Sourcing Hydrocarbons at Fire Training Areas: A Molecular Characterization of the Combusted and Evaporated Residues of Distillate Fuels

Stephen Emsbo-Mattingly, Battelle Memorial Institute, 397 Washington Street, Duxbury, MA 02332, Tel: 781-934-0571
Scott Stout, Battelle Memorial Institute, 397 Washington Street, Duxbury, MA 02332, Tel: 781-934-0571
Allen Uhler, Battelle Memorial Institute, 397 Washington Street, Duxbury, MA 02332, Tel: 781-934-0571
Kevin McCarthy, Battelle Memorial Institute, 397 Washington Street, Duxbury, MA 02332, Tel: 781-934-0571 

The use of petroleum accelerants at fire training areas was common prior to the 1970’s.  Typical accelerants included gasoline, kerosene, and diesel.  Specialized fire training exercises occasionally employed heavier petroleum products, like residual fuel and crude oils.  Consequently, the wide range of potential petroleum and combustion products at fire training areas presents complicated issues for parties interested in fate and transport, risk assessment, and environmental forensics.

Petroleum distillates can retain source signature information after severe environmental weathering.  In this study, kerosene and diesel reference samples were independently weathered to approximately 50% and more than 90% by mass using evaporation and combustion.  These reference samples were compared to field samples that contained severely degraded petroleum of unknown origin.  The environmental forensic methods used for this study focused on petrogenic volatiles (paraffins, isoparaffins, aromatics, naphthenes, olefins) and semivolatiles (alkylated PAH, alkanes, alkylcyclohexanes, sesquiterpanes, triterpanes, steranes).  The interpretive techniques included chemical fingerprinting, principal components analysis (PCA), and diagnostic ratios.  Collectively, the forensic analyte list and interpretive tools identified the likely origins of multiple weathered petroleum found at the site.

The Analysis of PCBs in New Bedford Harbor Sediments: Selecting and Optimizing Immunoassay, GC/ECD, and GC/MS Methods Based on Multiple Site-Specific DQOs

Stephen Emsbo-Mattingly, Battelle Memorial Institute, 397 Washington Street, Duxbury, MA 02332, Tel: 781-952-5246
Helen Douglas, Foster Wheeler Environmental Corporation, 133 Federal Street – 6^th floor, Boston, MA 02110, Tel: 617-457-8263
Andy Beliveau, U.S. EPA Environmental Services Division, 11 Technology Drive, North Chelmsford, MA  01863, Tel: 617-918-1443
Marie Wojtas, U.S. Army Corps of Engineers, New England District, 696 Virginia Rd, Concord, MA 01742, Tel: 978-318-8175
Yixian Zhang and Heather Ferro, Foster Wheeler Environmental Corporation, 133 Federal Street – 6^th floor, Boston, MA 02110, Tel: 617-457-8263

Electrical capacitor manufacturing plants released polychlorinated biphenyls (PCBs) into New Bedford Harbor (NBH) between the 1940s and 1970s. Past studies characterized the PCBs as mixtures of Aroclors 1242 and 1254 in variable states of degradation. A dredge design plan is under development for the delineation and remediation of PCBs in this 1000-plus acre water body relative to four cleanup goals established to protect a range of environmental receptors pursuant to the EPA the Record of Decision (ROD) of 1998.  This large-scale sediment delineation program required the use of multiple analytical methods for the dual purposes of maximizing data usability for site-specific data quality objectives (DQOs) and minimizing analytical costs. 

Immunoassay screening methods (EPA 4020) were used to identify samples with concentrations near the ROD cleanup levels and recover costs associated with the analysis of very clean or very contaminated sediment samples that might otherwise have been needlessly analyzed by more expensive methods.  Gas chromatographic (GC) methods were used when higher levels of precision and accuracy were required.  The majority of these PCB measurements were performed on a gas chromatograph equipped with an electron capture detector (GC/ECD, EPA 8082) calibrated for commonly occurring PCB congeners identified by the National Oceanic Atmospheric Association (NOAA).  However, the potential for site-specific PCB compositions necessitated the confirmation of total PCB concentrations using a GC equipped with a low-resolution mass spectrometer (GC/MS, EPA 8270) and calibrated for PCB homologues in order to monitor potential bias. 

This study presents the results of more than 4,000 samples analyzed by for NOAA PCB congeners with comparisons to approximately 450 immunoassay and 200 PCB homologue results.  These data demonstrated a poor correlation between the immunoassay and NOAA PCB congener methods (PCB_Immunoassay = 1.9 x PCB_SNOAA + 0, R² = 0.5).  However, the immunoassay data proved very useful when used in conjunction with a decision tree that properly managed the inter-method variability relative the site-specific DQOs.  By contrast, a good correlation existed between the NOAA PCB congener and PCB homologue methods (PCB_SHomologue = 2.6 x PCB_SNOAA + 0, R² = 0.9).  These relationships helped data users employ field and fixed laboratory methods at frequencies appropriate for the minimization of costly analyses (EPA 8082 and EPA 8270) and maximization the chemical information needed for developing the dredge design plan for NBH in accordance with the ROD.

