Jeffrey A. Adams, PhD, PE Krishna R. Reddy, PhD, PE, D.GE

The State-of-the-Practice of Characterization and Remediation of Contaminated Sites Jeffrey A. Adams, PhD, PE Krishna R. Reddy, PhD, PE, D.GE

Presentation Outline • Historical context and regulatory framework • Evolution in practice • Site characterization • Risk assessment • Site remediation • Questions

Petroleum Industry • Between 1950 and 1972, world energy consumption increased 179% • Doubled per capita consumption • Oil consumption rose from 29% of energy consumption in 1950 to 46% in 1972 • 47% of US energy consumption by 1973 • 64% of western Europe; 80% of Japan energy consumption by 1973 • Petrochemicals were rapidly replacing glass, wood, natural rubber, iron, copper, aluminum, and paper

Pesticide Use • Tenfold in pesticide expenditures between 1945 and 1972 • Pesticide production • Less than 100 million pounds in 1945 • Over 600 million pounds by 1960 • Herbicide use • 1952, 11% of corn and 5% of cotton acreage • 1982, risen to 95% of corn and 93% of cotton Source: livinghistoryfarm.org

Donora 1948 Smog Disaster • Monongahela River Valley mill town • In 5 days, 20 died and 7,000 became sick • Temperature inversion trapped noxious emissions • Sulfur dioxide • Carbon monoxide • Metal dust Source: www.pollutionissues.com

Los Angeles

Air Pollution Control Act • Passed in 1955 • Initial attempt at addressing growing air pollution • Acknowledged air pollution was a growing threat to public health • Limitations • Deferred authority to states • Did not include power to sanction or penalize

Cuyahoga River

1969 Santa Barbara Oil Spill • Blowout of oil well • 3 million gallons of crude oil spilled, fouling beachesand wildlife • Inspired the formation of Earth Day • Sierra Club membership reportedly doubled in the following 2 years

Grass Roots Inspiration and Reaction • 1962 – Silent Spring • Reaction to DDT spraying for mosquitoes • Contributed to ban in US • 1968 Apollo 8 mission • 1970 – Earth Day • Political groups • Business groups • Activist groups

Solid Waste Disposal Act (SWDA) • 1965, 1970 –first federal legislation regulating municipal solid waste • Reduction of solid waste volumes to protect human health and environment • Improvement of waste disposal practices • Provisions funds to individual states for solid waste management • 1970 Amendments • Encouraged further waste reduction and waste recovery • Created system of national disposal sites for hazardous waste National Environmental Policy Act (1969) • Council of Environmental Quality, a new executive branch agency Environmental Protection Agency • Environmental Impact Statement (EIS) for any federal project

Clean Water Act (CWA) and Safe Drinking Water Act (SDWA) • CWA 1977, 1981, and 1987 – Regulates discharges into U.S. waters • 129 priority pollutants were identified as hazardous wastes • National Pollutant Discharge Elimination System (NPDES) permitting • Dredged material discharge only allowed with permit • Wastewater discharge treatment requirements • Discharges from POTWs must meet pre-treatment standards • SDWA 1974, 1977, and 1986 – Protection of drinking water quality • MCLs, primary and secondary goals • Regulation of hazardous waste injections into subsurface • Designation and protection of aquifers

Toxic Substances Control Act (TSCA) • 1976 – Regulation and use of hazardous chemicals • Industries required to report/test chemicals that may pose an environmental or human health threat • Prohibition of the manufacture and import of chemicals that pose an unreasonable risk • Requirement of pre-manufacture notifications to the USEPA • Prohibition of PCBs • Management of asbestos

Unintended Consequences… • Many of the previous acts lacked enforcement ability and had loopholes • Encouraged “shortcut” behaviors • Few landfill regulations

Resource Conservation and Recovery Act (RCRA) - 1976 • Passed to manage nonhazardous/hazardous wastes, USTs • Emphasis on recovery/recycling instead of disposal • Subtitle C – control of hazardous wastes • Subtitle D – management of nonhazardous wastes • Subtitle I – UST regulations • Amendments in 1984 • Restrictions on liquid waste • New UST regulations • Landfill liner, leachate collection, and monitoring requirements • Small generator and TSDF requirements • USEPA authorized to inspect, enforce, and penalize

Love Canal • Toxics placed in canal; capped with clay • Residential and school construction on top of canal • Noxious odors and acute health problems observed • Confirmed presence of widespread soil and groundwater contamination • U.S. government paid for the relocation of hundreds of residents

