Environmental Forensic Analysis Using Enhanced Hydrocarbon

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Environmental Forensic Analysis Using Enhanced Hydrocarbon Testing Crude oil, coal, coal tar and creosote oil products contain Hydrocarbons (SHC), Polycyclic Aromatic Hydrocarbons complex mixtures of hydrocarbons. Due to the differences in (PAHs) and their alkylated homologs (aPAHs), and/or natural sources, as well as a wide variety of anthropogenic Petroleum Biomarkers, to perform their assessment. sources, environmental samples can have unique TestAmerica’s Analytical Approach – multi faceted to meet hydrocarbon fingerprints. These fingerprints can provide specific project requirements. the basis for identifying and distinguishing the sources of natural releases, released oil, coal tar or other oil products. Conventional lists of chemical compounds in U.S. EPA Methods do not include the important constituents of Lighter distillates, such as gasoline products, also present a petroleum, refined petroleum products, coal tar and complex mixture of components which require a creosote products. As a result, TestAmerica has modified sophisticated analytical approach for proper identification, standard U.S. EPA SW 846 methodologies to provide the quantification and generation of chemical fingerprints, data necessary for chemical fingerprinting and which can be utilized for these products, as well to identify environmental forensic investigations. Method potential sources of release. enhancements include: With these tools, environmental forensics can be utilized to • Expanded target analyte lists to characterize and investigate the spatial and temporal extent of releases of differentiate petroleum, coal, coal tar and creosote hydrocarbons into the environment using chemical products. fingerprinting. The unintended release of these compounds • Sufficient analytical sensitivity to achieve the low into the environment can require extensive and expensive detection levels required. environmental cleanup activities, as well as an assessment of • Instrument selectivity to minimize matrix interferences the potential damages to terrestrial, aquatic and/or marine and false positives. natural resources, and accurate source identification is • Applicability to a wide variety of matrices including oil, necessary in establishing proper apportionment. NAPL, coal tar, MGP oil, water, soil, sediments and tissues. TestAmerica’s Enhanced Hydrocarbon testing program offers a robust portfolio of analyses to provide unique The international industry standard for oil spill identification, testing solutions to the industry’s most challenging oil the Nordtest Methodology for Oil Spill Identification (2002 release situations. Revision), recommends a tiered testing and data treatment approach to oil release investigations. The first tier of testing Chemical Fingerprinting includes a qualitative analysis for Saturated Hydrocarbons Chemical fingerprinting allows for the comparison of unique (SHC) utilizing gas chromatography flame ionization diagnostic chemical features of potentially impacted detector methods. The evaluation can then continue environmental samples. Environmental Forensic Chemists through the next tier of testing which includes quantitative can use the data generated from specialized environmental analyses to determine concentrations of PAHs, aPAHs and hydrocarbon testing methods, such as those for Saturated petroleum biomarkers. Tier I – Saturated Hydrocarbon Testing by GC/FID concentration calculated, utilizing the parent response The first tier of the Nordtest methodology calls for factor. Quantification of the target compounds is based analysis of samples utilizing a high resolution gas on their response relative to their associated internal chromatography/ flame ionization detector (GC/FID). standard. TestAmerica utilizes a modified method based on U.S. EPA If required, biomarkers can be detected at low levels in SW 846 Method 8015 for the determination of the total the presence of other hydrocarbons utilizing SW 846 distribution of hydrocarbons from C8 to C40, as well as Method 8270M SIM. Estimation of concentrations for selected isoprenoids, pristane and phytane. This biomarker compounds is achieved by using the response qualitative methodology provides for a whole oil gas factor from a representative standard. TestAmerica uses chromatographic analysis, or chemical fingerprint, of the previously characterized crude oil in its assessment of samples. system performance. TestAmerica can also use project specific crude oils as analytical comparison oils for the fingerprinting evaluation of field