USE OF VPH/EPH/APH DATA TO  CHARACTERIZE RISKS TO HUMAN HEALTH & THE ENVIRONMENT FROM PETROLEUM EXPOSURES  1 st  Internati...
“ BETTER DEAD THAN INFRA-RED” Nicholas Anastas, MassDEP June 1997 “ VPH/EPH/APH”
WORKSHOP PROGRAM <ul><li>INTRODUCTION AND BACKGROUND TO MADEP VPH/EPH/APH APPROACH </li></ul><ul><ul><li>History </li></ul...
<ul><li>EXPOSURE POINT CONCENTRATIONS </li></ul><ul><ul><li>Soil - Hot Spots, Averages </li></ul></ul><ul><ul><li>Groundwa...
WORKSHOP PROGRAM <ul><li>USE OF VPH/EPH/APH APPROACH IN OTHER JURISDICTIONS </li></ul><ul><ul><li>EPA Regions </li></ul></...
INTRODUCTION AND BACKGROUND: History OF MADEP’S VPH/EPH/APH Approach <ul><li>KEY MADEP DOCUMENTS ON PETROLEUM CONTAMINATIO...
INTRODUCTION AND BACKGROUND: History OF MADEP’S VPH/EPH/APH Approach <ul><ul><li>May 1996  - Issues Paper:  Implementation...
INTRODUCTION AND BACKGROUND: History OF MADEP’S VPH/EPH/APH Approach <ul><ul><li>January 1998  - FINAL Laboratory Standard...
INTRODUCTION AND BACKGROUND: History OF MADEP’S VPH/EPH/APH Approach <ul><li>OTHER KEY PUBLICATIONS </li></ul><ul><ul><li>...
INTRODUCTION AND BACKGROUND: History OF MADEP’S VPH/EPH/APH Approach <ul><ul><li>Total Petroleum Hydrocarbon Criteria Work...
<ul><li>PETROLEUM FUELS </li></ul><ul><ul><li>Spills and releases of petroleum fuels are the leading source of environment...
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...
BACKGROUND:  Petroleum Chemistry TYPICAL COMPOSITION OF PETROLEUM PRODUCTS* Product Carbon Range Percent Aliphatic   Perce...
<ul><li>GENERAL PETROLEUM HYDROCARBON OBSERVATIONS: </li></ul><ul><ul><li>Main composition: Aliphatic (alkanes, alkenes/al...
BACKGROUND: MADEP’S VPH/EPH/APH Approach Analytical Methods Toxicology NEW VPH/EPH/APH PETROLEUM SITE ASSESSMENT APPROACH ...
<ul><li>TECHNICAL STRATEGY AND ISSUES </li></ul><ul><ul><li>Toxicology </li></ul></ul><ul><ul><ul><li>Divided broad chemic...
1 MADEP October  2001.  Fraction specific toxicity values only.   Consult U.S. EPA IRIS and/or  MADEP risk assessment guid...
BACKGROUND: Analytical Methods <ul><ul><li>MADEP developed analytical methods to quantify carbon fractions and target anal...
BACKGROUND: Analytical Methods <ul><ul><li>MADEP developed analytical methods to quantify carbon fractions and target anal...
Universe of Petroleum Hydrocarbons (C 5  - C 36 +) C 5 C 9 C 12 C 5  - C 8 Aliphatics BTEX/MtBE/NAPTH/BD C 9  - C 10 Aroma...
<ul><ul><ul><li>DEFINED AS PURGE AND TRAP, GC/PID/FID PROCEDURE   </li></ul></ul></ul><ul><ul><ul><li>ALLOWS COLLECTIVE QU...
BACKGROUND: Analytical Methods <ul><ul><ul><li>REPORTING LIMITS </li></ul></ul></ul><ul><ul><ul><ul><ul><li>Collective Fra...
BACKGROUND: Analytical Methods <ul><ul><ul><li>DEFINED AS SOLVENT EXTRACTION, FRACTIONATION, GC/FID PROCEDURE </li></ul></...
BACKGROUND: Analytical Methods <ul><ul><ul><li>REPORTING LIMITS </li></ul></ul></ul><ul><ul><ul><ul><ul><li>Collective Fra...
<ul><ul><ul><li>GC/MS PROCEDURE FOR AIR OR SOIL GAS SAMPLES </li></ul></ul></ul><ul><ul><ul><li>ALLOWS COLLECTIVE QUANTIFI...
BACKGROUND: Analytical Methods <ul><ul><ul><li>REPORTING LIMITS </li></ul></ul></ul><ul><ul><ul><ul><ul><li>Collective Fra...
BACKGROUND: FATE & TRANSPORT CONTAMINATED SOIL GROUNDWATER AMBIENT/ INDOOR AIR <ul><li>Petroleum Constituents Likely to Vo...
BACKGROUND: Fate and Transport <ul><li>FATE AND TRANSPORT </li></ul><ul><ul><li>Significant variability in behavior of pet...
BACKGROUND: Fate and Transport * MADEP VPH/EPH/APH Guidance   June 2001 .  Based on TPHWCG Vol. 3, 1997 MADEP RECOMMENDED ...
BACKGROUND: MCP Risk Characterization Methods <ul><li>DEVELOPMENT OF MCP NUMERICAL STANDARDS  * </li></ul><ul><ul><li>MCP ...
BACKGROUND: MCP Risk Characterization Methods <ul><ul><li>MCP  Soil Standards address health effects, ceiling concentratio...
BACKGROUND: MCP Risk Characterization Methods <ul><ul><li>Upper Concentration Limits (UCLs)*   </li></ul></ul><ul><ul><ul>...
BACKGROUND: MCP Risk Characterization Methods <ul><li>Reportable Concentrations (RCs)* </li></ul><ul><ul><li>Groundwater: ...
BACKGROUND: MCP Risk Characterization Methods <ul><li>THREE MCP RISK CHARACTERIZATION METHODS </li></ul><ul><ul><li>Select...
BACKGROUND: MCP Risk Characterization Methods <ul><li>METHOD 1 </li></ul><ul><ul><li>Comparison of Site CoC* Concentration...
BACKGROUND: MCP Risk Characterization Methods <ul><li>METHOD 2 </li></ul><ul><ul><li>Create Soil and/or Groundwater Standa...
BACKGROUND: MCP Risk Characterization Methods <ul><li>METHOD 3 </li></ul><ul><ul><li>Used to Address OHM Exposures in all ...
BACKGROUND: MCP Risk Characterization Methods <ul><li>Site-Specific Evaluation of Risk to Human Health, Safety, Public Wel...
BACKGROUND: MCP Risk Characterization Methods <ul><li>METHOD 3 (cont.) </li></ul><ul><ul><li>MADEP Optional Draft #2 Diese...
FIELD SAMPLING & ANALYSIS <ul><li>ENVIRONMENTAL SAMPLE COLLECTION AND ANALYSIS </li></ul><ul><ul><li>Regulatory Framework ...
SCREENING PROCEDURES <ul><li>VPH/EPH ANALYTICAL SCREENING TECHNIQUES </li></ul><ul><li>Technique   Range   Application   L...
SCREENING PROCEDURES VPH/EPH ANALYTICAL SCREENING TECHNIQUES Technique   Range   Application   Limitations   Recommendatio...
SCREENING PROCEDURES VPH/EPH ANALYTICAL SCREENING TECHNIQUES Technique   Range     Application   Limitations   Recommendat...
SCREENING PROCEDURES <ul><li>SINCE THE TOXICITY OF AROMATIC FRACTIONS>>ALIPHATICS: </li></ul><ul><ul><li>Better to use scr...
SCREENING PROCEDURES <ul><li>SMALL SITES  (e.g., residential USTs) </li></ul><ul><ul><li>Screening procedures used: </li><...
SCREENING PROCEDURES: VPH/EPH <ul><li>MINIMUM  NUMBER OF VPH/EPH SAMPLES: </li></ul><ul><ul><li>Required to characterize t...
SCREENING PROCEDURES <ul><li>KEY  SITE-SPECIFIC VARIABLES  ARE: </li></ul><ul><ul><li>Heterogeneity of site conditions (st...
SCREENING PROCEDURES: VPH/EPH HETEROGENEITY OF SITE CONDITIONS WEATHERING/DEGRADABILITY OF PETROLEUM PRODUCT LOW HIGH low ...
SCREENING PROCEDURES: VPH/EPH <ul><li>MADEP VPH/EPH RECOMMENDED SCREENING </li></ul><ul><li>SOIL AND GROUNDWATER SAMPLING ...
SCREENING PROCEDURES MADEP RECOMMENDED TARGET ANALYTES SOIL SAMPLING  * PETROLEUM PRODUCT GASOLINE  #2 FUEL/DIESEL (TOV > ...
SCREENING PROCEDURES MADEP RECOMMENDED TARGET ANALYTES GROUNDWATER SAMPLING  * PETROLEUM PRODUCT GASOLINE  #2 FUEL/DIESEL ...
VPH/EPH CAVEATS <ul><li>SPLIT SAMPLES </li></ul><ul><ul><li>For split samples analyzed by both VPH and EPH methods,  not  ...
VPH/EPH CAVEATS <ul><li>FILTRATION </li></ul><ul><ul><li>May be appropriate for EPH groundwater samples under certain cond...
VPH/EPH CAVEATS <ul><li>USE OF TPH DATA </li></ul><ul><ul><li>Compare  directly  to TPH RCs and Cleanup Standards (now  ba...
<ul><li>MADEP RECOMMENDED TPH COMPOSITIONAL ASSUMPTIONS FOR SOIL * </li></ul><ul><li>PETROLEUM </li></ul><ul><li>PRODUCT  ...
VPH/EPH CAVEATS <ul><li>MADEP RECOMMENDED COMPOSITIONAL ASSUMPTIONS FOR GROUNDWATER * </li></ul><ul><li>TPH DATA </li></ul...
VPH/EPH CAVEATS <ul><li>USE OF ASSUMPTIONS </li></ul><ul><ul><li>Unless it can be demonstrated that assumptions used repre...
VPH/EPH CAVEATS <ul><li>COMPOSITIONAL VARIABILITY SOLUTIONS </li></ul><ul><ul><li>Easy Way </li></ul></ul><ul><ul><ul><li>...
DATA VALIDATION <ul><li>DATA VALIDATION FOR VPH/EPH/APH METHODS  </li></ul><ul><ul><li>Samples collected and received by l...
DATA VALIDATION <ul><ul><ul><li>VPH </li></ul></ul></ul><ul><ul><ul><ul><li>Collective Fractions:  2 to 10 mg/kg (soil) </...
DATA VALIDATION <ul><ul><ul><li>APH </li></ul></ul></ul><ul><ul><ul><ul><li>Collective Fractions:  25 to 100 µg/m 3  (air/...
EXPOSURE POINT CONCENTRATIONS <ul><li>REPORTABLE CONCENTRATIONS (310 CMR 40.0350) </li></ul><ul><ul><li>Comparison of meas...
EXPOSURE POINT CONCENTRATIONS <ul><li>SOIL </li></ul><ul><ul><li>Hot Spot  </li></ul></ul><ul><ul><ul><li>Discrete area wh...
EXPOSURE POINT CONCENTRATIONS <ul><li>SOIL (cont.) </li></ul><ul><ul><li>Averages </li></ul></ul><ul><ul><ul><li>Arithmeti...
EXPOSURE POINT CONCENTRATIONS <ul><li>GROUNDWATER </li></ul><ul><ul><li>Monitoring wells -  considered individual exposure...
EXPOSURE POINT CONCENTRATIONS <ul><li>GROUNDWATER (cont.)  </li></ul><ul><ul><li>Modeled EPC  - based on fate and transpor...