Comprehensive Environmental Response, Compensation, and Liabilities Act (CERCLA), or “Superfund” (1980) • Addresses abandoned/uncontrolled hazardous waste sites necessitating immediate cleanup • Fund from taxes on chemical/petroleum companies • $1.6 Billion ($5 Billion in 2011 dollars) • Identified PRPs as current or past owners of site as well as generators and transporters • Hazard Ranking System • Population, degree/nature of contamination, pathways • Sites scoring “high enough” added to National Priorities List • Methods evolved to study sites • Remedial Investigation – characterizes site • Feasibility Study – considers remediation alternatives

Superfund Amendments and Reauthorization Act (SARA) • $8.5 billion for site cleanup; $500 million for USTs • $18.9 billion and $1.1 billion in 2011 dollars, respectively • Established community right-to-know provisions • Standard framework – Applicable or relevant and appropriate requirements (ARARs) – chemical specific, action specific, and location specific • Established liability for innocent purchasers and landowners • Gave rise to Phase I, II, and III studies • Also, annual hazardous substance release reporting requirements

CERCLA/RCRA – ESA1 • Often driven by property transaction • Many “flavors” (screen, update, PEA); “strongest” flavor provides liability protection – AAI – ASTM 1527-05 • Clear requirements about content, shelf life, etc. • Report summarizes site history • Radius report • Aerial photographs • Topographic maps • Title reports/lien search • File reviews of numerous agencies • Interviews • Identify data gaps • Recognized Environmental Conditions (RECs)

CERCLA/RCRA – ESA2 • Follow-up on findings of Phase One ESA • Field characterization • Soil, groundwater, soil vapor • First efforts often general; follow-up work may occur • Soil, groundwater, and/or soil vapor sampling • Laboratory analysis for target analytes • Consider results with screening values • MCLs, PRGs/RSLs, state criteria

CERCLA/RCRA – ESA3 • Goal: remediate the site to an acceptable level of risk for future use • Dependent on anticipated land use • Regulatory oversight – NFA status • Develop a remedial approach to mitigate site contamination • Cost-benefit analysis • Cash flow considerations • Tax incentives • “Real time” and post-remediation monitoring

CERCLA Progress • When enacted, 36,000 sites identified; 1,200 placed on NPL • As of end of FY 2010 • 1,627 sites remain on NPL • 475 sites have been closed • $40 million per site (2011 $); 11 years on average to close • $40 million x 1,627 = $65.1 billion • $1.2 billion / 400,000 LUSTs = $3,000 per LUST • $6 billion in trust in 1996 exhausted by 2003 (general Congressional appropriations since 2003)

CERCLA Progress (Cont.) • EPA Superfund 2008 FY progress: • Controlled all identified unacceptable human exposures at a net total of 24 sites, exceeding the annual target of 10” • “Controlled the migration of contaminated ground water through engineered remedies or natural processes at a net total of 20 sites, exceeding the target of 15 for the year” • Spent $500 million

Brownfields Concepts and Framework • Desire to pursue “land recycling” • remediate to anticipated land use and exposure • Small Business Liability Relief and Brownfields Revitalization Act (2002) • Promotes cleanup and reuse of brownfields • Liability relief to small businesses • Provides financial assistance • Enhanced state programs • Liability protection for prospective purchasers, contiguous property owners, and innocent landowners

Legal and Engineering Controls • Land use legal controls • Deed restrictions • Easements for long-term monitoring • Engineering controls • Vapor barriers • Venting systems • Long-term collection and treatment

Voluntary Site Remediation Programs • Collaborative local/state framework • Voluntary agreement between RP and agency • Often feature a formal agreement w/ timeline, cleanup goals, and reimbursement • Goal is to achieve a No Further Action (NFA) Status • Cost-benefit analyses are common to select remediation alternative

“Traditional” Soil and Groundwater Characterization • Soil sampling and laboratory analysis • Groundwater • Monitoring wells • “Grab samples” • Precise, quantitative (and expensive) data • USEPA SW-846 • Guidance for compliance with RCRA regulations • Basis for other methods

Direct Push Soil and Groundwater Sampling • Cost-effective alternative to conventional rotary drilling • Reduces IDW volume • Soil • Groundwater • “Grab” sampling • Temporary or permanent packed wells

Innovative Characterization Technologies • Analytics • Membrane Interface Probe • X-ray Fluorescence • Fiber Optic Chemical Sensors • Laser-induced Fluorescence • Immunoassays • Geophysics • Ground Penetrating Radar • Magnetics

Membrane Interface Probe (MIP) • Advanced with direct push rig • Continuous, real-time profile of hydrocarbon/VOC impacts • Three detectors used to analyze a range of contaminants • Electron capture detector (ECD) • Photo ionization detector (PID) • Flame ionization detector (FID) • Semi-quantitative locating of “hot spots”

Membrane Interface Probe (MIP)