samples, if requested. Analysis The typical reporting limits for each method are listed Saturated Hydrocarbons (SHC) below: n-C8 to n-C40 Isoprenoids pristane/n-C17 Analysis phytane/n-C18 Geochemical Biomarkers Saturated Hydrocarbons (SHC) Total Petroleum Hydrocarbons 2,2,4,4,6,8,8-Heptamethylnonane Isoprenoids 2,6,10-Trimethyldodecane pristane/n-C17 2,6,10-Trimethyltridecane phytane/n-C18 2,6,10-Trimethylpentadecane Geochemical Biomarkers Matrix Reporting Limit 2,2,4,4,6,8,8-Heptamethylnonane NAPL and Product 100 mg/kg 2,6,10-Trimethyldodecane Water 10 ug/L 2,6,10-Trimethyltridecane Soil and Sediment 0.33 mg/kg 2,6,10-Trimethylpentadecane 65 Parent and Alkylated Homologs PAHs Tier II – SHC, PAHs, aPAHs and Biomarkers by GC/MS 43 Biomarkers TestAmerica’s analytical approach for PAHs, aPAHs and Matrix Reporting Limit biomarkers utilizes a high resolution gas chromatography NAPL and SHC - 1 mg/kg; mass spectrometer (GC/MS), and a modified method Product PAH, aPAH and Biomarkers –1mg/kg based on U.S. EPA SW 846 Method 8270. TestAmerica’s Water SHC – 0.02 ug/L; method is modified to include additional PAHs which are not a part of the standard Method 8270 list. Utilizing this PAH, aPAH and Biomarkers – 0.02 ug/L method, analysis for PAHs and their alkylated homologs Soil and SHC – 0.66 ug/kg; can be performed simultaneously with the biomarker Sediment PAH, aPAH and Biomarkers – 0.66 ug/kg analysis. This method also provides for a “chemical fingerprint” of the sample. The GC/MS method is quantitative in nature, and the identification of calibrated target compounds is based on the detection of a peak at the appropriate retention time, except for the alkylated PAHs. The alkylated PAHs are identified, and the PIANO - Paraffins, Isoparaffins, Aromatics, Naphthenes, Certifications and Olefins TestAmerica’s certifications include: Gasoline is a complex mixture of hundreds of • NELAP – National Environmental Laboratory compounds, including hydrocarbons, oxygen containing Accreditation Program ethers, alcohols, sulfur and nitrogen containing moieties. • USDA Soil Import Permit Since no two refinery’s products are identical, gasoline • Comprehensive state certifications can be chemically fingerprinted to identify a potential release source. Hydrocarbons that are present in Reports and EDDs That Are Easy to Use gasoline occur in five compound classes: Paraffins, TestAmerica’s network of laboratories across the nation Isoparaffins, Aromatics, Naphthenes, and Olefins, often are connected by a single laboratory information collectively referred to as PIANO compounds. The PIANO management system (LIMS). This interconnected LIMS target compound list provides chemical fingerprinting allows for the creation of one comprehensive report and data for forensic purposes related to gasoline releases. electronic data deliverable (EDD), regardless of analysis location, saving our client’s time and reducing costs. TestAmerica’s Analytical Approach for PIANO TestAmerica’s PDF reports are searchable, color coded TestAmerica’s analytical approach for PIANO compounds and tabbed for easy navigation, reducing review time. utilizes a high resolution gas chromatography/mass spectrometer (GC/MS) instrument, with a modified TotalAccess® On-line Data Delivery method based on U.S. EPA SW 846 Method 8260. The TotalAccess®, TestAmerica’s 24/7, online data delivery modification includes a far wider range of target analytes solution, allows clients to track all aspects of their when compared to the traditional Method 8260 analysis, environmental data program. including 11 paraffins, 33 isoparaffins, 26 olefins, 26 • Rapid access to data and deliverables for real time naphthenes, 37 aromatic compounds, MTBE, TAME, DIPE, decision making. ETBE, Thiophene, benzo(b)thiophene, • Customizable EDD creation with comparison of 2–methylthiophene, 2–ethylthiophene, as well as C3- results to preloaded regulatory standards. C13. • Data trending capabilities by sample and analyte. • Consolidation of multiple events into one EDD. Tetraethyl Lead (TEL) • Budget tracking and deliverable storage. To maximize performance, various additives were For additional information on TestAmerica’s Enhanced blended into gasoline during production, including lead Hydrocarbon capabilities, contact: alkyls, in the early 1920’s. Tetraethyl Lead (TEL) was a lead alkyl substance added to automotive gasoline as an antiknock agent to improve octane performance. TEL was phased out of gasoline produced for road vehicles in the United States prior to 1996 (pre-1992 in California). The measurement of TEL can be associated with the time of release of the gasoline in the environment.

