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Evaluating the Petroleum Vapor Intrusion Pathway Studies of Natural Attenuation of Subsurface Petroleum Hydrocarbons & Recommended Screening Criteria AEHS 27nd Annual International Conference on Soil, Sediment, Water & Energy Amherst, Massachusetts Vapor Intrusion Workshop, Monday October 17, 2011, 8:00am-12:00pm by Robin V. Davis, P.G. Project Manager Utah Department of Environmental Quality Leaking Underground Storage Tanks [email protected] 801-536-4177 OBJECTIVE • Understand why so many LUST sites exist nationwide, but few report cases of petroleum vapor intrusion to indoor air • Develop guidance for screening/exclusion criteria to determine when PVI pathway is incomplete • Avoid unnecessary, $costly$ PVI investigations SCOPE • Petroleum Vapor Database: Compile basic, high-quality field data to evaluate vapor intrusion pathway: soil type, source extent & degree, LNAPL, DTW, contaminant concentrations in dissolved & vapor phases • Show mechanisms, characteristics & trends of petroleum hydrocarbon vapor biodegradation Recent Timeline & History 2002-2011 Work Groups & Studies of Petroleum Hydrocarbon Vapor Intrusion • 2002: EPA OSWER Draft Guide for Vapor Intrusion Evaluations - Comprehensive; cautious screening criteria - Recommends for chlorinated hydrocarbons, NOT petroleum LUST sites because biodegradation is not considered - Recommends forming work group to study VI pathway for petroleum • 2003-2005: EPA OUST/States Petroleum Vapor Intrusion Work Group - Studied behavior of subsurface petroleum associated with PVI pathway - Began compiling international database (U.S. & Canada) - Work Group “put on hold,” disbanded… • 2005-2009: Continued compiling, analyzing field data - American Petroleum Institute (API) Work Group, peer-reviews petroleum vapor database, compiles more data - Screening criteria for low-risk sites published (Davis, R.V., 2009, LUSTLine #61) • 2009-2011: EPA OUST/States PVI Work Group Revived - Database much larger, EPA OUST peer-review in process - Validating Bio Vapor Model: Analytical Model, accounts for biodegradation of petroleum hydrocarbons in the subsurface (DeVaull and McHugh, 2010) - EPA OUST preparing to publish PVI guidance by November 2012 Petroleum Vapor Database Compilation of soil vapor data from subsurface multi-depth & sub-slab sample points, paired with concurrent source strength data Canada ~170 Sites, ~1000 Measurements of Concurrent SV, GW & Soil Data 2/13 United States 56/304 MAP KEY 56 # Geographic Locations Australia (sites) Evaluated 112/608 Perth 304 # Paired concurrent Sydney measurements of benzene subsurface soil vapor & source strength (Davis, R.V., 2009, updated 2011) Tasmania (Wright, J., 2011, Australian data) Characterize Site • Know Full Extent & Degree of Gas Station Building UST system Petroleum Vapor Sources • Construct Conceptual Site Model Contaminated Soil, shallow Strong Vapor Source from LNAPL & Contaminated Soil Contaminated Soil & LNAPL RAOULT’S LAW Clean aerobic soil Weak Vapor Source from Dissolved Plume HENRY’S LAW Dissolved contamination Results of Field Data & Published