EXPOSURE POINT CONCENTRATIONS <ul><li>SURFACE WATER  </li></ul><ul><ul><li>Sampled Concentration </li></ul></ul><ul><ul><l...
EXPOSURE POINT CONCENTRATIONS <ul><li>AIR* </li></ul><ul><ul><li>Acute Exposures ( <  24 hrs) </li></ul></ul><ul><ul><ul><...
EXPOSURE POINT CONCENTRATIONS * Source:  MADEP Indoor Air Sampling and Evaluation Guide, Draft January 2000 <ul><li>AIR* <...
EXPOSURE POINT CONCENTRATIONS <ul><li>AIR (cont.) </li></ul><ul><ul><li>Modeled  - Target Compounds (VOCs, NAPTH, 2-MeNAPT...
EXPOSURE POINT CONCENTRATIONS <ul><li>AIR (cont.) </li></ul><ul><ul><li>Modeled  - Target Compounds (VOCs, NAPTH, 2-MeNAPT...
BACKGROUND SCREENING <ul><li>IDENTIFICATION OF CONTAMINANTS OF CONCERN </li></ul><ul><ul><li>SOIL </li></ul></ul><ul><ul><...
BACKGROUND SCREENING <ul><li>IDENTIFICATION OF CONTAMINANTS OF CONCERN   </li></ul><ul><ul><li>GROUNDWATER/SURFACE WATER <...
BACKGROUND SCREENING <ul><li>IDENTIFICATION OF CONTAMINANTS OF CONCERN </li></ul><ul><ul><li>MADEP LEVEL 1 SOIL GAS SCREEN...
BACKGROUND SCREENING <ul><li>IDENTIFICATION OF CONTAMINANTS OF CONCERN </li></ul><ul><li>MADEP LEVEL 2 SOIL GAS FRACTIONAL...
BACKGROUND SCREENING <ul><li>IDENTIFICATION OF CONTAMINANTS OF CONCERN </li></ul><ul><ul><li>* Time-weighted, indoor air s...
RISK CHARACTERIZATION <ul><li>METHOD 1 </li></ul><ul><ul><li>TPH </li></ul></ul><ul><ul><ul><li>Compare Exposure Point Con...
RISK CHARACTERIZATION <ul><li>METHOD 1 (cont.) </li></ul><ul><ul><li>VPH/EPH </li></ul></ul><ul><ul><ul><li>Compare indivi...
RISK CHARACTERIZATION <ul><li>METHOD 1 (cont.) </li></ul><ul><ul><li>VPH/EPH </li></ul></ul><ul><ul><ul><li>If odors prese...
RISK CHARACTERIZATION <ul><li>METHOD 2 </li></ul><ul><ul><li>Create Soil and/or Groundwater Standards for OHM when no Meth...
RISK CHARACTERIZATION <ul><li>METHOD 2 (cont.) </li></ul><ul><ul><ul><li>GW-3   :  Modification based on fate and transpor...
RISK CHARACTERIZATION <ul><li>METHOD 2 (cont.) </li></ul><ul><ul><ul><li>Soil Standards (S-1, S-2, S-3) cont. :  In lieu o...
<ul><li>METHOD 2 (cont.) </li></ul><ul><ul><li>Not applicable for media other than soil or groundwater </li></ul></ul><ul>...
RISK CHARACTERIZATION <ul><li>METHOD 3 </li></ul><ul><ul><li>Addresses all media (soil, groundwater, surface water, sedime...
RISK CHARACTERIZATION <ul><li>METHOD 3 (cont.) </li></ul><ul><ul><li>Optional Shortform for #2 Fuel/Diesel Oil Residential...
RISK CHARACTERIZATION <ul><li>METHOD 3 (cont.) </li></ul><ul><ul><li>Public Welfare </li></ul></ul><ul><ul><ul><li>Odors; ...
RISK CHARACTERIZATION <ul><li>METHOD 3 (cont.) </li></ul><ul><ul><li>Environment </li></ul></ul><ul><ul><ul><li>Stage I En...
RISK CHARACTERIZATION <ul><li>METHOD 3 (cont.) </li></ul><ul><ul><li>Environment </li></ul></ul><ul><ul><ul><li>Stage II E...
USE OF VPH/EPH APPROACH IN  OTHER JURISDICTIONS <ul><li>USEPA REGIONS </li></ul><ul><ul><li>REGIONS:  1, 2 , 4, 10 ???? </...
VPH/EPH FUTURE DEVELOPMENTS <ul><li>TOXICITY FACTORS </li></ul><ul><ul><li>MADEP continuing to evaluate appropriate Refere...
OPEN  DISCUSSION <ul><li>ISSUES </li></ul><ul><li>COMMENTS </li></ul><ul><li>AFTERNOON TEA  OR THE PUB? </li></ul>
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Ist Congress Vph Eph Aph (8 14 01)

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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

Published in: Technology, Economy & Finance
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  • Ist Congress Vph Eph Aph (8 14 01)

    1. 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. 2. “ BETTER DEAD THAN INFRA-RED” Nicholas Anastas, MassDEP June 1997 “ VPH/EPH/APH”
    3. 3. WORKSHOP PROGRAM <ul><li>INTRODUCTION AND BACKGROUND TO MADEP VPH/EPH/APH APPROACH </li></ul><ul><ul><li>History </li></ul></ul><ul><ul><li>Petroleum Chemistry </li></ul></ul><ul><ul><li>Toxicology </li></ul></ul><ul><ul><li>Analytical Methods </li></ul></ul><ul><ul><li>Fate and Transport </li></ul></ul><ul><ul><li>Risk Characterization Methods </li></ul></ul><ul><li>FIELD SAMPLING & ANALYSIS </li></ul><ul><ul><li>Screening </li></ul></ul><ul><ul><li>VPH/EPH/APH Approach </li></ul></ul><ul><ul><li>Caveats </li></ul></ul><ul><ul><li>Data Validation </li></ul></ul>
    4. 4. <ul><li>EXPOSURE POINT CONCENTRATIONS </li></ul><ul><ul><li>Soil - Hot Spots, Averages </li></ul></ul><ul><ul><li>Groundwater - Maximums, Averages & Modeled </li></ul></ul><ul><ul><li>Air - Monitored & Modeled </li></ul></ul><ul><ul><li>Surface Water - Monitored & Modeled </li></ul></ul><ul><li>BACKGROUND SCREENING </li></ul><ul><li>RISK CHARACTERIZATION </li></ul><ul><ul><li>MCP Methods 1, 2, and 3 </li></ul></ul><ul><ul><li>* Footnote: MCP = Massachusetts Contingency Plan (310 CMR 40.000) </li></ul></ul>WORKSHOP PROGRAM
    5. 5. WORKSHOP PROGRAM <ul><li>USE OF VPH/EPH/APH APPROACH IN OTHER JURISDICTIONS </li></ul><ul><ul><li>EPA Regions </li></ul></ul><ul><ul><li>Other States </li></ul></ul><ul><li>FUTURE DEVELOPMENTS </li></ul><ul><ul><li>Revised Toxicity Factors </li></ul></ul><ul><li>OPEN DISCUSSION </li></ul><ul><ul><li>Issues </li></ul></ul><ul><ul><li>Comments </li></ul></ul>
    6. 6. INTRODUCTION AND BACKGROUND: History OF MADEP’S VPH/EPH/APH Approach <ul><li>KEY MADEP DOCUMENTS ON PETROLEUM CONTAMINATION </li></ul><ul><ul><li>April 1991 - Policy for the Investigation, Assessment, and Remediation of Petroleum Releases, MADEP, BWSC, Policy #WSC-401-91 </li></ul></ul><ul><ul><li>August 1994 - Interim Final Report: Development of Health-Based Alternative to the Total Petroleum Hydrocarbon (TPH) Parameter* </li></ul></ul><ul><ul><li>August 1995 - Method for Determination of Volatile Petroleum Hydrocarbons (VPH), Public Comment Draft 1.0 </li></ul></ul><ul><ul><li>August 1995 - Method for Determination of Extractable Petroleum Hydrocarbons (EPH), Public Comment Draft 1.0 </li></ul></ul>
    7. 7. INTRODUCTION AND BACKGROUND: History OF MADEP’S VPH/EPH/APH Approach <ul><ul><li>May 1996 - Issues Paper: Implementation of VPH/EPH, Public Comment Draft* </li></ul></ul><ul><ul><li>January 1997 - Revisions to the Massachusetts Contingency Plan, 310 CMR 40.000 - Public Comment Draft </li></ul></ul><ul><ul><li>June 1997 - Beyond TPH Understanding and Using the New VPH/EPH Approach* </li></ul></ul><ul><ul><li>October 1997 - DRAFT Characterizing Risks Posed by Petroleum Contaminated Sites: Implementation of MADEP VPH/EPH Approach* </li></ul></ul><ul><ul><li>December 1997 - #2 Fuel/Diesel Shortform (Excel Spreadsheet)* </li></ul></ul><ul><ul><li>January 1998 - Reports on Results of VPH/EPH 1st and 2nd Round Robin Testing Programs* </li></ul></ul>
    8. 8. INTRODUCTION AND BACKGROUND: History OF MADEP’S VPH/EPH/APH Approach <ul><ul><li>January 1998 - FINAL Laboratory Standard Operating Procedures (SOPs). Methods for Volatile and Extractable Petroleum Hydrocarbons (VPH/EPH)* </li></ul></ul><ul><ul><li>October 1999 – Revisions to the Massachusetts Contingency Plan, 310 CMR 40.000 </li></ul></ul><ul><ul><li>February 2000 – Public Comment Draft 1.0 Method for Determination of Air-Phase Petroleum Hydrocarbons (APH)* </li></ul></ul><ul><ul><li>June 2001 – FINAL DRAFT Characterizing Risks Posed by Petroleum Contaminated Sites: Implementation of MADEP VPH/EPH Approach </li></ul></ul><ul><ul><li>* Footnote: </li></ul></ul><ul><ul><li> PDF downloadable files available at : </li></ul></ul><ul><ul><li>www.magnet.state.ma.us/dep/bwsc/pubs.htm </li></ul></ul>
    9. 9. INTRODUCTION AND BACKGROUND: History OF MADEP’S VPH/EPH/APH Approach <ul><li>OTHER KEY PUBLICATIONS </li></ul><ul><ul><li>Total Petroleum Hydrocarbon Criteria Working Group (TPHCWG) Series </li></ul></ul><ul><ul><ul><li>1998 - Volume 1. Analysis of Petroleum Hydrocarbons in Environmental Media </li></ul></ul></ul><ul><ul><ul><li>1998 - Volume 2. Composition of Petroleum Mixtures </li></ul></ul></ul><ul><ul><ul><li>1997 - Volume 3. Selection of Representative TPH Fractions Based on Fate and Transport Considerations </li></ul></ul></ul><ul><ul><ul><li>1997 - Volume 4. Development of Fraction Specific Reference Doses (RfDs) for Total Petroleum Hydrocarbons (TPH) </li></ul></ul></ul><ul><ul><ul><li>1998 - Volume 5. Human Health Risk-Based Evaluation of Petroleum Contaminated Sites: Implementation of the Working Group </li></ul></ul></ul>