TestAmerica’s Analytical Approach for TEL TestAmerica utilizes a high resolution gas chromatography /mass spectrometer (GC/MS) instrument for the determination of Tetraethyl Lead, with a modified method that is based on U.S. EPA SW 846 Method 8270 SIM. TestAmerica Nashville 615726.0177 [email protected] (mass g- Saturated Hydrocarbon (SHC) Analyte List

Short Code Long Code Short Code Long Code Short Code Long Code n-C8 n-Octane n-C17 n-Heptadecane n-C28 n-Octacosane n-C9 n-Nonane Pristane(C19 branched) n-C29 n-Nonacosane n-C10 n-Decane n-C18 n-Octadecane n-C30 n-Triacontane n-C11 n-Undecane Phytane(C20 branched) n-C31 n-Hentriacontane n-C12 n-Dodecane n-C19 n-Nonadecane n-C32 n-Dotriacontane n-C13 n-Tridecane n-C20 n-Icosane n-C33 n-Tritriacontane 2,2,4,4,6,8,8- n-C21 n-Heneicosane n-C34 n-Tetratriacontane Heptamethylnonane n-C22 n-Docosane n-C35 n-Pentatriacontane 2,6,10-Trimethyldodecane n-C23 n-Tricosane n-C36 n-Hexatriacontane n-C14 n-Tetradecane n-C24 n-Tetracosane n-C37 n-Heptatriacontane 2,6,10-Trimethyltridecane n-C25 n-Pentacosane n-C38 n-Octatriacontane n-C15 b- Pentadecane n-C26 n-Hexacosane n-C39 n-Nonatriacontane n-C16 n-Hexadecane n-C27 n-Heptacosane n-C40 n-Tetracontane 2,6,10-Trimethylpentadecane

Polycyclic Aromatic Hydrocarbons (PAH) and Alkylated PAH (aPAH) Homolog Analyte Lists

Standard PAH Analytes Alkylated PAH Analytes Decahydronaphthalene 1-Methylphenanthrene C1-Decalins C2-Phenanthrenes/Anthracenes Naphthalene Fluoranthene C2-Decalins C3-Dibenzothiophenes Benzo(b)thiophene Pyrene C1-Benzothiophenes C3-Phenanthrenes/Anthracenes 2-Methylnaphthalene Retene C3-Decalins C4-Dibenzothiophenes 1-Methylnaphthalene Naphthobenzothiophene C1-Naphthalenes C1-Fluoranthenes/pyrene 1,1'-Biphenyl Benzo[a]anthracene C4-Decalins C4-Phenanthrenes/Anthracenes 2,6-Dimethylnaphthalene Chrysene C2-Benzothiophenes C2-Fluoranthenes/Pyrene Acenaphthylene Benzo[b]fluoranthene C2-Naphthalenes C3-Fluoranthenes/Pyrene Acenaphthene Benzo[k]fluoranthene C3-Benzothiophenes C1-Naphthobenzothiophenes Dibenzofuran Benzo[e]pyrene C3-Naphthalenes C1-Chrysenes 2,3,5-Trimethylnaphthalene Benzo[a]pyrene C4-Benzothiophenes C4-Fluoranthenes/Pyrene Fluorene Perylene C4-Naphthalenes C2-Naphthobenzothiophenes Dibenzothiophene Indeno[1,2,3-cd]pyrene C1-Fluorenes C2-Chrysenes Phenanthrene Dibenz(a,h)anthracene C2-Fluorenes C3-Naphthobenzothiophenes Anthracene Benzo[g,h,i]perylene C1-Dibenzothiophenes C3-Chrysenes C1-Phenanthrenes/Anthracenes C4-Naphthobenzothiophenes C3-Fluorenes C4-Chrysenes C2-Dibenzothiophenes Biomarker Analyte List