Studies • Subsurface soil is a natural bioreactor: - Biodegradation of Petroleum Hydrocarbons by hundreds/thousands microbial genera/species proven by 100 years of published research - Characteristics of petroleum biodegradation & vapor attenuation are well-understood & predictable - Vapors attenuate with 5-8 feet thickness of clean (uncontaminated) oxygenated (aerobic) overlying soil - Clean soil contains sufficient Oxygen needed to attenuate vapors, ~4% O2 - Vapors attenuate up to 1,000,000-fold, most 1000-10,000-fold • No reported cases of petroleum vapor intrusion from low source strengths • Causes of petroleum vapor intrusion: - LNAPL, contaminated soil or high dissolved concentrations near or in direct contact with buildings, sumps, elevator shafts Recognize Signature Characteristics of Aerobic Biodegradation & Attenuation of Petroleum Hydrocarbon Vapors Vapor Monitoring Well NJ-VW-2 Beaufort, SC, Lahvis et al, 1999 Beaufort, SC NJ-VW2 Sand, fine-grained, silt Oxygen et al., 1999) vapors 8 ft clean(Lahvis, soil attenuates Carbon Dioxide Subsurface Bio-AF=7E-07 Benzene O2 & CO2 (% V/V) 0 5 10 15 20 25 Depth feet bgs 0 5 Benzene in GW 16,000 ug/L 10 15 1.E+00 1.E+02 1.E+04 Benzene (ug/m3) 1.E+06 1.E+08 Recognize Non-Attenuation of Vapors due to Lack of Clean Overlying Soil Conneaut, OH VMP-1 (Roggemans, 1998; Roggemans et al., 2001) Subsurface AF 7E-01 Bio-AF=7E-01 Oxygen Carbon Dioxide Benzene O2 & CO2 (% V/V) 0 5 10 15 20 0 Contaminated Soil (sand, silty sand) 5 10 15 1.E+00 1.E+02 1.E+04 1.E+06 Benzene (ug/m3) 1.E+08 Recognize Importance of Shallow Vapor Completion Points Example of apparent non-attenuation due to no shallow soil completion point in 2006 VW-11 Hal’s, Green River, Utah VW-11 Benzene SV, ug/m3 TPH SV, ug/m3 0 0 2 2 4 4 6 8 No attenuation within contaminated zone 6 8 10 10 12 12 14 1.00E+00 Benzene SV, ug/m3 TPH SV, ug/m3 6/27/07 6/27/07 Depth, feet bgs Depth, feet bgs VW-11 8/26/06 8/26/06 Shallow points confirm attenuation above contaminated zone 14 1.00E+03 1.00E+06 SV Concentration, ug/m3 1.00E+09 1.00E+00 1.00E+03 1.00E+06 SV Concentration, ug/m3 1.00E+09 Method for Expressing Magnitude of Subsurface Vapor Attenuation “Attenuation Factor” AF = ratio of shallow subsurface vapor concentration divided by deep Beaufort, SC NJ-VW2 (Lahvis, et al., 1999) Oxygen Carbon Dioxide AF = Shallow SV Benzene, ug/m3 0 Deep SV Benzene, ug/m3 AF = 145,000 ug/m3 5 10 15 20 25 0 5 Field Example: ~1 ug/m3 Benzene O2 & CO2 (% V/V) = 7E-06 ~1,000,000x contaminant reduction Benzene in GW 16,000 ug/L 10 15 1.E+00 1.E+02 1.E+04 1.E+06 1.E+08 Benzene (ug/m3) Low AF = Great attenuation of contaminants Distribution of Magnitude of Subsurface Petroleum Vapor Attenuation Benzene 150 120 90 60 30 0 TPH 3 Reasons for Insignificant AF 200 160 120 80 40 0 <1.E-04 TPH 1.E-03 1.E-02 >1.E-01 Subsurface Vapor Attenuation Factors Screen these out Reason 1: No Reason 2: Low Clean Source Overlying Soil Strength 1.E-01 Reason 3: Rapid Attenuation Near HighStrength Source Number of Soil Vapor Sample Events Number of Soil Vapor Sample Events Number of Soil Vapor Sample Events Benzene 100 80 60 Most events