    10. 10. INTRODUCTION AND BACKGROUND: History OF MADEP’S VPH/EPH/APH Approach <ul><ul><li>Total Petroleum Hydrocarbon Criteria Working Group (TPHCWG) Series (cont.) </li></ul></ul><ul><ul><ul><li>1997 - Volume 6. An Analytical Method for Petroleum Fate and Transport Fractions: The Direct Method </li></ul></ul></ul><ul><li>Footnote : TPHCWG publications available through: </li></ul><ul><li> </li></ul><ul><li>http://www.aehs.com/publications/catalog/contents/tph.htm </li></ul><ul><li>http://voyager.wpafb.af.mil </li></ul><ul><li>OTHER KEY PUBLICATIONS </li></ul><ul><ul><li>State of Wisconsin </li></ul></ul><ul><ul><ul><li>Studies of Sampling, Storage and Analysis of Soils Contaminated with Gasoline & Diesel * </li></ul></ul></ul><ul><li>* Footnote : Publication available as SCSSREP.ZIP at: </li></ul><ul><li>www.dnr.state.wi.us/org/aw/rr/errhw/index.htm </li></ul>
    11. 11. <ul><li>PETROLEUM FUELS </li></ul><ul><ul><li>Spills and releases of petroleum fuels are the leading source of environmental contamination in Massachusetts </li></ul></ul><ul><ul><li>Complex and highly variable nature of petroleum products pose site and risk characterization/management difficulties </li></ul></ul><ul><ul><li>Petroleum products are a mixture of hundreds of hydrocarbon compounds </li></ul></ul><ul><ul><li>Limitations in traditional “indicator only” (BTEX), whole product (gasoline, JP-5, JP-6) or TPH (C 4 to C 32 ) assessment approach </li></ul></ul>BACKGROUND
    12. 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. 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
    14. 14. <ul><li>GENERAL PETROLEUM HYDROCARBON OBSERVATIONS: </li></ul><ul><ul><li>Main composition: Aliphatic (alkanes, alkenes/alkynes, cycloalkanes), aromatic (BTEX) and polyaromatic (PAHs) hydrocarbon compounds + additives - analytical challenge </li></ul></ul><ul><ul><li>Key petroleum fractions are strongly associated with mobility in environmental media (aromatics >> aliphatics) </li></ul></ul><ul><ul><li>Aromatic hydrocarbons are more toxic than aliphatic compounds </li></ul></ul><ul><ul><li>Toxicity of aliphatic hydrocarbons inversely related to carbon number/molecular weight </li></ul></ul>BACKGROUND: Petroleum Chemistry/Toxicology
    15. 15. BACKGROUND: MADEP’S VPH/EPH/APH Approach Analytical Methods Toxicology NEW VPH/EPH/APH PETROLEUM SITE ASSESSMENT APPROACH Fate & Transport
    16. 16. <ul><li>TECHNICAL STRATEGY AND ISSUES </li></ul><ul><ul><li>Toxicology </li></ul></ul><ul><ul><ul><li>Divided broad chemical classes of petroleum hydrocarbons into subgroups/carbon fractions (alkanes, cycloalkanes, alkenes and aromatics) based on the number of carbon atoms, structure activity relationships, available toxicity information and common endpoints of toxicity </li></ul></ul></ul><ul><ul><ul><li>Identified individual carbon compounds with available toxicity values to use as “Surrogates” for the carbon fractions of interest identified </li></ul></ul></ul><ul><ul><ul><li>Findings used to supplement toxicity information for targeted analytes (1,3-Butadiene, MtBE, BTEX, PAHs) present in petroleum products </li></ul></ul></ul>BACKGROUND: Toxicology
    17. 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
    18. 18. BACKGROUND: Analytical Methods <ul><ul><li>MADEP developed analytical methods to quantify carbon fractions and target analytes in soil and groundwater in support of the risk characterization and management approach: </li></ul></ul><ul><ul><ul><li>Volatile Petroleum Hydrocarbons (VPH) </li></ul></ul></ul><ul><ul><ul><ul><li>C 5 - C 8 Aliphatics </li></ul></ul></ul></ul><ul><ul><ul><ul><li>C 9 - C 12 Aliphatics </li></ul></ul></ul></ul><ul><ul><ul><ul><li>C 9 - C 10 Aromatics </li></ul></ul></ul></ul><ul><ul><ul><li>Extractable Petroleum Hydrocarbons (EPH ) </li></ul></ul></ul><ul><ul><ul><ul><li>C 9 - C 18 Aliphatics </li></ul></ul></ul></ul><ul><ul><ul><ul><li>C 19 - C 36 Aliphatics </li></ul></ul></ul></ul><ul><ul><ul><ul><li>C 11 - C 22 Aromatics </li></ul></ul></ul></ul><ul><ul><ul><li>Targeted Analytes </li></ul></ul></ul><ul><ul><ul><ul><li>BTEX, MtBE, NAPTHs, PAHs </li></ul></ul></ul></ul>
    19. 19. BACKGROUND: Analytical Methods <ul><ul><li>MADEP developed analytical methods to quantify carbon fractions and target analytes in air in support of the risk characterization and management approach: </li></ul></ul><ul><ul><ul><li>Air-Phase Petroleum Hydrocarbons (APH) </li></ul></ul></ul><ul><ul><ul><ul><li>C 5 - C 8 Aliphatics </li></ul></ul></ul></ul><ul><ul><ul><ul><li>C 9 - C 12 Aliphatics </li></ul></ul></ul></ul><ul><ul><ul><ul><li>C 9 - C 10 Aromatics </li></ul></ul></ul></ul><ul><ul><ul><li>Targeted Analytes </li></ul></ul></ul><ul><ul><ul><ul><li>1,3-Butadiene, BTEX, MtBE, NAPTHs </li></ul></ul></ul></ul>
    20. 20. Universe of Petroleum Hydrocarbons (C 5 - C 36 +) C 5 C 9 C 12 C 5 - C 8 Aliphatics BTEX/MtBE/NAPTH/BD C 9 - C 10 Aromatics C 9 - C 12 Aliphatics C 5 C 9 - C 18 Aliphatics C 11 - C 22 Aromatics C 19 - C 36 Aliphatics 17 PAHs C 36 VPH/ APH EPH MADEP VPH/EPH/APH Guidance Document June 2001. RELATIONSHIP OF MADEP VPH/EPH/APH TO TPH AND GRO METHODS GRO TPH <ul><ul><li>c 12 </li></ul></ul>C 9 C 36 BACKGROUND: Analytical Methods
    21. 21. <ul><ul><ul><li>DEFINED AS PURGE AND TRAP, GC/PID/FID PROCEDURE </li></ul></ul></ul><ul><ul><ul><li>ALLOWS COLLECTIVE QUANTIFICATION </li></ul></ul></ul><ul><ul><ul><ul><ul><li>C 5 - C 8 and C 9 - C 12 Aliphatic Hydrocarbons 1 </li></ul></ul></ul></ul></ul><ul><ul><ul><ul><ul><li>C 9 - C 10 Aromatic Hydrocarbons 1 </li></ul></ul></ul></ul></ul><ul><ul><ul><li>ALLOWS INDIVIDUAL QUANTIFICATION </li></ul></ul></ul><ul><ul><ul><ul><ul><li>BTEX, Methyl-tertiary-butylether (MtBE) </li></ul></ul></ul></ul></ul><ul><ul><ul><ul><ul><li>Naphthalene (NAPTH) </li></ul></ul></ul></ul></ul><ul><ul><ul><li>SUITABLE FOR GASOLINE, MINERAL SPIRITS, AND CERTAIN </li></ul></ul></ul><ul><ul><ul><li>PETROLEUM NAPHTHAS </li></ul></ul></ul><ul><ul><ul><li>NOT SUITABLE FOR HYDROCARBONS > C12 (e.g., KEROSENE, JET FUEL, HEATING OILS, LUBRICATING OILS) </li></ul></ul></ul>1 Boiling Point Range Between 36 o C and 220 o C VPH ANALYTICAL METHOD OVERVIEW BACKGROUND: Analytical Methods
    22. 22. BACKGROUND: Analytical Methods <ul><ul><ul><li>REPORTING LIMITS </li></ul></ul></ul><ul><ul><ul><ul><ul><li>Collective Fractions: 2 to 10 mg/kg (soil) </li></ul></ul></ul></ul></ul><ul><ul><ul><ul><ul><li>(Aliphatic/Aromatic) 50 to 100 ug/L (water) </li></ul></ul></ul></ul></ul><ul><ul><ul><ul><ul><li>Target Analytes: 0 .1 to 0.2 mg/kg (soil) </li></ul></ul></ul></ul></ul><ul><ul><ul><ul><ul><li>(BTEX, MtBE, NAPTH) 1 to 10 ug/L (water) </li></ul></ul></ul></ul></ul><ul><ul><ul><li>Source : MADEP Method for the Determination of Volatile Petroleum Hydrocarbons, January 1998. </li></ul></ul></ul>VPH ANALYTICAL METHOD OVERVIEW (cont.)
    23. 23. BACKGROUND: Analytical Methods <ul><ul><ul><li>DEFINED AS SOLVENT EXTRACTION, FRACTIONATION, GC/FID PROCEDURE </li></ul></ul></ul><ul><ul><ul><li>ALLOWS COLLECTIVE QUANTIFICATION </li></ul></ul></ul><ul><ul><ul><ul><ul><li>C 9 - C 18 and C 19 - C 36 Aliphatic Hydrocarbons 1 </li></ul></ul></ul></ul></ul><ul><ul><ul><ul><ul><li>C 11 - C 22 Aromatic Hydrocarbons 1 </li></ul></ul></ul></ul></ul><ul><ul><ul><li>ALLOWS INDIVIDUAL QUANTIFICATION </li></ul></ul></ul><ul><ul><ul><ul><ul><li>17 PAH Target Analytes </li></ul></ul></ul></ul></ul><ul><ul><ul><li>SUITABLE FOR KEROSENE, FUEL OILS NOs. 2, 4, AND 6 DIESEL FUEL, JET FUEL AND CERTAIN LUBRICATING OILS </li></ul></ul></ul><ul><ul><ul><li>NOT SUITABLE FOR HYDROCARBONS < C9 or > C36 </li></ul></ul></ul>1 Boiling Point Range Between 150 o C and 500 o C EPH ANALYTICAL METHOD OVERVIEW
    24. 24. BACKGROUND: Analytical Methods <ul><ul><ul><li>REPORTING LIMITS </li></ul></ul></ul><ul><ul><ul><ul><ul><li>Collective Fractions: 2 to 10 mg/kg (soil) </li></ul></ul></ul></ul></ul><ul><ul><ul><ul><ul><li>(Aliphatic/Aromatic) 50 to 100 ug/L (water) </li></ul></ul></ul></ul></ul><ul><ul><ul><ul><ul><li>Target Analytes: 0.5 to 1 mg/kg (soil) </li></ul></ul></ul></ul></ul><ul><ul><ul><ul><ul><li>(PAHs) 1 to 5 ug/L (water) </li></ul></ul></ul></ul></ul><ul><ul><ul><li>Source : MADEP Method for the Determination of Extractable Petroleum Hydrocarbons, January 1998. </li></ul></ul></ul>EPH ANALYTICAL METHOD OVERVIEW (cont.)