Fingerprinting Organic Lead Species in Automotive Gasolines and Free Products Using Direct Injection GC/MS

Edward Healey, Battelle Environmental Forensics Investigation Group, 397 Washington Street, Duxbury, MA 02332, Tel: 781-952-5273, Fax: 781-934-2124, Email: healeye@battelle.org
S. Andrew Smith, Battelle Environmental Forensics Investigation Group, 397 Washington Street, Duxbury, MA 02332, Tel: 781-952-5248, Fax: 781-934-2124, Email: smithsa@battelle.org
Kevin J. McCarthy, Battelle Environmental Forensics Investigation Group, 397 Washington Street, Duxbury, MA 02332, Tel: 781-952-5226, Fax: 781-934-2124, Email: mccarthy@battelle.org
Scott A. Stout, Battelle Environmental Forensics Investigation Group, 397 Washington Street, Duxbury, MA 02332, Tel: 781-952-5234, Fax: 781-934-2124, Email: stouts@battelle.org
Richard M. Uhler, Battelle Environmental Forensics Investigation Group, 397 Washington Street, Duxbury, MA 02332, Tel: 781-952-5225, Fax: 781-934-2124, Email: uhlerr@battelle.org
Allen D. Uhler, Battelle Environmental Forensics Investigation Group, 397 Washington Street, Duxbury, MA 02332, Tel: 781-952-5225, Fax: 781-934-2124, Email: uhler@battelle.org
Stephen D. Emsbo-Mattingly, Battelle Environmental Forensics Investigation Group, 397 Washington Street, Duxbury, MA 02332, Tel: 781-952-5246, Fax: 781-934-2124
Email: emsbo-mattinglys@battelle.org
Gregory S. Douglas, Battelle Environmental Forensics Investigation Group, 397 Washington Street, Duxbury, MA 02332, Tel: 781-952-5393, Fax: 781-934-2124, Email: douglasg@battelle.org

Automotive gasoline has a long and complex history of compositional change.  Increasingly sophisticated refining techniques and performance enhancing additives have helped the US gasoline pool keep pace with the needs of the auto industry and the requirements of regulatory agencies.  Among the most important additives in the evolution of automotive gasoline was organic lead, specifically tetraethyl lead (TEL).  TEL was first introduced into automotive gasolines in 1923 as an antiknock agent.  TEL was the lone organic lead compound added to automotive gasoline until 1960, when tetramethyl lead (TML) was formulated, and various lead ‘packages’ were developed and introduced to the gasoline market.  Packages included both physical mixtures (PM) and reacted mixtures (RM) of TEL and TML.  Reacted mixtures are the end products of a catalyzed TEL: TML reaction that results in the formation of five organic lead species: tetramethyllead (TML), trimethylethyllead (TMEL), diethyldimethyllead (DEDML), methyltriethyllead (MTEL), and tetraethyllead (TEL).  TEL use, followed by RM and PM usage, increased steadily over time as the demand for increased engine performance and fuel economy grew.  Ultimately, the average levels of lead in the premium gasoline pool reached a high of approximately 3.0 grams lead per gallon (glpg) around 1970.  After 1970, Federally-mandated restrictions (1970 Clean Air Act and 1990 Clean Air Act Amendment) led to a systematic reduction in the maximum allowable lead levels and the introduction of low-lead and unleaded gasolines, culminating with a complete elimination of organic lead additives in automotive gasoline in the U.S. in 1996 (1992 in California). 

This poster will describe a specialized analytical method used in the molecular characterization of the five organic lead species found in historic automotive gasolines.  The analytical method includes quantitative high-resolution gas chromatography (GC) with mass spectrometry (MS) detection in the selected ion monitoring mode following adaptations of EPA Method 8270.   The analysis is performed using a direct injection technique for gasoline and free phase petroleum.  Interpretive forensic techniques, utilizing the organic lead results generated with this method will be discussed.  Two case studies where organic Pb fingerprinting, used in conjunction with conventional gasoline fingerprinting, was useful in determining liability at historic gasoline contaminated sites will be presented.

Allocation of Commingled Hydrocarbons Derived from Manufactured Gas Plant versus Petroleum Handling Operations

S. Andrew Smith, Battelle Environmental Forensics Investigation Group, 397 Washington Street, Duxbury, MA 02332, Tel: 781-952-5248, Fax: 781-934-2124, Email: smithsa@battelle.org
Edward Healey, Battelle Environmental Forensics Investigation Group, 397 Washington Street, Duxbury, MA 02332, Tel: 781-952-5273, Fax: 781-934-2124, Email: healeye@battelle.org
Kevin J. McCarthy, Battelle Environmental Forensics Investigation Group, 397 Washington Street, Duxbury, MA 02332, Tel: 781-952-5226, Fax: 781-934-2124, Email: mccarthy@battelle.org
Scott A. Stout, Battelle Environmental Forensics Investigation Group, 397 Washington Street, Duxbury, MA 02332, Tel: 781-952-5234, Fax: 781-934-2124, Email: stouts@battelle.org
Allen D. Uhler, Battelle Environmental Forensics Investigation Group, 397 Washington Street, Duxbury, MA 02332, Tel: 781-952-5225, Fax: 781-934-2124, Email: uhler@battelle.org
Stephen D. Emsbo-Mattingly, Battelle Environmental Forensics Investigation Group, 397 Washington Street, Duxbury, MA 02332, Tel: 781-952-5246, Fax: 781-934-2124, Email: emsbo-mattinglys@battelle.org
Gregory S. Douglas, Battelle Environmental Forensics investigation Group, 397 Washington Street, Duxbury, MA 02332, Tel: 781-952-5393, Fax: 781-934-2124, Email: douglasg@battelle.org