exhibit Benzene TPH very low AFs, significant attenuation (<10,000x) Reasonable application 100x to 1000x 40 20 0 <1.E-04 1.E-03 1.E-02 Subsurface Vapor Attenuation Factors Comparison of Field Data to Models Beaufort, South Carolina (Lahvis et al 1999) Very High-Strength Dissolved Source beneath Pavement BioVapor Model under-predicts subsurface attenuation by 100x to 10,000x Beaufort, SC (Lahvis et al, 1999) Soil Vapor Field Data Compared to BioVapor Model from dissolved source Beaufort, SC (Lahvis et al, 1999) Soil Vapor Field Data Compared to BioVapor Model from Dissolved Source TPH-gro Field-Measured, ug/m3 Benzene Field-Measured, ug/m3 TPH-gro Bio Vapor Prediction, ug/m3, AF=0.1, O2=1%, foc=0.5%, Bare Earth Benzene BioVapor Prediction, ug/m3, AF=0.1, O2=1%, foc=0.5%, Bare Earth TPH-gro Bio Vapor Prediction, ug/m3, AF=0.1, O2=1%, foc=0.5%, Pavement Benzene BioVapor Prediction, ug/m3, AF=0.1, O2=1%, foc=0.5%, Pavement TPH-gro Bio Vapor Prediction, ug/m3, AF=0.1, O2=1%, foc=0.5%, Aerobic Depth Speci 0 0 3 3 Depth, feet bls Depth, feet bls Benzene BioVapor Prediction, ug/m3, AF=0.1, O2=1%, foc=0.5%, Aerobic Depth=3.4 ft bls 6 9 6 9 Benzene in GW 16,000 ug/L 12 1.0E+00 1.0E+01 1.0E+02 1.0E+03 1.0E+04 1.0E+05 1.0E+06 1.0E+07 TPH in GW 67,100 ug/L 12 1.0E-01 1.0E+01 1.0E+03 1.0E+05 Benzene, ug/m3 TPH-gro, ug/m3 1.0E+07 1.0E+09 Chatterton, SG-BC 10-1-97 (Hers et al 2000) Soil VaporChatterton, Source over&Benzene-Rich LNAPL, Multi-Depth Sub-Slab BC, Sub-Slab Multi-Depth Beneath Building, 10-1-97 (Hers, 2006) Benzene Soil Vapor Field Data Compared to BioVapor Model BioVapor Model under-predicts subsurface attenuation by 10,000x to 1,000,000x Benzene Field-Measured, ug/m3 Benzene Bio Vapor Prediction, ug/m3, O2=1%, foc=0.5% Benzene Bio Vapor Prediction, ug/m3, O2=1%, foc=0.5%, Aerobic Depth 3.28 ft -5 Depth, feet bls Building Slab 0 5 10 1.0E+00 LNAPL, benzene rich 1.0E+02 1.0E+04 1.0E+06 Benzene, ug/m3 1.0E+08 Numerical Model Effect of Vapor Source Concentration & Depth Beneath Buildings Vapor source 100,000 ug/m3 (Abreu-Johnson Model, Abreu et al 2009, API #4775) Vapor source 1,000,000 ug/m3 Vapor source 10,000,000 ug/m3 Conclusions from Models BioVapor Model - Under-predicts subsurface attenuation & over-predicts PVI by 10xxxx for low-to-medium-high source strength - Very high-strength sources likely need PVI investigation Abreu-Johnson Numerical Model - Vapors associated with low-to-medium source strengths beneath average-size buildings are attenuated with a few feet of clean overlying soil - Oxygen occlusion beneath slab with high vapor concentrations at shallow depths Screening/Exclusion Criteria • PVI Database: line-by-line analysis of field data, plot data • Determine Thickness of Clean Overlying Soil Required to Attenuate Vapors Associated with: - Dissolved Sources - LNAPL & Soil Sources Method for Evaluating Vapor Attenuation from Dissolved Sources Multi-Depth Vapor Monitoring Well Beaufort, SC, Lahvis et al 1999 Feet bgs NJ-VW-2 0 5 8 feet Clean overlying soil 3 ft Benzene vapor concentrations at depth <1 ug/m3 4 ft 2,300 ug/m3 7 ft 16,700 ug/m3 Estimated Contaminated soil zone 10 DTW ~11 ft 