    25. 25. <ul><ul><ul><li>GC/MS PROCEDURE FOR AIR OR SOIL GAS SAMPLES </li></ul></ul></ul><ul><ul><ul><li>ALLOWS COLLECTIVE QUANTIFICATION </li></ul></ul></ul><ul><ul><ul><ul><ul><li>C 5 - C 8 and C 9 - C 12 Aliphatic Hydrocarbons 1 </li></ul></ul></ul></ul></ul><ul><ul><ul><ul><ul><li>C 9 - C 10 Aromatic Hydrocarbons 1 </li></ul></ul></ul></ul></ul><ul><ul><ul><li>ALLOWS INDIVIDUAL QUANTIFICATION </li></ul></ul></ul><ul><ul><ul><ul><ul><li>1,3-Butadiene, BTEX </li></ul></ul></ul></ul></ul><ul><ul><ul><ul><ul><li>Methyl-tertiary-butylether (MtBE) </li></ul></ul></ul></ul></ul><ul><ul><ul><ul><ul><li>Naphthalenes (NAPTHs) </li></ul></ul></ul></ul></ul><ul><ul><ul><li>SUITABLE FOR GASOLINE, MINERAL SPIRITS (Volatile fractions), KEROSENE, #2/DIESEL FUEL OIL, JET FUELS, AND CERTAIN PETROLEUM NAPHTHAS </li></ul></ul></ul><ul><ul><ul><li>NOT SUITABLE FOR PARTICULATE-PHASE CONCENTRATIONS OF HEAVIER MOLECULAR WEIGHT HYDROCARBONS </li></ul></ul></ul>BACKGROUND: Analytical Methods APH ANALYTICAL METHOD OVERVIEW 1 Approximate Boiling Point Range Between 28 o C and 245 o C
    26. 26. BACKGROUND: Analytical Methods <ul><ul><ul><li>REPORTING LIMITS </li></ul></ul></ul><ul><ul><ul><ul><ul><li>Collective Fractions: 25 to 100 µg/m 3 (air/soil gas) </li></ul></ul></ul></ul></ul><ul><ul><ul><ul><ul><li>(Aliphatic/Aromatic) </li></ul></ul></ul></ul></ul><ul><ul><ul><ul><ul><li>Target Analytes: 2 to 20 µg/m 3 (air/soil gas) </li></ul></ul></ul></ul></ul><ul><ul><ul><ul><ul><li>(1,3-BD, BTEX, MtBE, NAPTH) </li></ul></ul></ul></ul></ul><ul><ul><ul><li>Source : MADEP Method for the Determination of Air-Phase Petroleum Hydrocarbons (APH), February 2000. </li></ul></ul></ul>APH ANALYTICAL METHOD OVERVIEW (cont.)
    27. 27. BACKGROUND: FATE & TRANSPORT CONTAMINATED SOIL GROUNDWATER AMBIENT/ INDOOR AIR <ul><li>Petroleum Constituents Likely to Volatilize: </li></ul><ul><li>Alkanes (butane, heptane, pentane) </li></ul><ul><li>Aromatics (benzene, ethylbenzene, </li></ul><ul><li>toluene, xylenes, naphthalene, </li></ul><ul><li>2-methylnaphthalene) </li></ul><ul><li>MtBE, 1-3 Butadiene </li></ul><ul><li>Petroleum Constituents Likely to Remain: </li></ul><ul><li>High molecular weight alkanes (decane) </li></ul><ul><li>High molecular weight aromatic </li></ul><ul><li>and polyaromatics (benzo(a)pyrene ) </li></ul><ul><li>Petroleum Constituents Likely to Leach: </li></ul><ul><li>Naphthalene, 2-methylnaphthalene </li></ul><ul><li>C 9 - C 10 and C 11 - C 22 Aromatics </li></ul>
    28. 28. BACKGROUND: Fate and Transport <ul><li>FATE AND TRANSPORT </li></ul><ul><ul><li>Significant variability in behavior of petroleum hydrocarbons in the environment </li></ul></ul><ul><ul><li>Key petroleum fractions are strongly associated with mobility in environmental media (aromatics >> aliphatics) </li></ul></ul><ul><ul><li>Behavior dictated by compound or fraction’s physical-chemical properties </li></ul></ul><ul><ul><li>MADEP identified fate and transport parameters for VPH/EPH/APH approach based on information compiled by the TPHWCG (Volume 3, 1997) </li></ul></ul>
    29. 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 *
    30. 30. BACKGROUND: MCP Risk Characterization Methods <ul><li>DEVELOPMENT OF MCP NUMERICAL STANDARDS * </li></ul><ul><ul><li>MCP Groundwater Standards : </li></ul></ul><ul><ul><ul><li>GW-1 addresses health effects, ceiling concentration, odor threshold, background and PQL (Drinking Water - MCL; MMCL) </li></ul></ul></ul><ul><ul><ul><li>GW-2 addresses health effects, ceiling concentration, odor threshold, fate and transport, background and PQL (Indoor Air - H x 0.1,0.01; 5E-04 DAT) </li></ul></ul></ul><ul><ul><ul><li>GW-3 addresses freshwater and marine toxicity, dilution and attenuation, ceiling concentration, background and PQL (Surface Waters - DAT x WQG) </li></ul></ul></ul><ul><ul><li>* Sources : MADEP Background Document for Development of MCP Numerical Standards, April 1994; MADEP October, 1997; MADEP - VPH/EPH Spring Training 1997. </li></ul></ul><ul><ul><li> MADEP May 2001 “Proposed MCP Soil and Groundwater Standards.” </li></ul></ul>
    31. 31. BACKGROUND: MCP Risk Characterization Methods <ul><ul><li>MCP Soil Standards address health effects, ceiling concentration, background, PQL, direct contact, leaching: </li></ul></ul><ul><ul><ul><li>S-1 (Residential - HF/HI focus - surficial 0<= 3 ft., unpaved) </li></ul></ul></ul><ul><ul><ul><li>S-2 (Work environment/passive recreational setting - </li></ul></ul></ul><ul><ul><ul><li>HF/LI focus - surficial; potentially accessible 3<= 15ft. </li></ul></ul></ul><ul><ul><ul><li>unpaved or 0<= 15 ft. paved ) </li></ul></ul></ul><ul><ul><ul><li>S-3 (Short, intense work environment - LF/HI focus - surficial, potentially accessible and isolated subsurface > 15 ft. or beneath footprint of building or permanent structure) </li></ul></ul></ul><ul><ul><li>Abbreviations : H = High; L = Low; F = Frequency; I = Intensity </li></ul></ul>
    32. 32. BACKGROUND: MCP Risk Characterization Methods <ul><ul><li>Upper Concentration Limits (UCLs)* </li></ul></ul><ul><ul><ul><li>Soil UCLs derived from highest Soil Standard (S-X/GW-X) x 10, and lowest value of product or ceiling concentration. Capped at 10,000 mg/kg or 1%. Exceptions for Risk Management at 20,000 mg/kg (C 9 - C 12 , C 9 - C 18 and C 19 - C 36 Aliphatics) </li></ul></ul></ul><ul><ul><ul><li>Groundwater UCLs derived from highest Groundwater Standard (GW-X) x 10 and lowest value of product or ceiling concentration. Capped at 100,000 ug/L or 0.01% and adjusted for solubility. Exception for Risk Management (C 9 - C 10 Aromatics) </li></ul></ul></ul><ul><ul><ul><li>NAPL UCL set at  0.5 in. NAPL in groundwater monitoring well. Issue with Apparent vs. Actual thickness of NAPL layer. </li></ul></ul></ul><ul><ul><ul><li>* Footnote : UCLs used to evaluate risk of harm to Public Welfare and the Environment (310 CMR 40.0996). See MADEP June 2001 VPH/EPH/APH Guidance for NAPL details. </li></ul></ul></ul>
    33. 33. BACKGROUND: MCP Risk Characterization Methods <ul><li>Reportable Concentrations (RCs)* </li></ul><ul><ul><li>Groundwater: </li></ul></ul><ul><ul><ul><li>RCGW-1 lowest GW-X value (Current and potential drinking water resources) </li></ul></ul></ul><ul><ul><ul><li>RCGW-2 lowest GW-2 or GW-3 value (Other than above) </li></ul></ul></ul><ul><ul><li>Soil: </li></ul></ul><ul><ul><ul><li>RCS-1 lowest S-1/GW-1, S-1/GW-2, S-1/GW-3, S-2/GW-1 or S-3/GW-1 value (Residential homes and zones, schools, parks) </li></ul></ul></ul><ul><ul><ul><li>RCS-2 lowest S-2/GW-2, S-2/GW-3, S-3/GW-2 or S-3/GW-3 value (Other than above) </li></ul></ul></ul><ul><li>* Footnote : RCs used to determine MCP notification requirements for OHM release, pursuant to 310 CMR 40.0300. </li></ul>
    34. 34. BACKGROUND: MCP Risk Characterization Methods <ul><li>THREE MCP RISK CHARACTERIZATION METHODS </li></ul><ul><ul><li>Selection of Method: 310 CMR 40.0942* </li></ul></ul><ul><ul><ul><li>Method 1 [310 CMR 40.0970] </li></ul></ul></ul><ul><ul><ul><li>Method 2 [310 CMR 40.0980] </li></ul></ul></ul><ul><ul><ul><li>Method 3 [310 CMR 40.0990] </li></ul></ul></ul><ul><ul><li>*Footnote : See also MADEP Guidance for Disposal Site Risk Characterization, BWSC & ORS. Interim Final Policy BWSC/ORS-95-141, July 1995 and 1996 Update, and MADEP June 2001 VPH/EPH/APH Guidance Document. </li></ul></ul>
    35. 35. BACKGROUND: MCP Risk Characterization Methods <ul><li>METHOD 1 </li></ul><ul><ul><li>Comparison of Site CoC* Concentrations (Soil and/or Groundwater Only ) to MCP Soil and/or Groundwater Standards </li></ul></ul><ul><ul><li>Protective of Human Health, Public Welfare and the Environment (Not Safety)** </li></ul></ul><ul><ul><li>Not Applicable to Other Media (e.g., Air, Sediments) or if OHM present in soil (0 - 2 ft.) can bioaccumulate </li></ul></ul><ul><ul><li>Time/Cost Effective (“Look-Up” Table Approach) </li></ul></ul><ul><ul><li>Footnote: * CoC – Compound of Concern </li></ul></ul><ul><ul><li>** Characterization of Risk to Safety - see 310 CMR 40.0960 </li></ul></ul>
    36. 36. BACKGROUND: MCP Risk Characterization Methods <ul><li>METHOD 2 </li></ul><ul><ul><li>Create Soil and/or Groundwater Standards for OHM* when no Method 1 Standards are available </li></ul></ul><ul><ul><li>Modification of Method 1 Standards to Address Site-Specific Fate and Transport Considerations </li></ul></ul><ul><ul><li>Protective of Human Health, Public Welfare and the Environment (Not Safety)* </li></ul></ul><ul><ul><li>Not Applicable to Other Media (e.g., Air, Sediments) or if OHM present in soil (0 - 2 ft.) can bioaccumulate </li></ul></ul><ul><ul><li>Footnote: * OHM – Oil and Hazardous Material </li></ul></ul><ul><ul><li>** Characterization of Risk to Safety - see 310 CMR 40.0960 </li></ul></ul>
    37. 37. BACKGROUND: MCP Risk Characterization Methods <ul><li>METHOD 3 </li></ul><ul><ul><li>Used to Address OHM Exposures in all media (Soil, Groundwater, Air, Surface Water, Sediments) </li></ul></ul><ul><ul><li>Site-Specific Evaluation of Risk to Human Health, Safety, Public Welfare and the Environment: </li></ul></ul><ul><ul><ul><li>Human Health - Cumulative receptor risk analysis using site-specific exposure assumptions; comparison of CoC EPC* to Applicable or Suitably Analogous Health Standards. </li></ul></ul></ul><ul><ul><ul><li>Safety - Risk of physical harm or bodily injury; comparison of EPC* to Suitably Analogous Safety Standards. </li></ul></ul></ul><ul><ul><ul><li>Public Welfare - Odors; loss of property values; unilateral restrictions; degradation of resources; comparison of CoC EPC* to UCLs. </li></ul></ul></ul><ul><ul><li>Footnote : *EPC - Exposure Point Concentration </li></ul></ul>
