Petroleum Hydrocarbons

Petroleum Hydrocarbons A. Introduction (1) Specific procedures and evaluation criteria have been developed for sites with petroleum hydrocarbon contamination. This criteria has been developed to simplify the contaminant analyses required to characterize the site and to establish site-specific remediation goals (RGs). Petroleum hydrocarbon indicator compounds (i.e., Benzene, Toluene, PAHs, etc.) may not be quantifiable at the Tier 1 TRG Table concentrations because high petroleum hydrocarbon concentrations in the sample may cause analytical interferences resulting in either of the following: (a) Dilution of the extract, which would cause elevated detection limits and useless surrogate recovery data; and/or (b) Inaccurate compound identification and quantification, due to a poor peak separation or an elevated baseline during chromatography. (2) In addition, of the 250 individual compounds identified in petroleum, only 95 have toxicity data. Of these 95 compounds with toxicity data, only 25 have sufficient data to develop toxicity criteria. The interactive effects of all compounds present in TPH cannot be determined by data on 25 individual compounds. Therefore, to account for these unknowns, as well as to account for instances as described in Rule 2.2.7(A)(1), these procedures have been developed. (3) To evaluate human health and environmental risks specific to a Site under the circumstances in Rule 2.2.7(A)(1)(a) and (b), MDEQ has developed procedures for petroleum hydrocarbon contaminated Sites. B. Petroleum Hydrocarbon Evaluation Procedures (1) The Applicant shall utilize the procedures presented herein for the evaluation of potential human health and environmental risks from petroleum hydrocarbons in soil and groundwater. (2) A Tier 1 Evaluation of indicator compounds of petroleum hydrocarbons and TPH is required to establish the vertical and horizontal extent of indicator compound concentrations and TPH below the unrestricted values of the Tier 1 TRG Table. (3) A Site Ecological Checklist must be completed. (4) Petroleum-impacted soil and groundwater shall be assessed using the petroleum hydrocarbon indicator compounds, TPH-GRO, and TPH-DRO as presented in Appendix B, Table 1. Petroleum hydrocarbon categories presented in Appendix B, Table 1 represent typical hydrocarbon products. The Applicant shall correlate the site-specific hydrocarbon release and/or knowledge of the released hydrocarbon product to the appropriate category listed in Appendix B, Table 1. If the specific product that has been released is unknown, then a complete analytical evaluation must be conducted. (5) The Applicant shall perform soil and groundwater laboratory testing for the following indicator compounds: (a) Volatile Organic Compounds, including MTBE by SW-846 Method 8260B, or other Method approved by MDEQ.1 (b) Polycyclic Aromatic Hydrocarbons (PAHs) by Method 8310, with appropriate sample extraction, clean-up and instrumental finish. Analysis to be conducted for the PAHs listed in Appendix B, Table 1, or other Method approved by MDEQ. (c) Metals2 by SW-846 Method 6010, 6020, or the appropriate 7000 series, or other Method approved by MDEQ. (d) Methyl ethyl ketone2 by SW-846 Method 8260B, or other Method approved by MDEQ. (e) Methyl isobutyl ketone2 by SW-846 Method 8260B, or other Method approved by MDEQ. Note: 1All soil samples collected for VOC analysis must be collected in a manner consistent with MDEQ's Guidance for Collecting Volatile Organic Compounds in Soil, unless otherwise approved by MDEQ. 2When suspected to be present. (6) Although lead (organic and inorganic) has not been used as a gasoline additive for some time (since the late 1970's to early 1980's), there may be sites where lead (organic and inorganic) may be present due to historical activities on the Site. At sites where lead is suspected to be present as a potential site-related compound, inorganic lead and organic lead (specifically tetraethyl lead) must be identified as target analytes by appropriate analytical methods approved by MDEQ. C. Tier 1 Petroleum Hydrocarbon Evaluation (1) A Tier 1 Evaluation of indicator compounds of petroleum hydrocarbons, TPH- GRO, and TPH-DRO is required to establish the extent of indicator compound concentrations and TPH-GRO/DRO below the Tier 1 TRG Table. (2) Results of the indicator compound analysis, TPH-GRO, and TPH-DRO shall be compared with the TRGs presented in the Tier 1 TRG Table in Appendix A utilizing the Tier 1 Evaluation