11 ft 145,000 ug/m3 Benzene in GW 16,000 ug/L 15 FORMULA: 11 ft – 3 ft = 8 ft clean overlying soil Screening Criteria for Dissolved Benzene & TPH (Exterior + Sub-Slab) Benzene: Soil Vapor & Dissolved Paired Measurements TPH: Soil Vapor & Dissolved Paired Measurements Near-Slab Multi-Depth, Sub-Slab= 97 total TPH: 73 exterior/near-slab + 24 sub-slab Benzene: 199 Near-Slab exterior/near-slab + 37 sub-slab Multi-Depth, Sub-Slab = 236 total All Soil Types All Soil Types Thickness Clean Soil Required to Attenuate TPH Vapors, feet Thickness Clean Soil Required to Attenuate Benzene Vapors, feet 10 9 8 7 6 5 4 3 2 1 0 1 10 100 1,000 10,000 100,000 10 9 8 7 6 5 4 3 2 1 0 1 100 10,000 1,000,000 Benzene, dissolved, ug/L TPH, dissolved, ug/L 5 ft Clean Overlying Soil Attenuates Vapors Associated with Dissolved Benzene <1,000 ug/L, TPH 10,000 ug/L Separation Distance vs Source Strength: Benzene Soil Gas Concentrations Associated with Source Strengths (ug/m3) Dissolved phase, B(SG) < 50 µg/m 3 Dissolved phase, B(SG) > 50 and <1000 µg/m 3 LNAPL, B(SG) < 50 µg/m3 LNAPL, B(SG) > 50 and < 1,000 µg/m3 LNAPL, B(SG) > 1,000 and <100,000 µg/m3 LNAPL, B(SG) > 100,000 µg/m3 1.5 m (~5 ft) clean soil required to attenuate vapours associated with Benzene in GW <1 mg/L Separation Distance, Source to Soil Gas measurement (m) (slide courtesy of Jackie Wright, Environmental Risk Sciences, Sydney, Australia) Field-Based Screening/Exclusion Distances from Soil Gas Data (Lahvis, M., 2011) 100% BENZENE 1000000 100000 20 SITES 89 LOCATIONS 335 SAMPLES 90% 80% PROBABILITY (%) SOIL GAS CONCENTRATION (ug/m3) 10000000 10000 1000 100 10 BENZENE 60% < 50 ug/m3 50% < 100 ug/m3 40% < 200 ug/m3 30% 20% measured non detect 1 70% DETECTS 10% 0% 0.1 0 10 20 30 40 DISTANCE ABOVE SOURCE (ft) 50 0 5 10 15 20 25 DISTANCE ABOVE WATER TABLE (ft) Example: Robin Davis (Utah DEQ) and Jackie Wright (Australia) soil-gas databases 1245 soil-gas measurements from 155 retail* sites and 664 sampling locations For gasoline sources, dissolved and LNAPL Exclusion distances based on conditional probability P ( soil gas <100 ug/m3 | source distance > 5 ft) = 1 – (134/335) = 60% P ( soil gas < 100 ug/m3 | source distance > 15 ft) = 1 – (17/335) = 95% 30 2 Methods for Evaluating Vapor Attenuation from LNAPL & Soil Sources Hals’, Green River, Utah (UDEQ) Oxygen VW-7 6/26/07 Carbon Dioxide Benzene O2 & CO2 (% v/v) 0 5 10 15 20 Method 1 Formula: 20 ft DTW – 11 clean SV= 9 feet TOTAL soil thickness 0 Method 2 Formula: 15 ft top contam – 11 ft top clean soil = 4 feet CLEAN soil needed to attenuate vapors Depth feet bgs 5 10 contaminated soil zone 15 20 1.E+00 1.E+02 1.E+04 1.E+06 Benzene (ug/m3) 1.E+08 Method 1 Results for LNAPL Sources (All soil types. 