    38. 38. BACKGROUND: MCP Risk Characterization Methods <ul><li>Site-Specific Evaluation of Risk to Human Health, Safety, Public Welfare and the Environment (cont.) : </li></ul><ul><ul><li>Environment </li></ul></ul><ul><ul><ul><li>Stage I Environmental Screening - Physical evidence; receptor identification; exposure pathway analysis; comparison of CoC EPC* to Applicable or Suitably Analogous Standards, Criteria, or Secondary Benchmark Values. </li></ul></ul></ul><ul><ul><ul><li>Stage II Environmental Risk Characterization - Potential for and/or evidence of ecological harm; identification of indicator species; comparison of CoC EPC* to Applicable or Suitably Analogous Standards, Criteria, or Secondary Benchmark Values; toxicity testing; field studies. </li></ul></ul></ul>
    39. 39. BACKGROUND: MCP Risk Characterization Methods <ul><li>METHOD 3 (cont.) </li></ul><ul><ul><li>MADEP Optional Draft #2 Diesel/Fuel Oil Residential Shortform for screening risks (MADEP December 1997, MADEP June 2001) </li></ul></ul><ul><ul><ul><li>Addresses : </li></ul></ul></ul><ul><ul><ul><ul><li>VPH (C 5 -C 8 and C 9 -C 12 aliphatics; C 9 -C 10 aromatics) </li></ul></ul></ul></ul><ul><ul><ul><ul><li>EPH (C 9 -C 18 and C 19 -C 36 aliphatics; and C 11 -C 22 aromatics) </li></ul></ul></ul></ul><ul><ul><ul><ul><li>BTEX, NAPTH, 2-MeNAPTH, acenaphthene and phenanthrene </li></ul></ul></ul></ul><ul><ul><ul><li>Limitations : </li></ul></ul></ul><ul><ul><ul><ul><li>Standardized exposure assumptions and toxicological profiles </li></ul></ul></ul></ul><ul><ul><ul><ul><li>Does not address heavier fuel oils or all potential gasoline constituents </li></ul></ul></ul></ul><ul><ul><ul><ul><li>Risk of harm to Safety, Public Welfare, and the Environment not addressed </li></ul></ul></ul></ul><ul><ul><ul><ul><li>Some toxicity values require updating </li></ul></ul></ul></ul>
    40. 40. FIELD SAMPLING & ANALYSIS <ul><li>ENVIRONMENTAL SAMPLE COLLECTION AND ANALYSIS </li></ul><ul><ul><li>Regulatory Framework - 310 CMR 40.0017* </li></ul></ul><ul><ul><li>Data must be scientifically valid and defensible </li></ul></ul><ul><ul><li>Soil Gas screening techniques vs. field and laboratory analytical approach </li></ul></ul><ul><ul><li>Documentation required for: </li></ul></ul><ul><ul><ul><li>Sampling Procedures </li></ul></ul></ul><ul><ul><ul><li>Analytical Methods </li></ul></ul></ul><ul><ul><ul><li>Method Performance </li></ul></ul></ul><ul><ul><ul><li>Data validation </li></ul></ul></ul><ul><ul><li>*Footnote : See also MADEP January 1998 and June 2001. </li></ul></ul>
    41. 41. SCREENING PROCEDURES <ul><li>VPH/EPH ANALYTICAL SCREENING TECHNIQUES </li></ul><ul><li>Technique Range Application Limitations Recommendations* </li></ul><ul><li>PID/FID VPH Gasoline Not for heavy For gasoline, HS > </li></ul><ul><li>Headspace Kerosene mineral/lube/fuel 100 ppm = all VPH </li></ul><ul><li> Soil & GW oils or weathered fractions < 100ug/g, </li></ul><ul><li>diesel/#2 fuel oil except in clay or organic </li></ul><ul><li> soils </li></ul><ul><li>PID/FID VPH Soil gas/ Low flow rates Gasoline - assume </li></ul><ul><li>Soil Gas Indoor air High moisture PID = individual C 5 -C 8 </li></ul><ul><li> (>GW-2) VOCs > 150 ppm and C 9 -C 12 aliphatic </li></ul><ul><li> and C 11 -C 22 aromatic </li></ul><ul><li> concentrations. </li></ul><ul><li> Fuel Oil - assume PID = </li></ul><ul><li> individual C 9 -C 18 aliphatic </li></ul><ul><li> and C 11 -C 22 aromatic concs. </li></ul><ul><li> FID - aliphatics only. </li></ul>
    42. 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. 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
    44. 44. SCREENING PROCEDURES <ul><li>SINCE THE TOXICITY OF AROMATIC FRACTIONS>>ALIPHATICS: </li></ul><ul><ul><li>Better to use screening methods that accurately quantify collective aromatic hydrocarbons, and estimate aliphatics, than vice versa. </li></ul></ul>
    45. 45. SCREENING PROCEDURES <ul><li>SMALL SITES (e.g., residential USTs) </li></ul><ul><ul><li>Screening procedures used: </li></ul></ul><ul><ul><ul><li>to direct soil removal </li></ul></ul></ul><ul><ul><ul><li>identify areas for assessment and/or confirmatory VPH/EPH analysis </li></ul></ul></ul><ul><li>LARGER SITES </li></ul><ul><ul><li>Screening procedures used as a substitute and complement to VPH/EPH analysis </li></ul></ul><ul><ul><li>Example : For a budget of $1500, could take 8 EPH samples ($150) and 8 - 20 field screening samples, rather than 10 EPH samples. </li></ul></ul>
    46. 46. SCREENING PROCEDURES: VPH/EPH <ul><li>MINIMUM NUMBER OF VPH/EPH SAMPLES: </li></ul><ul><ul><li>Required to characterize the nature and extent of petroleum contamination </li></ul></ul><ul><ul><li>Provide confidence in the screening data </li></ul></ul><ul><ul><li>Provide an adequate data set for the risk characterization </li></ul></ul><ul><ul><li>- IS SITE-SPECIFIC </li></ul></ul>
    47. 47. SCREENING PROCEDURES <ul><li>KEY SITE-SPECIFIC VARIABLES ARE: </li></ul><ul><ul><li>Heterogeneity of site conditions (stratigraphic and </li></ul></ul><ul><ul><li>microbiological) </li></ul></ul><ul><ul><li>Source vs. migration areas </li></ul></ul><ul><ul><li>Degradability of petroleum products </li></ul></ul>
    48. 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
    49. 49. SCREENING PROCEDURES: VPH/EPH <ul><li>MADEP VPH/EPH RECOMMENDED SCREENING </li></ul><ul><li>SOIL AND GROUNDWATER SAMPLING * </li></ul><ul><li>PETROLEUM PRODUCT </li></ul><ul><li>GASOLINE </li></ul><ul><li>FRESH DIESEL/#2 FUEL OIL </li></ul><ul><li>WEATHERED DIESEL/#2 FUEL OIL 2,3 </li></ul><ul><li>#3 - #6 FUEL OILS 3 </li></ul><ul><li>WASTE (CRANKCASE) OIL </li></ul><ul><li>JET FUEL JP-4/JP-8 </li></ul><ul><li>JET FUEL Jet A/KEROSENE 3 </li></ul><ul><li>MINERAL/DIELECTRIC OILS 3 </li></ul><ul><li>UNKNOWN OILS/SOURCES </li></ul><ul><li>* MADEP VPH/EPH/APH Guidance June 2001; 2 Soil/GW Headspace TOV < 100 ppmv; </li></ul><ul><li>3 VPH Recommended for GW-1 . </li></ul>X X X X X X X X X X X X VPH EPH
    50. 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. 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
    52. 52. VPH/EPH CAVEATS <ul><li>SPLIT SAMPLES </li></ul><ul><ul><li>For split samples analyzed by both VPH and EPH methods, not necessary to quantify VPH value for C 9 -C 12 Aliphatics - already accounted for in C 9 -C 18 aliphatics in EPH test method </li></ul></ul><ul><ul><li>In general, EPH method provides more accurate data for this aliphatic fraction </li></ul></ul><ul><li>VPH TESTING </li></ul><ul><ul><li>Eliminate need based upon VOC screening </li></ul></ul><ul><ul><li>Recommended for GW-1 Resource Areas and drinking water wells impacted by any petroleum products </li></ul></ul>
    53. 53. VPH/EPH CAVEATS <ul><li>FILTRATION </li></ul><ul><ul><li>May be appropriate for EPH groundwater samples under certain conditions. Do not filter samples from potable water supplies, nor generally wells outside the “source area” of release. </li></ul></ul><ul><li>ETHANOL </li></ul><ul><ul><li>MCP hazardous material – oxygenate replacement for MtBE. If use is known or suspected (especially for gasoline contamination of groundwater where MtBE is found) need to test for ethanol. </li></ul></ul><ul><ul><li>Ethanol’s high biochemical oxygen demand can readily deplete oxygen (and nutrient levels) in area of contamination, which, along with its co-solvency, can aid dispersion of contaminant plume. </li></ul></ul>
    54. 54. VPH/EPH CAVEATS <ul><li>USE OF TPH DATA </li></ul><ul><ul><li>Compare directly to TPH RCs and Cleanup Standards (now based on EPH C 11 -C 22 aromatic fraction - worst case) </li></ul></ul><ul><ul><li>Old and new TPH/screening data used indirectly by “converting” TPH value into EPH fractional concentrations based upon: </li></ul></ul><ul><ul><ul><ul><li>chemistry/weathering of release </li></ul></ul></ul></ul><ul><ul><ul><ul><li>available VPH/EPH data </li></ul></ul></ul></ul><ul><ul><ul><ul><li>default compositional assumptions </li></ul></ul></ul></ul>
    55. 55. <ul><li>MADEP RECOMMENDED TPH COMPOSITIONAL ASSUMPTIONS FOR SOIL * </li></ul><ul><li>PETROLEUM </li></ul><ul><li>PRODUCT </li></ul><ul><li>DIESEL/#2 & 60% 40% 0% </li></ul><ul><li>CRANKCASE </li></ul><ul><li>#3- #6 FUEL OIL 70% 30% 0% </li></ul><ul><li>KEROSENE & JET FUEL 30% 70% 0% </li></ul><ul><li>MINERAL OIL/ 20% 40% 40% </li></ul><ul><li>DIELECTRIC FLUID </li></ul><ul><li>UNKNOWN OIL 100% 0% 0% </li></ul><ul><li>* MADEP VPH/EPH/APH Guidance June 2001 </li></ul>VPH/EPH CAVEATS C 11 -C 22 Aromatics C 19 -C 36 Aliphatics C 9 -C 18 Aliphatics