Environmental forensic investigations routinely involve characterizing industrial sites that have a complex and multi-use history.   In the case of hydrocarbon contamination, many industrial sites’ histories often parallel the Nation’s energy history, particularly the shift in our reliance from coal to petroleum, including natural gas.  As a result, environmental forensic investigations of industrial properties where (or near) historic (~1870’s to 1940’s) manufactured gas plants (MGPs) that subsequently were used to handle petroleum, are common.  Such investigations are often focused on distinguishing hydrocarbons derived from the residues and by-products of MGP versus those derived from petroleum operations.   Although hydrocarbons from these two source categories can be readily distinguished by using conventional hydrocarbon fingerprinting techniques (e.g., alkylated PAH and biomarker analysis), the commingled character of MGP wastes and petroleum at many sites can complicate allocation of any liability for clean-up or damages.  Unraveling these mixtures based upon the mass, volume, or percent of soil impacted by hydrocarbons from MGP wastes versus those derived from petroleum, can provide a fair basis for successfully resolving liability.  

In this study, a novel analytical method and the interpretive techniques used to accurately allocate hydrocarbon sources when faced with commingled materials at a contaminated site is described.  The analytical method relies upon quantitative high-resolution gas chromatography (GC) with simultaneous flame ionization detection (FID) and mass spectrometry (MS) detection.  Known incremental mixtures of fresh and weathered coal tar and diesel fuel #2 (commonly encountered hydrocarbon mixtures) were prepared and analyzed using this combination of detection techniques. Various integrations and ion extraction techniques were evaluated and the resulting hydrocarbon masses were compared to the known starting percentages.   The optimal method(s) for ‘unmixing’ these known mixtures using the multiple detection techniques was identified and compared to the results that could be obtained from each detection method used alone.  The advantages of the simultaneous FID and MS detectors, and shortcomings of their individual use alone, will be presented and discussed.  The results of the laboratory ‘mixing’ study are then applied to a field case study where soils have been impacted with both coal tar and petroleum contamination.  

Passive Diffusion Bag Sampler Results From Multiple DoD Installations

John Tunks, Parsons, 1700 Broadway, Ste. 900, Denver, CO. 80290, Tel: 303-764-8740, Fax: 303-831-8208
John Hicks, Parsons, 1700 Broadway, Ste. 900, Denver, CO. 80290, Tel: 303-764-1941, Fax: 303-831-8208
Javier Santillan, AFCEE/ERT, 3207 North Road, Brooks AFB, TX. 78235-5363, Tel: 210-536-5207, Fax: 210-536-5989
Raphael Vazquez, AFCEE/ERT, 3207 North Road, Brooks AFB, TX. 78235-5363, Tel: 210-536-1431, Fax: 210-536-4330  

Groundwater sample collection using passive diffusion bag samplers (PDBSs) represents a relatively new technology that employs passive sampling methods for monitoring volatile organic compounds (VOCs) in groundwater.  The potential benefits and cost savings associated with using PDBS for long-term monitoring are significant, as no purge waters are generated, and labor requirements for sampler installation and retrieval are minimal.  Results of a field-scale PDBS demonstration performed at 14 Department of Defense installations between May 2001 and February 2002 will be presented.  The primary objective of the PDBS demonstration is to assess the effectiveness of the PDBS method by comparing groundwater analytical results for VOCs obtained using the current (conventional) sampling method with results obtained using the PDBS method.  The comparison of the conventional and diffusion sampling results will allow assessment of the appropriateness of implementing diffusion sampling for VOCs at each sampled well.  Details will include a general description of the work performed, the common findings for all installations sampled, and an analysis of the effectiveness of the technology.  If possible, a list of operational parameters that promote the usability of PDBS, and a list of operational parameters that indicate when poor performance is likely to occur will be presented.  A cost and performance analysis also will be developed that includes implementation costs, cost comparison to conventional sampling, sampling cost avoidance generated by PDBS, and a return on investment assessment.

Weight of Evidence Evaluation of Net Sedimentation and Natural Attenuation Rates, Lower Fox River (WI)

Timothy J. Dekker, Gregory J. Gerstner, Richard D. McCulloch, Cynthia P.E. Valente, and John R. Wolfe, Limno-Tech, Inc. (LTI), 501 Avis Drive, Ann Arbor, MI 48108, Tel: 734-332-1200, Fax: 734-332-1212

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