43 paired SV benzene & LNAPL Events) Sample events beneath buildings Thickness of Overlying Soil, feet 30 25 30 ft TOTAL (clean + contaminated smear zone) soil attenuates benzene vapors associated with LNAPL Refineries 20 15 10 5 0 Chillum Chatterton Coachella-2 Hal’s Coachella-3 Mission Valley Refinery, Unknown US Location Method 2 Results for LNAPL & Soil Sources Benzene 48 exterior/near-slab + 23 sub-slab = 71 total Benzene SV Sample Event over LNAPL & Soil Sources TPH 17 exterior/near-slab + 19 sub-slab = 36 total TPH SV Sample Event over LNAPL & Soil Sources Near-Slab Multi-Depth, Sub-Slab 10 9 8 7 6 5 4 3 2 1 0 Thickness of Clean Soil Overlying LNAPL Required to Attenuate Vapors, feet Thickness of Clean Soil Overlying LNAPL Required to Attenuate Vapors, feet Near-Slab Multi-Depth, Sub-Slab 10 9 8 7 6 5 4 3 2 1 0 ~8 ft CLEAN overlying soil attenuates vapors associated with LNAPL/Soil Sources Screening Criteria–Published & Cited Values (after Lahvis & DeVaull, 2011) Reference Davis, R.V. (2009, 2010) Lahvis (2011) McHugh et al (2010) Peargin & Kolhatkar (2011) Wright, J. (2011) California Indiana New Jersey Wisconsin Database & Site Type International Petroleum Vapor Database R.V. Davis & J. Wright (retail sites only, no refineries) Benzene Soil Gas Screening Level (ug/m3) Screening/Exclusion Distance (feet) Screening/Exclusion Concentration Benzene (ug/L) complete attenuation 5 <1000 8 LNAPL 0 <12,000 15 LNAPL 10 Dissolved phase only 30 LNAPL 0 <520 15 >520 5 <1000 30 LNAPL 5 <100 no SG Oxygen measured 5 <1000 with SG Oxygen measured >4% (?) 10 <1000 no SG Oxygen measured 30 LNAPL 5 <1000 10 <1000 30 LNAPL 5 <100 no SG Oxygen measured 5 <1000 with SG Oxygen measured >4% (?) 10 <1000 no SG Oxygen measured 30 15 5 <1000 20 >1000 30 LNAPL 100 various publications, professional judgement Chevron, all sites Australia & U.S. sites, all sites + refineries various references, R.V. Davis, McHugh et al various references, R.V. Davis, McHugh et al various references, R.V. Davis, McHugh et al Davis, R.V., 2009 , Luo et al 2009, McHugh et al, 2010 300 10, 50, 100, 1000 Other Criteria 5 feet for TPH <10,000 ug/L Dissolved phase only NONE NONE SG Oxygen requirement Distances apply vertically & horizontally NONE NONE Horizontal distance required from building structure to Benzene 15 ug/L Distances apply vertically & horizontally Screening Criteria–Published & Cited Values (after Lahvis & DeVaull, 2011), continued Reference Database & Site Type Benzene Soil Gas Screening Level (ug/m3) Screening/Exclusi on Distance (feet) Screening/Exclusion Concentration Benzene (ug/L) EPA OSWER (2002) (1) (1) 100 Dissolved phase only 100 LNAPL 30 Dissolved phase only 100 LNAPL 0 <1000 60 LNAPL ASTM E 2600-08 (2008) Atlantic PIRI (2006) (2) Modeling (Abreu & Johnson, 2005) (2) NONE (1) based on measured indoor data for one or more dissolved chlorinated solvent groundwater plumes in Colorado. (2) based on EPA OSWER (2002) Other Criteria Spatial Data Behavior of Vapors Beneath & Exterior to Buildings Chatterton Research Site, British Columbia, Canada (Hers, et al 2000) Building SG-BC, 10/1/97 0 Fill, sandy silt SG-BR 5/14/97 <1000 11% 10 % <1000 10% 80,000 8% Depth, feet bls 55,000 6% 5 Fill, dredged river sand Bare soil 3% 50,000,000 25,000,000 1.0% KEY SG-BC 50,000,000 1.0% Vapor sample point identifier Sub-Slab vapor sample point 60,000,000 Sub-Surface vapor sample point 50,000,000 1.0% Benzene, ug/m3 Oxygen, % LNAPL, benzene-rich 10 FIELD RESULTS: Oxygen is NOT occluded by small building ~9 ft above LNAPL source 0 20 Feet, horizontal