Compound Type Common Name Short Code Long Name Sterane 5-beta(H)Cholane 5-beta(H)Cholane Sterane S4-Diacholestane 27dbS 13B(H),17a(H),20S-cholestane Sterane S5-Diacholestane 27dbR 13B(H),17a(H),20R-cholestane Sterane S14-Cholestane(20R) 27bbR 5a(H),14B(H),17B(H),20R-cholestane Sterane S15-Cholestane(20S) 27bbS 5a(H),14B(H),17B(H),20S-cholestane Sterane Alpha,alpha,alpha20R-Cholestane 27aaR 5a(H),14a(H),17a(H),20R-cholestane Sterane 5.alpha.-Chlorest-3-ene 5.alpha.-Chlorest-3-ene Sterane S22-Methylcholestane(20R) 28bbR 24-methyl-5a(H),14B(H),17B,20R-cholestane Sterane S23-Methylcholestane(20S) 28bbS 24-methyl-5a(H),14B(H),17B,20S-cholestane Sterane S24-Methylcholestane 28aaR 24-methyl-5a(H),14a(H),17a,20R-cholestane Sterane S26-Ethylcholestane(20R) 29bbR 24-ethyl-5 α( H), 14β( H), 17β( H), 20( R)- cholestane Sterane S25-Ethylcholestane 29aaS 24-ethyl-5 α( H), 14α( H), 17α( H), 20( S)- cholestane Sterane S27-Ethylcholestane(20S) 29bbS 24-ethyl-5 α( H), 14β( H), 17β( H), 20( S)- cholestane Sterane S28-Ethylcholestane 24-ethyl-5 α( H), 14α( H), 17α( H), 20( R)- cholestane Terpane T11-Trisnorhopane(TS) 27Ts 18a(H)-22,29,30-trisnorhopane Terpane T12-Trisnorhopane(TM) 27Tm 17a(H)-22,29,30-trisnorhopane Terpane T13a-29,30-Bisnorhopane T13a-29,30-Bisnorhopane Terpane T13-Trisnorhopane 27B 17 β( H)-22,29,30- trisnorhopane Terpane T15-C29-Norhopane 29ab 17a(H),21B(H)-30-norhopane Terpane T16-Norneohopane 29Ts 18a(H)-30-norneohopane Terpane 17a(H)-diahopane 30d 15a-methyl-17a(H)-27-norhopane Terpane T17-C30-Normoretane 29ba 17B(H)-21a(H)-30-norhopane Terpane T18-C30-Oleanane 30O 18a(H)-oleanane Terpane T19-C30-Hopane 30ab 17a(H), 21B(H)-hopane Terpane T20-Moretane 30ba 17B(H),21a(H)-hopane Terpane T21-C31-Homohopane(S) 31abS 17a(H),21B(H),22S-homohopane Terpane T22-C31-Homohopane(R) 31abR 17a(H),21B(H),22R-homohopane Terpane T22a-Gammacerane 30G Gammacerane Terpane T26-C32-Bishomohopane(S) 32abS 17a(H),21B(H),22S-bishomohopane Terpane T27-C32-Bishomohopane(R) 32abR 17a(H),21B(H),22R-bishomohopane Terpane T30-C33-Trishomohopane(S) 33abS 17a(H),21B(H),22S-trishomohopane Terpane T31-C33-Trishomohopane(R) 33abR 17a(H),21B(H),22R-trishomohopane Terpane T32-Tetrakishomohopane(S) 34abS 17a(H),21B(H),22S-tetrakishomohopane Terpane T33-Tetrakishomohopane(R) 34abR 17a(H),21B(H),22R-tetrakishomohopane Terpane T34-Pentakishomohopane(S) 35abS 17a(H),21B(H),22S-pentakishomohopane Terpane T35-Pentakishomohopane(R) 35abR 17a(H),21B(H),22R-pentakishomohopane Triaromatic Steriod A1-C20-TAS C20TA C20-triaromatic steroid Triaromatic Steriod A2-C21-TAS C21TA C21-triaromatic steroid Triaromatic Steriod A3-C26-TAS(20S) SC26TA C26,20S-triaromatic steroid Triaromatic Steriod A4-C26/C27-TAS RC26TA/SC27TA C26,20R- C27,20S-triaromatic steroid Triaromatic Steriod A6-TAS(20S) SC28TA C28,20S,triaromatic steroid Triaromatic Steriod A5-C27-TAS(20R) RC27TA C27,20R,triaromatic steroid Triaromatic Steriod A7-TAS(20R) RC28TA C28,20R,triaromatic steroid