    56. 56. VPH/EPH CAVEATS <ul><li>MADEP RECOMMENDED COMPOSITIONAL ASSUMPTIONS FOR GROUNDWATER * </li></ul><ul><li>TPH DATA </li></ul><ul><ul><li>Since most water soluble fractions of petroleum products are aromatics, assume all non-targeted PAHs to be C 11 -C 22 Aromatics (i.e., subtract out targeted PAHs such as NAPTH) </li></ul></ul><ul><li>GASOLINE RANGE ORGANIC DATA </li></ul><ul><ul><li>Assume all non-BTEX, MtBE hydrocarbons to be the most conservative VPH fractional standard of interest, usually </li></ul></ul><ul><ul><li>C 9 -C 10 aromatics (i.e., subtract out targeted VOCs) </li></ul></ul><ul><ul><li>* MADEP VPH/EPH/APH Guidance June 2001 </li></ul></ul>
    57. 57. VPH/EPH CAVEATS <ul><li>USE OF ASSUMPTIONS </li></ul><ul><ul><li>Unless it can be demonstrated that assumptions used represent “worst case,” then it is not considered appropriate to use them to evaluate risks for Critical Exposure Pathways (e.g., drinking water wells; indoor air). </li></ul></ul><ul><li>COMPOSITIONAL VARIABILITY </li></ul><ul><ul><li>Fate and transport processes influence chemical composition of petroleum contamination upon release to the environment; hence one VPH/EPH sample is not usually adequate to define aliphatic and aromatic percentages across an entire site </li></ul></ul>
    58. 58. VPH/EPH CAVEATS <ul><li>COMPOSITIONAL VARIABILITY SOLUTIONS </li></ul><ul><ul><li>Easy Way </li></ul></ul><ul><ul><ul><li>Conduct VPH/EPH analyses on all samples </li></ul></ul></ul><ul><ul><li>Harder Way </li></ul></ul><ul><ul><ul><li>Collect VPH/EPH data from key areas and critical exposure pathways </li></ul></ul></ul><ul><ul><ul><li>Supplement with screening/TPH data </li></ul></ul></ul><ul><ul><ul><li>Evaluate fate and transport characteristics of petroleum product, VPH/EPH data and default conservative compositional findings </li></ul></ul></ul><ul><ul><ul><li>Determine conservative fractional composition for Risk Assessment </li></ul></ul></ul>
    59. 59. DATA VALIDATION <ul><li>DATA VALIDATION FOR VPH/EPH/APH METHODS </li></ul><ul><ul><li>Samples collected and received by laboratory in appropriate containers with correct preservation - Chain-of-Custody completed </li></ul></ul><ul><ul><li>Trip Blank and Method Blank are “Below Reporting Limits” (BRLs) </li></ul></ul><ul><ul><li>Laboratory Control Sample recoveries for duplicates, fortified blanks and matrix standards and QC surrogate standards are within QC Limits </li></ul></ul><ul><ul><li>Sample QC Surrogate recoveries are within QC Limits </li></ul></ul><ul><ul><li>VPH/EPH range concentrations have been adjusted </li></ul></ul><ul><ul><li>Sample Reporting Limits are within acceptable ranges </li></ul></ul>
    60. 60. DATA VALIDATION <ul><ul><ul><li>VPH </li></ul></ul></ul><ul><ul><ul><ul><li>Collective Fractions: 2 to 10 mg/kg (soil) </li></ul></ul></ul></ul><ul><ul><ul><ul><li>(Aliphatic/Aromatic) 50 to 100 ug/L (water) </li></ul></ul></ul></ul><ul><ul><ul><ul><li>Target Analytes: 0 .1 to 0.2 mg/kg (soil) </li></ul></ul></ul></ul><ul><ul><ul><ul><li>(BTEX, MtBE, NAPTH) 1 to 10 ug/L (water) </li></ul></ul></ul></ul><ul><ul><ul><li>EPH </li></ul></ul></ul><ul><ul><ul><ul><li>Collective Fractions: 2 to 10 mg/kg (soil) </li></ul></ul></ul></ul><ul><ul><ul><ul><li>(Aliphatic/Aromatic) 50 to 100 ug/L (water) </li></ul></ul></ul></ul><ul><ul><ul><ul><li>Target Analytes: 0.5 to 1 mg/kg (soil) </li></ul></ul></ul></ul><ul><ul><ul><ul><li>(PAHs) 1 to 5 ug/L (water) </li></ul></ul></ul></ul><ul><ul><ul><li>Source : MADEP Method for the Determination of Volatile Petroleum Hydrocarbons, January 1998. </li></ul></ul></ul><ul><ul><li>MADEP ACCEPTABLE REPORTING LIMITS </li></ul></ul>
    61. 61. DATA VALIDATION <ul><ul><ul><li>APH </li></ul></ul></ul><ul><ul><ul><ul><li>Collective Fractions: 25 to 100 µg/m 3 (air/soil gas) </li></ul></ul></ul></ul><ul><ul><ul><ul><li>(Aliphatic/Aromatic) </li></ul></ul></ul></ul><ul><ul><ul><ul><li>Target Analytes: 2 to 20 µg/m 3 (air/soil gas) </li></ul></ul></ul></ul><ul><ul><ul><ul><li>(BTEX, MtBE, NAPTHs) </li></ul></ul></ul></ul><ul><ul><ul><li>Source : MADEP Method for the Determination of Air-Phase Petroleum Hydrocarbons, February 2000 </li></ul></ul></ul><ul><ul><li>MADEP ACCEPTABLE REPORTING LIMITS </li></ul></ul>
    62. 62. EXPOSURE POINT CONCENTRATIONS <ul><li>REPORTABLE CONCENTRATIONS (310 CMR 40.0350) </li></ul><ul><ul><li>Comparison of measured OHM levels to RCs. If OHM level is = or > RC, MCP notification required (310 CMR 40.0300) </li></ul></ul><ul><ul><ul><li>Gasoline, Kerosene, Aviation Fuel - use RCs for applicable aliphatic and aromatic hydrocarbon fractions listed in 310 CMR 40.1600 </li></ul></ul></ul><ul><ul><ul><li>For other oils - use RCs for TPH or the applicable aliphatic and aromatic hydrocarbon fractions listed in 310 CMR 40.1600 </li></ul></ul></ul><ul><ul><li>Note : Notification not required solely on basis of TPH RC, if OHM level does not = or > RC for applicable aliphatic and aromatic hydrocarbon fractions listed in 310 CMR 40.1600 </li></ul></ul>
    63. 63. EXPOSURE POINT CONCENTRATIONS <ul><li>SOIL </li></ul><ul><ul><li>Hot Spot </li></ul></ul><ul><ul><ul><li>Discrete area where OHM level is > x 100 that of the surrounding area </li></ul></ul></ul><ul><ul><ul><li>Discrete area where OHM level difference is > x10 but less than 100 fold that of surrounding area unless : </li></ul></ul></ul><ul><ul><ul><ul><li>no evidence that discrete area would be associated with </li></ul></ul></ul></ul><ul><ul><ul><ul><li>any greater exposure potential than that of surrounding area </li></ul></ul></ul></ul><ul><ul><ul><ul><li>site-specific considerations (e.g., background variability, OHM distribution) indicate otherwise </li></ul></ul></ul></ul><ul><ul><li>VPH/EPH Considerations for Hot Spot Evaluation </li></ul></ul><ul><ul><ul><li>Each VPH/EPH fraction treated as a single OHM value </li></ul></ul></ul>
    64. 64. EXPOSURE POINT CONCENTRATIONS <ul><li>SOIL (cont.) </li></ul><ul><ul><li>Averages </li></ul></ul><ul><ul><ul><li>Arithmetic soil levels, using one-half the detection limit for non-detects for averaging purposes - appropriate for evaluation of random, areal exposures outside of hot spots </li></ul></ul></ul><ul><ul><ul><li>Pursuant to 310 CMR 40.0926(3)(b)(2)(a) for averaging > 25% of OHM data points may exceed applicable MCP Soil Standard, and no value can be greater than x 10 the Standard </li></ul></ul></ul>
    65. 65. EXPOSURE POINT CONCENTRATIONS <ul><li>GROUNDWATER </li></ul><ul><ul><li>Monitoring wells - considered individual exposure points - use of maximum or average concentrations depends on exposure scenario: </li></ul></ul><ul><ul><ul><li>Maximum or average OHM conc. of most recent quarterly round of monitoring - GW-1 area </li></ul></ul></ul><ul><ul><ul><li>Average OHM conc., if monitoring well zones of influence demonstrated to overlap </li></ul></ul></ul>
    66. 66. EXPOSURE POINT CONCENTRATIONS <ul><li>GROUNDWATER (cont.) </li></ul><ul><ul><li>Modeled EPC - based on fate and transport considerations, for impact on downgradient GW-1 resource areas 1 : </li></ul></ul><ul><ul><ul><li>MADEP Default Dilution Factor (DF) for VOCs = x 0.1 </li></ul></ul></ul><ul><ul><ul><li>Dissolved VPH/EPH Fractions 1,2,3 </li></ul></ul></ul><ul><ul><ul><ul><li>10 ft. x 10 ft. Source Area, DF = 177 (distance in feet) -1.455 , r 2 =0.099 </li></ul></ul></ul></ul><ul><ul><ul><ul><li>30 ft. x 30 ft. Source Area, DF = 303 (distance in feet) -1.365 , r 2 =0.099 </li></ul></ul></ul></ul><ul><ul><ul><ul><li>60 ft. x 60 ft. Source Area, DF = 237 (distance in feet) -1.214 , r 2 =0.099 </li></ul></ul></ul></ul><ul><ul><li>Source : 1 MADEP June 2001 – based on Domenico and Robbins (1985) transport model. 2 Assumptions: distance to resource > 100 ft.; depth of source area < 6 ft.; groundwater flow limited to overburden aquifer; no preferential flow paths; </li></ul></ul><ul><ul><li>3 OHM concentration ≤ UCL. </li></ul></ul>
    67. 67. EXPOSURE POINT CONCENTRATIONS <ul><li>SURFACE WATER </li></ul><ul><ul><li>Sampled Concentration </li></ul></ul><ul><ul><li>Modeled EPC - based on fate and transport considerations for groundwater to surface water discharge: 1 </li></ul></ul><ul><ul><ul><li>MADEP Default Dilution Factor (DF) for VOCs = x 0.1 </li></ul></ul></ul><ul><ul><ul><li>Dissolved VPH/EPH Fractions 1,2,3 </li></ul></ul></ul><ul><ul><ul><ul><li>10 ft. x 10 ft. Source Area, DF = 177 (distance in feet) -1.455 , r 2 =0.099 </li></ul></ul></ul></ul><ul><ul><ul><ul><li>30 ft. x 30 ft. Source Area, DF = 303 (distance in feet) -1.365 , r 2 =0.099 </li></ul></ul></ul></ul><ul><ul><ul><ul><li>60 ft. x 60 ft. Source Area, DF = 237 (distance in feet) -1.214 , r 2 =0.099 </li></ul></ul></ul></ul><ul><ul><ul><li>Note: Additional DF of x 0.1 applied to account for groundwater/surface water mixing </li></ul></ul></ul><ul><ul><li>Source : 1 MADEP June 2001 – based on Domenico and Robbins (1985) transport model. 2 Assumptions: distance to surface water > 100 ft.; depth of source area < 6 ft.; groundwater flow limited to overburden aquifer; no preferential flow paths; </li></ul></ul><ul><ul><li>3 OHM concentration ≤ UCL. </li></ul></ul>
