oil & gas activities • Noncancer risk (acute or chronic) below health-based guidelines
Sources department visits, school loss days, and premature mortality
N-Butane Ethylene ATSDR • Measured 90 speciated NM VOCs • Cautions: Measurements only once every 6 (or 12) days; Measurements
° New source performance standard for sulfur dioxide • USEPA developing permitting guidance with a broad definition of diesel fuel
• Air N-Pentane Methane PM2.5 (regulated as a criteria pollutant) can cause premature mortality for adults and infants, (1,3-Butadiene, Benzene, Ethylbenzene, at single station for each location; Reflect emissions from other sources
(e.g., physical and chemical characteristics of diesel such as BTEX) Pavillion Garfield County Leroy Township
heart attacks and hospital admissions. Also can cause asthma attacks, acute and chronic ° Air toxics standard for oil and natural gas production Toluene, 1,2,4-Trimethylbenzene, too; Risk estimates use conservative, regulatory values
° Exploration Drilling
bronchitis, hospital and emergency room visits, work loss days, restricted activity days, and 1,3,5-Trimethylbenzene, others) Analyte
— Relatively short term from exposure perspective respiratory symptoms. ° Air toxics standard for natural gas transmission and storage Rulemaking on the Disclosure of Chemicals Used in Hydraulic Fracturing (USEPA)
every 6 days (mg/L) Deep Shallow
Residential
• Includes requirement to capture 95% of VOC emissions • EPA starting rulemaking process under Toxic Substance Control Act (TSCA) • Measured carbonyls (acetaldehyde, (Monitoring (Residential Baseline Studies Groundwater Baseline
Well1
° Development and Production
formaldehyde, crotonaldehyde, others) Wells) Wells)
to require disclosure of information on the chemicals used in hydraulic
— Longer term ° Largely through capturing natural gas that currently escapes into the
fracturing. every 12 days
Air Toxics 130,000 Including benzene, others. air, making that gas available for sale Benzene ND - 256 ND – 0.54 ND ND – 1.0
— Leaks and venting (methane)
Acetaldeyde Benzene
Can cause cancer and other serious, irreversible health effects . ° Will also reduce emissions of methane and air toxics ° In a response to a petition filed by Earthjustice and 120 other
Toluene Ethyl benzene
° Support activities organizations Toluene ND - 617 ND – 0.71 ND ND – 14.0
Xylenes 1,3-Butadiene Regulated through the Clean Air Act.
— Truck and engine exhaust BTEX NR
Aggregation of Air Emissions ° Will limit disclosure to substances used in hydraulic fracturing
— Fugitive dust potential pollution source rank by site Ethylbenzene ND - 67 ND ND ND – 1.0
• Several pending litigation actions address aggregation ° Will attempt to avoid duplication of “the well-by-well disclosure
• Water GHG 16 million Reacts in the air to form ozone (see above). programs already being implemented in several states,” and will
Xylenes ND - 750 ND ND ND – 1.5
Methane (300,000 MMTCO2e) ° Process of determining whether emissions from multiple operations “focus on providing aggregate pictures of the chemical substances 1st 2nd 3rd
° Surface water A potent GHG. Once emitted into the atmosphere, it absorbs terrestrial infrared radiation, which should be combined, or aggregated, into a single source for air and mixtures used in hydraulic fracturing”
contributes to increased global warming and continuing climate change. permitting purposes Napthalenes ND – 6.1 ND – 0.39 NR NA NR
° Groundwater
° Advanced notice of proposed rulemaking expected in 2012 Boulder Mobile Source Secondary Formation Evaporative
• If emissions from individual operations are combined, they could constitute
° Waste water
Adapted From: EPA (July 2011) Overview of proposed new regulations “major stationary source” or “major facility” for purposes of the Prevention Isopropanol 212 - 581 ND NA NA
— Volatilization from pits or impoundments Proposed Regulations Related to Hydraulic Fracturing on Public Lands (US Longmont Evaporative Secondary Formation Mobile Source
of Significant Deterioration, New Source Review and Title V permitting Department of the Interior)
programs under the Clean Air Act Arsenic 3.6 – 41.8 ND - .089 4.82 4.12 ND – 1.8
