USE OF VPH/EPH/APH DATA TO CHARACTERIZE RISKS TO HUMAN HEALTH & THE ENVIRONMENT FROM PETROLEUM EXPOSURES  1st International Congress on Petroleum Contaminated Soils, Sediments, and Water Analysis, Assessment and Remediation Imperial College, London, U.K. Workshop No. 05 14 August 2001

1. USE OF VPH/EPH/APH DATA TO CHARACTERIZE RISKS TO HUMAN HEALTH & THE ENVIRONMENT FROM PETROLEUM EXPOSURES 1 st International Congress on Petroleum Contaminated Soils, Sediments, and Water Analysis, Assessment and Remediation Imperial College, London, U.K. Workshop No. 05 14 August 2001 Presented By: Peter W. Woodman, Ph.D. Risk Management Incorporated Acton, MA 01720-5676, USA (978) 266-2878

2. “ BETTER DEAD THAN INFRA-RED” Nicholas Anastas, MassDEP June 1997 “ VPH/EPH/APH”

12. CARBON RANGES FOR FUEL PRODUCTS Carbon Number C 1 C 5 C 10 C 15 C 20 C 25 C 30 Gasoline JP-4 No. 2 Fuel Oil/Diesel No. 6 Fuel Oil BACKGROUND: Petroleum Chemistry

13. BACKGROUND: Petroleum Chemistry TYPICAL COMPOSITION OF PETROLEUM PRODUCTS* Product Carbon Range Percent Aliphatic Percent Aromatic Gasoline C 4 - C 12 35% - 80% 10% - 40%** #2/Diesel C 8 - C 21 60% - 70% 30% - 40% #3-#6 Fuel Oil C 8 - C 30+ 20% - 50% 30% - 40%+ Jet Fuel/ C 9 - C 16 60% - 80% 5% - 20% Kerosene Dielectric C 12 - C 22 (?) 80%+ ? Oils Waste Oil C 15 - C 50+ 50% - 90% 10% - 30% (Crankcase) *Source: MADEP 1997 - VPH/EPH Spring Training Seminar **: Includes BTEX

15. BACKGROUND: MADEP’S VPH/EPH/APH Approach Analytical Methods Toxicology NEW VPH/EPH/APH PETROLEUM SITE ASSESSMENT APPROACH Fate & Transport

17. 1 MADEP October 2001. Fraction specific toxicity values only. Consult U.S. EPA IRIS and/or MADEP risk assessment guidance for Target Analyte toxicity values (cancer and non-cancer). RECOMMENDED MADEP VPH/EPH/APH TOXICITY VALUES 1 BACKGROUND: Toxicology

29. BACKGROUND: Fate and Transport * MADEP VPH/EPH/APH Guidance June 2001 . Based on TPHWCG Vol. 3, 1997 MADEP RECOMMENDED VPH/EPH/APH FRACTIONAL PROPERTIES *

42. SCREENING PROCEDURES VPH/EPH ANALYTICAL SCREENING TECHNIQUES Technique Range Application Limitations Recommendations* UV Fluorescence VPH/EPH Diesel/#2 Fuel Not for aliphatics Calibrate for direct and Absorbency Gasoline. - mineral oils or measurement of aromatics. Targets more dielectric fluids. Diesel/#2 Fuel Oil - toxic aromatics. Humic acid assume aliphatic content interference. x2 aromatic. Over-predict highly weathered diesel/#2 Fuel Oil. Emulsion-Based EPH Diesel/#2 Fuel Aliphatics and Diesel/#2 Fuel Oil - TPH Methods Oil- “TPH” aromatics not assume 60% C 11 -C 22 screening value differentiated aromatics and 40% (aliphatics and C 9 -C 18 aliphatics aromatics)

43. SCREENING PROCEDURES VPH/EPH ANALYTICAL SCREENING TECHNIQUES Technique Range Application Limitations Recommendations* Immunoassay VPH/EPH BTEX Not for lube/ Currently none Test Kits PAHs hydraulic oils. “ TPH” – based on naphthalene . Soil & GW. Fiber-Optic VPH/EPH In-situ vapor Response decreases Currently none Chemical measurement. as solubility increases. Sensors p-Xylene Benzene response is response. x10 < p-xylene. GW. Calibration/cleaning critical. *Source - MADEP VPH/EPH/APH Guidance June 2001

48. SCREENING PROCEDURES: VPH/EPH HETEROGENEITY OF SITE CONDITIONS WEATHERING/DEGRADABILITY OF PETROLEUM PRODUCT LOW HIGH low variability in time and space 10-20% VPH/EPH confirmation HIGH MINERAL/#6 FUEL OIL JET FUEL/GASOLINE #2/#4/DIESEL FUEL OIL moderate variability in time and space 20-40% VPH/EPH confirmation moderate variability in time and space 20-40% VPH/EPH confirmation high variability in time and space 40-60% VPH/EPH confirmation

50. SCREENING PROCEDURES MADEP RECOMMENDED TARGET ANALYTES SOIL SAMPLING * PETROLEUM PRODUCT GASOLINE #2 FUEL/DIESEL (TOV > 100 ppmv) #2 FUEL/DIESEL (TPH > 500 ug/g) #3 - #6 FUEL OILS JET FUEL/KEROSENE LUBE OILS HYDRAULIC OILS WASTE OILS (TOV > 10 ppmv) * MADEP VPH/EPH/APH Guidance June 2001; 2 add TEtPb, TMePb, EDB for leaded gasoline; 3 Omit BTEX/VOCs if TOV < 10 ppmv BTEX, MtBE, NAPTH TARGET ANALYTES BTEX, MtBE, NAPTH 2 Acenaphthene, NAPTH, 2-MeNAPTH, Phenanthrene BTEX/VOCs, PAHs, heavy metals 3 For TOV > 100 ppmv BTEX, NAPTH and PAHs as appropriate

51. SCREENING PROCEDURES MADEP RECOMMENDED TARGET ANALYTES GROUNDWATER SAMPLING * PETROLEUM PRODUCT GASOLINE #2 FUEL/DIESEL #3 - #6 FUEL OILS JET FUEL/KEROSENE LUBE OILS HYDRAULIC OILS WASTE OILS * MADEP VPH/EPH/APH Guidance June 2001; 2 add TEtPb, TMePb, EDB for leaded gasoline In shallow GW or GW-1, BTEX, MtBE, Acenaphthene, NAPTH, 2-MeNAPTH, Phenanthrene TARGET ANALYTES BTEX, MtBE, NAPTH 2 BTEX/VOCs, PAHs, PCBs, heavy metals In shallow GW or GW-1, BTEX and PAHs as appropriate