Perth, Australia Very Large Building 0 410 <2 30-ft wide concrete apron Uncovered open ground 19,000,000 <0.5% Depth, feet bls (B. Patterson & G. Davis, ES&T 2009) <50,000 10.7% <50,000 19.9% <50,000 18.8% Lateral Extent of Oxygen & Biodegradation 5 35,000,000 <0.5% Sand 35,000,000 <0.5% 10 <50,000 8.2% <50,000 14.5% <50,000 15.9% 1,200,000 8.2% <50,000 4.5% <50,000 4.6% LNAPL, kerosene, low BTEX FIELD RESULTS: Oxygen is occluded by large building, but reaches to ~30 ft laterally beneath building. Exterior vapor attenuation with ~5 ft clean soil & ~8 ft total soil above LNAPL. KEY Outdoor air sample Indoor air sample Sub-slab vapor sample Sub-surface vapor sample 1,200,000 Total Petroleum Hydrocarbons, ug/m3 8.2% Oxygen, % 0 20 Feet, horizontal Temporal Data Behavior of Vapors Beneath & Exterior to Buildings Over Time Chatterton Research Site, British Columbia, Canada SG-BC Beneath Building Chatterton SG-BC Beneath Building Hers et al 2000 0 Building foundation slab Benzene SV 9/2/97 (Hers et al, 2000) SG-BR ~16 ft from Building Edge Chatterton SG-BR ~16 ft from Building edge Benzene SV 10/1/97 Hers et al 2000 Benzene SV 11/1/97 Benzene SV 3/18/98 0 Bare soil Ben z en e S V 7/25/97 < Detection limits Ben z en e S V 12/1/97 Depth, feet bgs ft bgs Depth, feet bgs ft bgs 6 Ben z en e S V 3/18/98 8 4 Ben z en e S V 11/1/98 Ben z en e S V 2/19/99 6 8 10 1.E+00 Ben z en e S V 7/2/97 2 4 Ben z en e S V 5/14/97 Ben z en e S V 6/24/97 Benzene SV 6/1/98 2 Ben z en e S V 3/11/97 1.E+02 1.E+04 1.E+06 Benzene SV, ug/m3 1.E+08 1.E+10 10 1.E+00 1.E+02 FIELD RESULTS: Small building ~9 feet above LNAPL. Vapors are attenuated below building slab for all events near-slab, & sub-slab except the first. 1.E+04 1.E+06 Benzene SV, ug/m3 1.E+08 1.E+10 1 Characterize Site (non-emergency conditions) 2 3 4 Decision Matrix Compare Dissolved/LNAPL/Soil Field Data to Screening Criteria No Exceedance Collect Soil Vapor Data & Evaluate Attenuation No Exceedance Compare IA/OA to Screening or HealthBased Criteria No Exceedance 6 5 Mitigate No Exceedance No Further PVI Evaluation Needed Conclusions • PVI pathway not complete when following Criteria apply: Dissolved Sources - 5 feet CLEAN soil overlying Benzene <1,000 ug/L, TPH <10,000 ug/L LNAPL Sources - 8 feet CLEAN soil overlying top of LNAPL smear zone or soil sources - 30 feet TOTAL including smear zone; poorly-characterized sites Soil Sources - 5 feet CLEAN soil = TPH <100 mg/kg, PID <10 ppm-v, O2 ~4% Vapor Sources - Vapors are attenuated below the receptor Recommendations • Fully characterize sites • Collect & use ALL lines of evidence to determine if PVI pathway is complete • Apply Screening/Exclusion Criteria in decision-making THANK YOU Acknowledgments EPA OUST/ORD/States PVI Work Group API Petroleum Vapor Intrusion Work Group Bruce Bauman, Roger Claff, Harley Hopkins George DeVaull, Shell Global Solutions Blayne Hartman, Hartman Environmental Geoscience Tom McHugh, GSI Environmental John Menatti, Utah DEQ Tom Peargin, Chevron-Texaco Lynn Spence, P.E., Spence Engineering Todd Ririe, BP Matt Lahvis, Shell Global Solutions Jackie Wright, Environmental Risk Sciences