    68. 68. EXPOSURE POINT CONCENTRATIONS <ul><li>AIR* </li></ul><ul><ul><li>Acute Exposures ( < 24 hrs) </li></ul></ul><ul><ul><ul><li>1-Hour grab sample (qualitative / gross screening) </li></ul></ul></ul><ul><ul><ul><li>2-24 hour sample (comparison to guidelines / standards) </li></ul></ul></ul><ul><ul><li>Subchronic Exposures (2 weeks to 7 years) </li></ul></ul><ul><ul><ul><li>Time-weighted sample (2-24 hours; seasonal) </li></ul></ul></ul><ul><ul><ul><li>Passive sample (3-4 weeks) </li></ul></ul></ul><ul><ul><li>Chronic Exposures ( > 7 years ) </li></ul></ul><ul><ul><ul><li>Time-weighted sample (2-24 hours; seasonal) </li></ul></ul></ul><ul><ul><ul><li>Badge sample (several weeks) </li></ul></ul></ul><ul><ul><li>* Source: MADEP Indoor Air Sampling and Evaluation Guide, Draft January 2000 </li></ul></ul>
    69. 69. EXPOSURE POINT CONCENTRATIONS * Source: MADEP Indoor Air Sampling and Evaluation Guide, Draft January 2000 <ul><li>AIR* </li></ul>
    70. 70. EXPOSURE POINT CONCENTRATIONS <ul><li>AIR (cont.) </li></ul><ul><ul><li>Modeled - Target Compounds (VOCs, NAPTH, 2-MeNAPTH) </li></ul></ul><ul><ul><ul><li>Soil </li></ul></ul></ul><ul><ul><ul><ul><li>Soil to soil gas, using RTI model (EPA-453/R-94-08A, November 1994. Air Emissions Models for Waste and Wastewater) or Johnson & Ettinger (Heuristic Model for Predicting the Intrusion Rate of Contaminant Vapors into Buildings. Env. Sci. Technol., 1445-1452, 1991 + errata) </li></ul></ul></ul></ul><ul><ul><ul><ul><li>Soil gas to indoor air through permeable slab (Gas Research Institute. Management of Manufactured Gas Plant Sites. Appendix C. Analytical Models, 1996 ) </li></ul></ul></ul></ul><ul><ul><ul><ul><li>Dispersion of soil gas to outdoor air, using simple near field box model (Pasquill 1975 and Horst 1979. Lagrangian Similarity Modeling of Vertical Diffusion from a Ground Level Source. Int. Appld. Met., 18, 733-740) </li></ul></ul></ul></ul>
    71. 71. EXPOSURE POINT CONCENTRATIONS <ul><li>AIR (cont.) </li></ul><ul><ul><li>Modeled - Target Compounds (VOCs, NAPTH, 2-MeNAPTH ) </li></ul></ul><ul><ul><ul><li>Groundwater </li></ul></ul></ul><ul><ul><ul><ul><li>Groundwater to air using USEPA Water8, lagoon unit (EPA-453/R-94-08A, November 1994. Air Emissions Models for Waste and Wastewater) or GRI model (1994). Obtain atmospheric conc., mass flux; or emission rate </li></ul></ul></ul></ul><ul><ul><li>Modeled - Target Compounds (VOCs, NAPTH, 2-MeNAPTH) </li></ul></ul><ul><ul><ul><li>Groundwater </li></ul></ul></ul><ul><ul><ul><ul><li>Groundwater to indoor air using Johnson & Ettinger (Heuristic Model for Predicting the Intrusion Rate of Contaminant Vapors into Buildings. Env. Sci. Technol., 1445-1452, 1991 + errata) and GRI Model (1996) to calculate a combined convection/diffusion attenuation factor for vadose zone and concrete slab (  ) x Henry’s Law constant (dimensionless) x MADEP-derived Dilution Factor (0.1 for VOCs; 0.01 for VPH/EPH Fractions) </li></ul></ul></ul></ul><ul><ul><li>Modeled - Immiscible Liquids (Product) </li></ul></ul><ul><ul><ul><li>Vadose Zone </li></ul></ul></ul><ul><ul><ul><ul><li>Product to soil gas using ASTM E 1739-95, Table X3.1 equation for maximum vapor concentrations when immiscible hydrocarbon is present </li></ul></ul></ul></ul><ul><ul><ul><ul><li>(C v,eq = x i P i v M w /RT) </li></ul></ul></ul></ul>
    72. 72. BACKGROUND SCREENING <ul><li>IDENTIFICATION OF CONTAMINANTS OF CONCERN </li></ul><ul><ul><li>SOIL </li></ul></ul><ul><ul><ul><li>VPH/EPH - Background levels assumed to be zero for screening purposes </li></ul></ul></ul><ul><ul><ul><li>Target Analytes </li></ul></ul></ul><ul><ul><ul><ul><li>VOCs - considered anthropogenic; background levels assumed to be zero </li></ul></ul></ul></ul><ul><ul><ul><ul><li>PAHs - considered ubiquitous and may be compared to MADEP urban/suburban background levels. Currently, the MADEP Background level for PAHs is 0.5 mg/kg. MADEP (May 1997) has proposed to increase individual PAH background levels up to 1, 2, 3 or 4 mg/Kg. More recently (MADEP May 2001), even higher urban residential (S-1) and commercial/industrial (S-2/S-3) PAH background levels proposed (e.g., benzo(a)pyrene 2/7.4 mg/Kg). </li></ul></ul></ul></ul><ul><ul><ul><ul><li>PAHs – use of coal/coal ash/ wood ash, and binder from bituminous asphalt MCP Reporting Exemptions (310 CMR 40. 0317(9) and (12). </li></ul></ul></ul></ul>
    73. 73. BACKGROUND SCREENING <ul><li>IDENTIFICATION OF CONTAMINANTS OF CONCERN </li></ul><ul><ul><li>GROUNDWATER/SURFACE WATER </li></ul></ul><ul><ul><ul><li>VPH/EPH and Target Analytes - considered anthropogenic; background concentrations assumed to be zero </li></ul></ul></ul><ul><ul><li>INDOOR AIR – BACKGROUND SCREENING 1 </li></ul></ul><ul><ul><ul><li>Level 1 – Soil Gas Screening, using PID/FID Meters for VPH/EPH fractions where groundwater concentration exceeds MCP Method 1 GW-2 Standard </li></ul></ul></ul><ul><ul><ul><li>Level 2 – Soil Gas Analysis, using GC field screening, modified VPH method, or APH analysis of VPH/EPH fractions </li></ul></ul></ul><ul><ul><ul><li>Level 3 – Indoor Air Sampling and APH analysis for VPH/EPH fractions and Target Analytes </li></ul></ul></ul><ul><ul><li>1 MADEP VPH/EPH/APH Guidance June 2001 </li></ul></ul>
    74. 74. BACKGROUND SCREENING <ul><li>IDENTIFICATION OF CONTAMINANTS OF CONCERN </li></ul><ul><ul><li>MADEP LEVEL 1 SOIL GAS SCREENING LEVELS FOR EVALUATION OF INDOOR AIR IMPACTS* </li></ul></ul><ul><ul><li>C 5 -C 8 Aliphatics (VPH) </li></ul></ul><ul><ul><li>C 9 -C 12 Aliphatics (VPH) </li></ul></ul><ul><ul><li>C 9 -C 10 Aromatics (VPH) </li></ul></ul><ul><ul><li>C 9 -C 18 Aliphatics (EPH) </li></ul></ul><ul><ul><li>Fraction > METHOD </li></ul></ul><ul><ul><li>1 GW-2 STD. </li></ul></ul><ul><ul><li>PID (ppmv) – Isobutylene Response </li></ul></ul><ul><ul><li>FID (ppmv) - </li></ul></ul><ul><ul><li>Methane Response </li></ul></ul><ul><ul><li>45 </li></ul></ul><ul><ul><li>45 </li></ul></ul><ul><ul><li>30 </li></ul></ul><ul><ul><li>30 </li></ul></ul><ul><ul><li>35 </li></ul></ul><ul><ul><li>35 </li></ul></ul><ul><ul><li>30 </li></ul></ul><ul><ul><li>30 </li></ul></ul>< 10.1 eV 10.1 – 11.4 eV N/A 35 35 10 15 5 > 11.5 eV 15 5 * MADEP VPH/EPH/APH Guidance June 2001 – Indoor air impact unlikely if PID/FID readings are below screening levels. Note : Values may not be protective for earthen floors or in presence of standing groundwater .
    75. 75. BACKGROUND SCREENING <ul><li>IDENTIFICATION OF CONTAMINANTS OF CONCERN </li></ul><ul><li>MADEP LEVEL 2 SOIL GAS FRACTIONALCONCENTRATIONS FOR EVALUATION OF INDOOR AIR IMPACTS </li></ul><ul><ul><ul><li>VPH/EPH - Measurable indoor air impacts unlikely if analyzed 1 fractional concentrations are below MADEP value 2 : </li></ul></ul></ul><ul><ul><ul><ul><li>C 5 -C 8 Aliphatics (VPH) - 170,000 µg/m 3 </li></ul></ul></ul></ul><ul><ul><ul><ul><li>C 9 -C 12 Aliphatics (VPH) - 180,000 µg/m 3 </li></ul></ul></ul></ul><ul><ul><ul><ul><li>C 9 -C 10 Aromatics (VPH) - 160,000 µg/m 3 </li></ul></ul></ul></ul><ul><ul><ul><ul><li>C 9 -C 18 Aliphatics (EPH) - 200,000 µg/m 3 </li></ul></ul></ul></ul><ul><ul><li>1 GC Field Screening, modified VPH analysis (direct injection/desorption), or APH analysis </li></ul></ul><ul><ul><li> of soil gas sample collected in a Tedlar ® Bag, SUMMA ® canister, or gas-tight syringe. </li></ul></ul><ul><ul><li>2 MADEP VPH/EPH/APH Guidance June 2001. Note : Values may not be protective for </li></ul></ul><ul><ul><li> earthen floors or in presence of standing groundwater. </li></ul></ul>
    76. 76. BACKGROUND SCREENING <ul><li>IDENTIFICATION OF CONTAMINANTS OF CONCERN </li></ul><ul><ul><li>* Time-weighted, indoor air sample collected in SUMMA ® canister under “worst-case conditions” for APH analysis </li></ul></ul><ul><ul><li>1 MADEP VPH/EPH/APH Guidance June 2001 . 2 MADEP October 1992. Risk Assessment Shortform. Residential Exposure Scenario. Policy #WSC/ORS-142-92. 3 MADEP May 2001. Proposed MCP Soil and Groundwater Standards. </li></ul></ul><ul><ul><li>MADEP LEVEL 3 – INDOOR AIR ANALYSIS* </li></ul></ul><ul><ul><ul><li>Target Analytes 2 </li></ul></ul></ul><ul><ul><ul><ul><li>Benzene - 21 µg/m 3 </li></ul></ul></ul></ul><ul><ul><ul><ul><li>Toluene - 29 µg/m 3 </li></ul></ul></ul></ul><ul><ul><ul><ul><li>Ethylbenzene - 10 µg/m 3 </li></ul></ul></ul></ul><ul><ul><ul><ul><li>Xylenes - 40 µg/m 3 and 72 µg/m 3 3 </li></ul></ul></ul></ul><ul><ul><ul><ul><li>Naphthalene - 5 µg/m 3 </li></ul></ul></ul></ul><ul><ul><ul><ul><li>2-Methylnaphthalene – 2 µg/m 3 3 </li></ul></ul></ul></ul><ul><ul><ul><li>VPH/EPH - MADEP Estimated </li></ul></ul></ul><ul><ul><ul><li>Generic Indoor Air Background </li></ul></ul></ul><ul><ul><ul><li>Concentrations 1 : </li></ul></ul></ul><ul><ul><ul><ul><li>C 5 -C 8 Aliphatics (VPH) - 85 µg/m 3 </li></ul></ul></ul></ul><ul><ul><ul><ul><li>C 9 -C 12 Aliphatics (VPH) - 90 µg/m 3 </li></ul></ul></ul></ul><ul><ul><ul><ul><li>C 9 -C 10 Aromatics (VPH) - 80 µg/m 3 </li></ul></ul></ul></ul><ul><ul><ul><ul><li>C 9 -C 18 Aliphatics (EPH) - 100 µg/m 3 </li></ul></ul></ul></ul>
    77. 77. RISK CHARACTERIZATION <ul><li>METHOD 1 </li></ul><ul><ul><li>TPH </li></ul></ul><ul><ul><ul><li>Compare Exposure Point Concentrations (EPCs) for Compounds of Concern (CoC) directly to applicable TPH Soil and/or Groundwater Cleanup Standards (now based on EPH C 11 -C 22 aromatic fraction - worst case) </li></ul></ul></ul><ul><ul><ul><li>Old and new TPH data used indirectly by “converting” TPH value into EPH fractional EPCs for comparison to EPH Soil and/or Groundwater Cleanup Standards </li></ul></ul></ul>