Procedures outlined in Rule 2.2.3.B of this Subchapter 2. (3) The Applicant shall address a hydrocarbon release using TPH analyses using SW- 846 Method 8015B or other Method approved by MDEQ and by analyzing the indicator compounds as described in Rule 2.2.7.A. (4) In areas of the site where the indicator compounds cannot be quantified to the Tier 1 Target Remedial Goal concentrations, the Applicant has the option of either: (a) conducting a Tier 1 Evaluation utilizing the Tier 1 Evaluation Procedures outlined in Rule 2.2.3.B of this Subchapter 2 for TPH-GRO and TPH- DRO; (b) conducting a Tier 2 Evaluation using TPH Fractioning; or (c) conducting a Tier 3 Evaluation using methods approved by MDEQ. D. Tier 2 Petroleum Hydrocarbon Evaluation - TPH Fractioning (1) A Tier 2 Petroleum Hydrocarbon Evaluation is primarily utilized in cases as described in Rule 2.2.7.A of this Subchapter 2 where indicator compound concentrations cannot be determined due to dilution and interference and where the concentrations of TPH-GRO/DRO exceed the restricted Tier 1 TRG levels for TPH-GRO/DRO. Along with the required comparison of indicator compounds as described in 2.2.7.C(2) of this Subchapter 2, the Applicant shall have the option of utilizing the TPH Carbon Fraction TRGs in Table 2 of Appendix B. (2) Massachusetts Method (a) The Massachusetts Department of Environmental Protection (MADEP) VPH/EPH Approach may be utilized to evaluate petroleum hydrocarbons under Tier 2. This method quantifies the total petroleum hydrocarbon fractions into collective aliphatic and aromatic ranges. To account for the hydrocarbon ranges present in contaminated media, MADEP's Volatile Petroleum Hydrocarbon (VPH) method and Extractible Petroleum Hydrocarbon (EPH) method have been developed. A detailed description of the MADEP VPH/EPH Approach may be found on the MADEP Web Site at (http://www.state.ma.us/dep/bwsc/vph_eph.htm). (b) The following principles form the basis for this approach: (1) Petroleum products are comprised mainly of aliphatic/alicyclic and aromatic hydrocarbon compounds. (2) Aromatic hydrocarbons appear to be more toxic than aliphatic compounds. (3) The toxicity of aliphatic compounds appear to be related to their carbon number/molecular weight. (c) Under this approach, the non-cancer toxicity of petroleum contaminated soil or water has been established by (1) determining the collective concentrations of specified ranges of aliphatic and aromatic hydrocarbons, and (2) assigning a toxicity value to each range. Well-characterized compounds within specified ranges have been selected as "surrogate" indicators to define the toxicity of the entire range. Toxicological Approach for Non-Carcinogens Hydrocarbon Fraction Analytical Fraction Analytical Method Surrogate Compound Reference Dose (mg/kg/d) C5-C8 Aliphatics C5-C8 VPH n-Hexane 0.06 C9-C18 Aliphatics C9-C12 C9-C18 VPH EPH n-Nonane n-Nonane 0.06 0.06 C19-C36 Aliphatics C19-C36 EPH Eicosane 6.0 C9-C22 Aromatics C9-C10 C11-C22 VPH EPH Pyrene Pyrene 0.03 0.03 (d) Carcinogenic and additional non-carcinogenic effects must be evaluated for the indicator constituents listed in Table 1 of Appendix B. (e) The EPH method separates the TPH Carbon Ranges (Fractions) into 3 sub-fractions and indicator PAH compounds. The VPH method separates the GRO Carbon Ranges (Fractions) into 3 sub-fractions and indicator compounds (i.e., BTEX, MTBE and naphthalene). (f) The VPH Method is a Purge and Trap, GC/PID/FID procedure and the EPH Method is a solvent extraction/fractionation GC/FID procedure. (g) The unrestricted TRGs listed in Table 2 of Appendix B have been adopted by MDEQ and correlate with the GW-1 groundwater zone the S-1 soil zone as defined by MADEP. (h) The restricted TRGs listed in Table 2 of Appendix B have been adopted by MDEQ and correlate to the GW-1 groundwater zone and the S-3 soil zone as defined by MADEP. (i) The Applicant must ensure and provide documentation to MDEQ that the Laboratory conducting the MADEP VPH/EPH Methodology is equipped to so do and will utilize appropriate Standard Operating Procedures (SOPs) as required by this methodology. (3) MDEQ may approve other TPH risk evaluation methodologies (e.g., TPHWG Methodology) or combinations thereof under Tier 2. E. Tier 3 Petroleum Hydrocarbon Evaluation (1) Alternative petroleum hydrocarbon Remedial Goals (RGs) may be established using a Tier 3 Risk Assessment approach. The alternative RGs shall be reviewed and approved or disapproved by MDEQ on a case-by-case basis.