A Comparison of XRF Data with ICP/AA Data
Timothy J. Boyle, MA DEP, Wilmington, MA
John Fitzgerald, MA DEP, Wilmington, MA

Characterization or Identification of Organic Compounds by Ion Compostition Elucidation (ICE) using Gas Chromatography/High Resolution Mass Spectrometry
Andrew H. Grange, US EPA, NERL, Las Vegas, NV
G. Wayne Sovocool, US EPA, NERL, Las Vegas, NV

Molecular Characterization of Anthropogenic PAHs in sediments of the Thea Foss/Wheeler Osgood Waterways, Tacoma, Washington
Scott A. Stout, Ph.D., Battelle, Duxbury, MA
Allen D. Uhler, Ph.D., Battelle, Duxbury, MA  

Approaches for Fingerprinting PCBs at Contaminated Waste Sites
Henry Camp, Arthur D. Little, Inc., Cambridge, MA
Eric Butler, Gradient Corporation, Cambridge, MA
Linda Cook, Arthur D. Little, Inc., Cambridge, MA  

Sourcing PAH with Innovative Methodologies
Stephen Emsbo-Mattingly, Battelle Memorial Institute, Duxbury, MA
Andrew Coleman, Ph.D., Electric Power Research Institute, Palo Alto, CA
Arthur Chin, Ph.D., ExxonMobil Environmental Remediation, Linden, NJ 
Scott Stout, Ph.D., Battelle Memorial Institute, Duxbury, MA
Paul Boehm, Ph.D., Battelle Memorial Institute, Duxbury, MA
Allen Uhler, Ph.D., Battelle Memorial Institute, Duxbury, MA
Kevin McCarthy, Battelle Memorial Institute, Duxbury, MA

Distribution of Lead Contamination in Soils of Florida Shooting Ranges
Ming Chen, University of Florida, Belle Glade, FL
Lena Q. Ma, University of Florida, Gainesville, FL
Samira H. Daroub, University of Florida, Belle Glade, FL
Xinde Cao, University of Florida, Gainesville, FL
Willie G. Harris, University of Florida, Gainesville, FL  

A Comparison of XRF Data with ICP/AA Data

Timothy J. Boyle and John Fitzgerald, MA Dept. of Env. Protection, 205A Lowell Street, Wilmington, MA  01887, Tel: 978-661-7683, Fax: 978-661-7615

For the past three years MADEP has been using a Niton Corporation XL-700 series multi-element X-ray fluorescence unit (XRF) to collect data on metals concentrations in soil during state funded response actions.  The Department has been primarily interested in lead and arsenic concentrations in surface soils at these sites.  During the course of these efforts, agency staff have submitted split samples for laboratory analysis for three sites: 13 samples from a former electronic manufacturing site, 59 samples from a major railroad maintenance yard and 13 samples from a former junk yard that has been redeveloped for residential use.  The XRF was used as a survey/screening instrument and as a replacement for laboratory analysis in situations where laboratory accuracy was not needed and/or time was a critical factor.  The procedure used when screening soil samples was to combine 5 grab samples in a sealed polyethylene bag and shake for at least one minute.  The XRF unit was then placed on the bag in three locations to generate three individual contaminant concentrations that were then used to develop an average concentration for the bag/sampling grid.  A sub-sample of this bag was subsequently obtained and analyzed at a laboratory using standard Inductively Coupled Plasma (ICP) and/or Atomic Absorption (AA) Spectrometry procedures. A second analysis/preparation technique was used to generate data with better accuracy than that obtained in the screening mode.  The preparation of these samples consisted of grinding and sieving the samples to ensure a uniform particle size and to attempt to homogenize the sample prior to its analysis.  In addition, these samples were placed in analysis cups developed and obtained from Niton Corp.  The accuracy of the unit when used for lead contamination has been excellent.  The accuracy when assessing arsenic contamination was found to be variable depending on the lead concentration and the mode in which the unit was used.  The best results were achieved when the soil samples were prepared prior to their XRF analysis.

Characterization or Identification of Organic Compounds by Ion Composition Elucidation (ICE)  using Gas Chromatography/High Resolution Mass Spectrometry

Andrew H.  Grange, Ph. D. and G.  Wayne Sovocool, Ph. D., Environmental Sciences Division, NERL, U.S. EPA, PO Box 93478, Las Vegas, NV 89193-3478

Only a small fraction of the compounds found in contaminated sites and water supplies is found in mass spectral libraries or has known toxicological effects. The EPA lists 2800 high production volume chemicals.  These compounds, byproducts, and degradation products might be found in drinking water sources, air, and contaminated sites.  Identification of these compounds is necessary to assess risk to humans and aquatic ecosystems. Hence, there is a need for more powerful analytical techniques to identify such compounds.  To limit tedious pre-analysis fractionations, compound identification techniques must isolate signals from low-level contaminants in complex mixtures.  Excellent component separation is realized by high resolution gas chromatography (separation in time) coupled to high resolution mass spectrometry (selection by exact mass).

Ion Composition Elucidation (ICE) employs a software adaptation for double focusing mass spectrometers to measure the exact masses and relative abundances of the mass peak profiles of monoisotopic ions and the profiles higher in mass by 1 and 2 amu that arise from heavier isotopes such as ¹³C, ¹⁵N, ¹⁸O, and ³⁴S.  Three measured exact masses and two relative abundances are entered into a Profile Generation Model to provide the composition of the molecular ion or fragment ion.  Tables of ion compositions limit the number of possible compounds that could produce the mass spectrum and make feasible library searches of chemical and commercial literature to reach tentative identifications.  If a standard can be obtained, the tentative identification can be confirmed.  If not, the compound can be tracked to its source using the compound’s retention time and ion compositions, which provide greater specificity than a low resolution mass spectrum.