• Drafting regulation for shale gas production on public lands Lyons Secondary Formation Evaporative Mobile Source
Ingestion • Definition of “adjacent” likely to be applied differently in some of the
• In addition to chemical disclosure provisions, the rules are expected Uranium NA NA NR 1.5 - 47 ND - .023
litigation cases Niwot Ridge Secondary Formation Mobile Source Evaporative
• Methane to address wellbore integrity following hydraulic fracturing and the
° Clean Air Council v. DEP (EHB Docket No 2011-072-R), pending management of wastewater
• Naturally Occurring Radioactive Material (NORM) South Boulder Mobile Source Evaporative Secondary Formation After valve release at well pad
1
2
Mean value 3 Unknown methane origin: ND (not detected) NA (not analyzed) NR (not reported)
before Pennsylvania’s Environmental Hearing Board (USEPA Region 3)
• Salts (brine)
° Citizens for the Future of Pennsylvania v. Ultra Resources, 4:11-cv- Other Regulatory or Industry Activities From: University of Colorado Air Toxics Study (2007-2008)
• Various chemicals from injected fluids 01360-JEJ, pending in the US District Court for the Middle District of
DOE Shale Gas Subcommittee: Recommendations for immediate implementation
Pennsylvania (USEPA Region 3)
Sources • Federal agencies
° Summit Petroleum Corporation v. EPA (Case No. 09-4348) pending
• Well construction failure – casing and cement integrity
before the federal Sixth Circuit Court of Appeals (EPA Region 5). ° Measures to reduce emissions of air pollutants, ozone precursors and
• Direct contact with and disposal of wastewater methane as quickly as practicable (USEPA)
• Possible hydraulic connections between deep and shallow aquifers
° Others
° Interagency planning effort to acquire data and analyze the overall CONCLUSIONS • Hydrogen sulfide
Water
• If different interpretations across different USEPA regions, likely USEPA will ° Occurs in formations with lots of pyrite, like the Marcellus Baseline studies are integral to interpreting data from groundwater studies Precautionary Principle often cited…
• Hydraulic connections created by historical drilling in regions being greenhouse gas footprint of natural gas use Air associated with nearby hydraulic fracturing activities.
attempt to resolve conflicting ° Others: formaldehyde, diesel exhaust, 1,4-dioxane,
developed • Do no harm
• States While many of the chemicals associated with fracking are toxic (at some hydrochloric acid, methanol
Congressional bills The data and conclusions from one groundwater study are not generally • Prove scientifically that what you are doing is not harmful
• Wastewater release concentration)…. Air exposures found to be minimal
° Encourage shale-gas production companies and regulators to expand applicable to potential impacts in another region.
• HR 1204: Bringing Reductions to Energy’s Airborne Toxic Health Effects Act immediately efforts to reduce air emissions using proven technologies • Often not detectable ...but to date the facts do not support health risks
• Benzene, toluene, ethylbenzene, xylene (BTEX), other VOC
(“BREATHE” Act) • Differences in underlying hydrogeology
and practices. Federal funding at $5m/y for state regulators/NGOs/ • Below health-based benchmarks • Still, need to move forward cautiously with air and water
° Stationary and truck Diesel engines, flaring, venting,
industry will encourage planning • Variability in stratography of residential wells
° Eliminates NESHAP exemption to have aggregated wells viewed as produced water storage, dehydration of natural gas • Dissipate as you move away from the site monitoring to make sure...
“major sources” to use best available control technology • Industry • Potential for domestic/agricultural/municipal impacts to groundwater
• Methane • Other sources of same VOC
vary by region
° Sponsored by Rep Jared Polis (D-Colorado 2nd District)
From: Zielinska et al 2010 ° Enlisting a subset of producers in different basins to design and field a ° Greenhouse gas (GHG) Odor detection is not necessarily toxic
system to collect air emissions data
° Status: Bill in the first step in the legislative process.
www.environcorp.com
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