speciation of c5 – c12 aliphatic hydrocarbons and c6 ... · microsoft powerpoint -...
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Steve Jones, Ph.D.Jones Environmental, Inc.Santa Fe Springs, CA
Speciation of C5 – C12 Aliphatic Hydrocarbons and C6 – C12 Aromatic Hydrocarbons Using EPA 8260B for
Vapor Intrusion Risk Assessment Evaluations
Outline• Regulations• TPH Toxicity Criteria – MADEP/DTSC• GC/MS Advantages• Hydrocarbon Types• Mass Spec Interpretation of Hydrocarbons• Spectrum Plot of Different Hydrocarbons• Oxidative Degradation of Hydrocarbons• Compounds in TPH Results that are NOT Hydrocarbons• Conclusions
Regulations• MDEQ – “Method for the Determination of Air-Phase
Petroleum Hydrocarbons (APH)”, Massachusetts Department of Environmental Protection, Office of Research and Standards, Bureau of Waste Site Cleanup. December 2009, Table 7, page 33.
• DTSC – “Evaluating Health Risk from TPH”, June 16, 2009, section 5.0, page 8.
• DTSC – “Preliminary Endangerment Assessment Guidance Manual, January 1994 (Interim Final – Revised October 2013), section 2.5.2.3 5), Table 2-6 “TPH Toxicity Criteria”, page 45.
Regulations – Table 2-6 TPH Toxicity Criteria
# 0.03 mg/kg/day may be used instead of 0.004 if naphthalenes and methylnaphthalenes have been analyzed and evaluated individually
^ Value is for C9 – C32
* Not developed due to low volatility of the COPCs in this hydrocarbon range. Although inhalation exposure to C17+TPH may occur via TPH bound to airborne dust HERD does not recommend performing a quantitative evaluation of inhalation exposure for C17+ not be performed because of the significant uncertainty involved.
Regulations – Risk Assessment• DTSC/HERD recommends the use of the following six
groups of hydrocarbons for which chemical surrogates for toxicity have been selected.• C5 – C8 (aliphatics)• C6 – C8 (aromatics)• C9 – C18 (aliphatics – Reported as C9+)• C9 – C16 (aromatics – Reported as C9+)• C19+ (aromatics)• C17+ (aromatics)
• If the analytical method used during the site investigation did not provide speciation into aromatics and aliphatics then an assumption of a composition of 50% aromatics and 50% aliphaticscan be made for most sites.
GC/MS Advantages• Identification of each component – Fingerprint Technique
• No second column confirmations required
• Identification of unknowns – NIST Library searches
• Selecting individual compounds
• Simplified chromatographic patterns
• Screening techniques for organic compounds
Hydrocarbon Types• Aliphatic/Alkanes/Saturated Hydrocarbons
• Olefins/Alkenes/Unsaturated Hydrocarbons
• Aromatics/Benzene Ring Compounds
• Naphthenic/Cyclic HydrocarbonsPyrene Benzene
Cyclohexane
Mass Spec Interpretation of Hydrocarbonsn-Hexane
H = 1amu C = 12 amu O = 16 amu N = 14 amu F = 19 amu Cl = 35 & 37 amuS = 32 amu Br = 79 & 81 amu
C4 C5 C6
C7 C8 C9
Oxidative Degradation of Hydrocarbons• R-CH2-CH3 : Alkane
• R-CH2-CH2-OH : Primary Alcohol
• R-CHOH-CH3 : Secondary Alcohol
• R-CH2-CHO : Aldehyde
• R-CO-CH3 : Ketone
• R-CH2COOH : Organic Acid
Substantially Weathered Hydrocarbon Pattern
Conclusions• A simple, easy to use way to calculate different
hydrocarbon compounds using already existing EPA 8260B methodology.
• The same methodology can be used to eliminate/identify degraded hydrocarbons, natural products, and heteroatom compounds in soil gas samples.
Thank you!