    78. 78. RISK CHARACTERIZATION <ul><li>METHOD 1 (cont.) </li></ul><ul><ul><li>VPH/EPH </li></ul></ul><ul><ul><ul><li>Compare individual VPH or EPH fraction EPCs to applicable MCP Method 1 Soil and/or Groundwater Standards </li></ul></ul></ul><ul><ul><ul><li>OHM included in the VPH/EPH hydrocarbon ranges are not considered distinct CoCs, unless there is an MCP Method 1 Standard available for that chemical </li></ul></ul></ul><ul><ul><ul><li>Example : Trimethylbenzenes are included in the C 9 -C 10 aromatics, therefore are not considered CoCs </li></ul></ul></ul>
    79. 79. RISK CHARACTERIZATION <ul><li>METHOD 1 (cont.) </li></ul><ul><ul><li>VPH/EPH </li></ul></ul><ul><ul><ul><li>If odors present indoors or in ambient air (not a Test Pit) - need to evaluate - potential Method 3 because of “another environmental medium” issue </li></ul></ul></ul><ul><ul><li>EPCs equal to or less than MCP Standards indicate a condition of “No Significant Risk” of harm to human health, public welfare and the environment </li></ul></ul>
    80. 80. RISK CHARACTERIZATION <ul><li>METHOD 2 </li></ul><ul><ul><li>Create Soil and/or Groundwater Standards for OHM when no Method 1 Standards are available </li></ul></ul><ul><ul><li>Modification of Method 1 Standards to address site-specific fate and transport considerations </li></ul></ul><ul><ul><ul><li>GW-1 : No modifications allowed (310 CMR 40.0982(1)) </li></ul></ul></ul><ul><ul><ul><li>GW-2 : Modification of VPH/EPH Standards limited to a demonstration of “No Impact” on indoor air: </li></ul></ul></ul><ul><ul><ul><ul><li>Use of Level 1 and 2 Soil Gas Screening </li></ul></ul></ul></ul><ul><ul><ul><ul><li>Level 3 Indoor Air Monitoring </li></ul></ul></ul></ul><ul><ul><ul><li>GW-2 : Modification of MCP DAT factor of 5E-04 for target analytes, using site-specific input parameters in Johnson & Ettinger model (1991) </li></ul></ul></ul>
    81. 81. RISK CHARACTERIZATION <ul><li>METHOD 2 (cont.) </li></ul><ul><ul><ul><li>GW-3 : Modification based on fate and transport considerations (e.g., Dilution Factors) and/or “No Impact” demonstration. However, modified GW-3 Standard > UCL </li></ul></ul></ul><ul><ul><ul><li>Soil Standards (S-1, S-2, S-3) : Limited to adjustment of the leaching component of the Method 1 Soil Standard, using site-specific input values for the SESOIL and AT123D models (e.g., point of compliance >10m for monitoring well, relative to zone of soil contamination). </li></ul></ul></ul><ul><ul><ul><li>Note : Only the C 11 -C 22 aromatic fraction, naphthalene and 2-methylnaphthalene soil standards are based on the leaching component. Modified Soil Standard cannot exceed the S-1, S-2, or S-3 Direct Contact Human Health Standard. </li></ul></ul></ul>
    82. 82. RISK CHARACTERIZATION <ul><li>METHOD 2 (cont.) </li></ul><ul><ul><ul><li>Soil Standards (S-1, S-2, S-3) cont. : In lieu of predictive models, use groundwater monitoring to evaluate site-specific leaching. </li></ul></ul></ul><ul><ul><ul><li>Works best for: </li></ul></ul></ul><ul><ul><ul><ul><li>Releases > 24 months old </li></ul></ul></ul></ul><ul><ul><ul><ul><li>Depth between contamination zone in soil and GW table is < 6 ft. </li></ul></ul></ul></ul><ul><ul><ul><ul><li>Surface overlying contamination is pervious </li></ul></ul></ul></ul><ul><ul><ul><ul><li>Adequate number of wells to characterize GW quality below and downgradient of soil contamination zone </li></ul></ul></ul></ul><ul><ul><ul><ul><li>Temporal monitoring data to evaluate seasonal trends </li></ul></ul></ul></ul>
    83. 83. <ul><li>METHOD 2 (cont.) </li></ul><ul><ul><li>Not applicable for media other than soil or groundwater </li></ul></ul><ul><ul><li>Compare individual VPH or EPH fraction and Target Analyte EPCs to applicable modified MCP Method 1 Soil and/or Groundwater Standards </li></ul></ul><ul><ul><li>EPCs equal to or less than MCP Standards indicate a condition of “No Significant Risk” of harm to human health, public welfare and the environment </li></ul></ul>RISK CHARACTERIZATION
    84. 84. RISK CHARACTERIZATION <ul><li>METHOD 3 </li></ul><ul><ul><li>Addresses all media (soil, groundwater, surface water, sediments, air, soil gas) </li></ul></ul><ul><ul><li>More flexible use of TPH and VPH/EPH data </li></ul></ul><ul><ul><li>Human Health </li></ul></ul><ul><ul><ul><li>Cumulative Non-cancer Risk Limit (Hazard Index) = 1 </li></ul></ul></ul><ul><ul><ul><ul><li>VPH/EPH and Target Analytes - if HI > 1, need to re-evaluate non-cancer risk by endpoint of toxicity (e.g., nephrotoxicity, neurotoxicity, skin irritation) </li></ul></ul></ul></ul><ul><ul><ul><li>Excess Lifetime Cancer Risk Limit (ELCR) 1 in 100,000 </li></ul></ul></ul><ul><ul><ul><ul><li>Focus on Class A and B carcinogens </li></ul></ul></ul></ul><ul><ul><ul><li>Comparison of CoC EPCs to all Applicable or Suitably Analogous Health Standards </li></ul></ul></ul>
    85. 85. RISK CHARACTERIZATION <ul><li>METHOD 3 (cont.) </li></ul><ul><ul><li>Optional Shortform for #2 Fuel/Diesel Oil Residential Health Assessment (MADEP September 1997) – useful for screening risks. </li></ul></ul><ul><ul><ul><li>Limitations: </li></ul></ul></ul><ul><ul><ul><ul><li>Addresses VPH/EPH fractions and target analytes for #2 Fuel/Diesel Oil </li></ul></ul></ul></ul><ul><ul><ul><ul><li>Conservative, default exposure assumptions </li></ul></ul></ul></ul><ul><ul><ul><ul><li>Does not evaluate risk to public welfare, safety or the environment </li></ul></ul></ul></ul><ul><ul><ul><ul><li>Some exposure assumptions and toxicity values need to be updated </li></ul></ul></ul></ul>
    86. 86. RISK CHARACTERIZATION <ul><li>METHOD 3 (cont.) </li></ul><ul><ul><li>Public Welfare </li></ul></ul><ul><ul><ul><li>Odors; loss of property values; unilateral restrictions; degradation of resources </li></ul></ul></ul><ul><ul><ul><li>UCLs for Soil and Groundwater </li></ul></ul></ul><ul><ul><ul><ul><li>Current vs. Future Risk - Neither = Permanent Solution </li></ul></ul></ul></ul><ul><ul><ul><ul><li>If CoC arithmetic average EPCs > UCL, Temporary Solution, unless soil contamination > 15 ft. bgs, or use Activity and Use Limitation (AUL) and engineered barrier </li></ul></ul></ul></ul><ul><ul><ul><ul><li>< 0.5 inch mobile NAPL = Permanent Solution </li></ul></ul></ul></ul>
    87. 87. RISK CHARACTERIZATION <ul><li>METHOD 3 (cont.) </li></ul><ul><ul><li>Environment </li></ul></ul><ul><ul><ul><li>Stage I Environmental Screening </li></ul></ul></ul><ul><ul><ul><ul><li>Identify critical receptors and complete exposure pathways </li></ul></ul></ul></ul><ul><ul><ul><ul><li>Use MADEP (June 2001) VPH/EPH Ambient Water Quality Guidelines for screening against CoC EPCs: </li></ul></ul></ul></ul><ul><ul><ul><ul><ul><li>C 5 -C 8 Aliphatics (VPH) – 390 µg/L </li></ul></ul></ul></ul></ul><ul><ul><ul><ul><ul><li>C 9 -C 12 Aliphatics (VPH) – 1,800 µg/L </li></ul></ul></ul></ul></ul><ul><ul><ul><ul><ul><li>C 9 -C 10 Aromatics (VPH) – 430 µg/L </li></ul></ul></ul></ul></ul><ul><ul><ul><ul><ul><li>C 9 -C 18 Aliphatics (EPH) – 1,800 µg/L </li></ul></ul></ul></ul></ul><ul><ul><ul><ul><ul><li>C 19 -C 36 Aliphatics (EPH) – 2,100 µg/L </li></ul></ul></ul></ul></ul><ul><ul><ul><ul><ul><li>C 11 -C 22 Aromatics (EPH) – 300 µg/L </li></ul></ul></ul></ul></ul>
    88. 88. RISK CHARACTERIZATION <ul><li>METHOD 3 (cont.) </li></ul><ul><ul><li>Environment </li></ul></ul><ul><ul><ul><li>Stage II Environmental Risk Characterization </li></ul></ul></ul><ul><ul><ul><ul><li>Refined screening process, field surveys </li></ul></ul></ul></ul><ul><ul><ul><ul><li>Use of site-specific Screening Criteria, Secondary Benchmark Values </li></ul></ul></ul></ul><ul><ul><ul><ul><li>Toxicity Testing </li></ul></ul></ul></ul><ul><ul><ul><li>UCLs - comparison to CoC arithmetic average EPCs </li></ul></ul></ul><ul><ul><li>Safety - per 310 CMR 40.0960 </li></ul></ul><ul><ul><ul><li>Physical and bodily harm </li></ul></ul></ul><ul><ul><ul><li>Explosive atmospheres </li></ul></ul></ul><ul><ul><ul><li>Comparison of CoC EPCs to Applicable or Suitably Analogous Safety Standards </li></ul></ul></ul>
    89. 89. USE OF VPH/EPH APPROACH IN OTHER JURISDICTIONS <ul><li>USEPA REGIONS </li></ul><ul><ul><li>REGIONS: 1, 2 , 4, 10 ???? </li></ul></ul><ul><li>STATES AND OTHER JURISDICTIONS </li></ul><ul><ul><li>New Jersey, Virgin Islands, Georgia, Washington, ??? </li></ul></ul>
    90. 90. VPH/EPH FUTURE DEVELOPMENTS <ul><li>TOXICITY FACTORS </li></ul><ul><ul><li>MADEP continuing to evaluate appropriate Reference Concentration (RfC) toxicity values for the VPH/EPH fractions, including values suggested by the TPHCWG </li></ul></ul><ul><ul><li>Current MADEP chronic inhalation RfC values: </li></ul></ul><ul><ul><ul><ul><li>C 5 -C 8 Aliphatics (VPH) – 200 µg/m 3 </li></ul></ul></ul></ul><ul><ul><ul><ul><li>C 9 -C 12 Aliphatics (VPH) – 2,000 µg/m 3 </li></ul></ul></ul></ul><ul><ul><ul><ul><li>C 9 -C 10 Aromatics (VPH) – 60 µg/m 3 </li></ul></ul></ul></ul><ul><ul><ul><ul><li>C 9 -C 18 Aliphatics (EPH) – 2,000 µg/m 3 </li></ul></ul></ul></ul><ul><ul><ul><ul><li>C 19 -C 36 Aliphatics (EPH) – N/A </li></ul></ul></ul></ul><ul><ul><ul><ul><li>C 11 -C 22 Aromatics (EPH) – 71 µg/m 3 </li></ul></ul></ul></ul>
    91. 91. OPEN DISCUSSION <ul><li>ISSUES </li></ul><ul><li>COMMENTS </li></ul><ul><li>AFTERNOON TEA OR THE PUB? </li></ul>

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