X-Ray Fluorescence • Hand-held field unit or direct-push system • Soil bombarded with x-rays; induces fluorescence • “Hits” are unique to element (more hits = higher concentration) • Portable, fast, multiple analyses; best for metals • Detection limits exceed action levels for some analytes • Licensing issues due to radioactive source

Fiber Optic Chemical Sensors (FOCS) • Optical fiber used to transport light • Interaction of the analyte with fiber creates a detected reaction • Absorbance • Reflectance • Fluorescence • Light polarization • Detected intrinsically or extrinsically • Real-time, transmits a long distance, multi-compound analysis • High detection limits, gross estimation, time and temperature sensitivities

Laser-Induced Fluorescence • Fiber optic-based, direct push system • Induces fluorescence of aromatic compounds or PAHs • Peak wavelength and intensity used to infer contaminant type or relative concentration • Real-time; semi-quantitative • No cuttings, continuous logging, minimally invasive • Cost-prohibitive on small projects • Select minerals and organic matter may cause interference

Immunoassays • Use of biological systems to detect target analytes (organic compounds, some metals) • Colorimetric analysis based on analyte and relative concentration • Compared with standard chart or with photometer • Fast, easy, portable, inexpensive low detection limits • Pre-prediction of target analytes, some analytes yield questionable results, field conditions can affect reactions

Ground Penetrating Radar (GPR) • GPR uses high frequency pulsed electromagnetic waves • Energy is propagated downward and reflected back, showing contrasts • Locate pipes, drums, tanks, cables, and boulders, landfill and trench boundaries, mapping contaminants • Easy; non-intrusive; in-field data review possible • Interpretation requires skilled personnel; depth of penetration affected by subsurface conditions

Magnetics • Used for locating subsurface ferrous alloys • The stronger the force, the greater the ferrous mass • Used to locate drums, tanks, pipes, ordnance, abandoned well casings, boundaries of landfills (if ferrous metal present), and mineralized iron ores • Simple, portable, easy to operate, accurate, less susceptible to interference • Limited information on depth, specific applicability

Special Challenges and Approaches in Site Characterization

Fractured Rock • Contamination presents several challenges • Contaminant movement along bedding planes, joints, fractures • Fluid diffusion into the matrix • NAPL flow very complex • Capillarity, gravity, viscosity considerations • Downhole geophysical methods • Televiewers (optical and acoustic) • Coring methods • Groundwater flow modeling • Pumping tests • Monitoring wells • Tracer testing • Flowmeter testing

Dense Nonaqueous Phase Liquids (DNAPLs) • Heavier than water; low solubility; pooling issues • Often difficult to find source • Traditional soil and groundwater sampling is “hit-or-miss” • Geophysical methods • Innovative characterization technologies • Membrane interface probe • Laser-induced fluorescence

Triad - EPA • EPA framework for site characterization and remediation that incorporates three key principles: • Systemic planning – key decisions, conceptual site model, identifying and mitigating potential uncertainty • Dynamic work strategies – characterization and monitoring; flexibility to make decisions based on incoming data • Real-time measurement – rapid lab TAT, mobile lab, characterization technologies

Soil Vapor Sampling • Vapor samples collected directly from subsurface • Temporary or permanent sampling wells • Replacing modeling and passive indoor sampling • Leak detection methods • Common compounds applied at connections • Positive pressure inert gas environment (“shroud”)

Mass Flux/Mass Discharge Approach • Alternative to analysis based on point concentrations • Mass flux – mass/time/area • Mass discharge – mass/time • Parameters can help answer: • Is plume stable? • How will remediation affect fate/transport? • When to introduce additional remedial technologies? • Transect method, well pumping, or in-well meters

Pre-Risk Era (Early 80s) • Remediation goals often set to “pristine” condition/restoration • e.g., groundwater MCLs • Proved to be cost and time prohibitive

Emergence of Risk Era • National Research Council/National Academy of Sciences (NRC/NAS) • RED BOOK (1983) Risk Assessment in the Federal Government: Managing the Process • Addressed health risk assessments across all Federal Agencies • Defined four-step risk assessment process • Steps used in several EPA statutes but with different methods (e.g., RCRA, CERCLA, FIFRA, TSCA)

Four Steps of Risk Assessment and Risk Management

Hazard Identification • Determines if a compound is causally linked to health effects at environmentally relevant concentrations • Select Chemicals of Potential Concern (COPC) • Establish relationship between each COPC and adverse health effects (review tox. data) • Determine “critical” health effect for each COPC • Evaluate scientific weight-of-evidence for “critical” health effects (cancer and non-cancer)

Jeffrey A. Adams, PhD, PE Krishna R. Reddy, PhD, PE, D.GE