Two applications of ICE will be discussed: identification of isomeric compounds found in a municipal well that served Toms River, NJ, and characterization of two families of compounds found in Superfund sites S one chemical byproducts and one of  microbial origin.

Notice: The U.S. Environmental Protection Agency (EPA), through its Office of Research and Development (ORD), funded this research and approved this abstract as a basis for an oral presentation.  The actual presentation has not been peer reviewed by EPA.

Molecular Characterization of Anthropogenic PAHs in Sediments of the Thea Foss/Wheeler Osgood Waterways, Tacoma, Washington

Scott A. Stout, Ph.D. and Allen D. Uhler, Ph.D., BATTELLE, 397 Washington St., Duxbury, MA  02332, Tel: 781-934-0571, Fax: 781-934-2124  

The character of anthropogenic polycyclic aromatic hydrocarbons (PAHs) in surface and near-surface sediments of the Thea Foss and Wheeler-Osgood Waterways in Tacoma, Washington, were investigated with the objective of determining the general source(s).  Our investigation differed from previous studies that had focused on the remediation needs of the Waterways.  In this study, 42 sediment samples from the Waterways were collected and analyzed for their (1) concentration of 43 individual or groups of PAH, (2) total extractable hydrocarbon “fingerprint” and concentration, (3) grain size and (4) total organic carbon content.  Analysis of the sediment data, including comparisons to standard reference materials, indicated that all but two samples contained PAH derived from a pyrogenic source(s), i.e., a non-petroleum source(s).  The high concentrations and characteristic distributions of PAH in some sediment samples were consistent with the occurrence of coal-derived liquid(s), particularly in some sediments proximal to the historic coal gasification operations near the head of the Thea Foss Waterway.  Most sediment samples throughout the Waterways contained PAH distributions attributable to varying degrees of weathering and/or mixing of pyrogenic source material(s), e.g., urban run-off, coal-derived liquids, or pitch.  Two sediment samples clearly containing PAH derived from petrogenic sources, i.e., petroleum-derived sources, were found near the head of the Thea Foss Waterway. 

It was apparent that the PAH in sediments throughout the Thea Foss and Wheeler-Osgood Waterways were overwhelmingly derived from pyrogenic sources, which may be, in part, attributable to historic coal gasification operations.  It is reasonable that decades of sediment re-distribution and past dredging activities within the Waterways have contributed to the spreading and mixing of this contamination with other persistent pyrogenic sources, e.g., urban run-off. 

Approaches for Fingerprinting PCBs at Contaminated Waste Sites

Henry Camp, Arthur D. Little, Inc., Acorn Park, Cambridge, Massachusetts 02140,Tel: 617-498-5000 Fax:  617-498-7200, Email: camp.henry@adlittle.com
Eric Butler, Gradient Corporation, 238 Main Street, Cambridge, Massachusetts 02142, Tel: 617-395-5000, Fax: 617-395-5001, Email: ebutler@gradientcorp.com
Linda Cook, Arthur D. Little, Inc., Acorn Park, Cambridge, Massachusetts 02140, Tel: 617-498-5000, Fax: 617-498-7296, Email: cook.linda.l@adlittle.com

Contamination by polychlorinated biphenyls (PCBs) in the environment, while not as frequently encountered as petroleum, poses a specific set of issues. From a regulatory point of view, sites involving PCBs take on generally higher importance because of the lower action thresholds. The regulatory framework also adds a higher financial burden to the cleanup and disposal of contaminated material. In addition (the debate over the risks to human and ecological health notwithstanding), PCBs are perceived by the public as a serious threat.  Allocation of liability in cases involving PCB are obviously sensitive. Many analytical methods have been developed to identify and measure PCBs in environmental samples. Early approaches utilized basic gas chromatography with compound-specific detectors. These were improved with the refinement in sample preparation and separation technology to minimize analytical interference. Current advanced methods couple sample preparation procedures with mass spectrometry (GC/MS) instrumental techniques and allow a cost-effective means to definitively measure a large subset of the possible 209 PCB congeners. Similar to the analysis for individual hydrocarbons to fingerprint petroleum contaminants, congener-specific analysis can be used to identify and measure individual PCB congeners. This allows for better evaluation of PCB patterns or signatures and for the identification of sample relationships. Further, combined with process knowledge and site history, original PCB sources – Aroclor and other PCB containing fluids and solids - can be identified.  When supported by a scientific understanding of changes due to environmental weathering, PCB source identification can be a central argument in allocation disputes. The paper will discuss use of congener-specific analysis in environmental investigations.  It will present the analytical technique, its limitations, and how the data can be interpreted.  The effects of weathering and the identification of stable, Aroclor-specific source ratios will be presented.  Select case studies will be referenced to illustrate the applications.  Approaches for developing supporting lines of evidence, such as co-contaminants, formulation and process knowledge, and site history, will also be discussed.

Sourcing PAH in Sediments with Innovative Methodologies

Stephen Emsbo-Mattingly, M.S., Battelle Memorial Institute, 397 Washington Street, Duxbury, MA 02332, Tel: 781-934-0571
Andrew Coleman, Ph.D., Electric Power Research Institute, 3412 Hillview Avenue, Palo Alto, CA 94304, Tel: 650-855-2249
Arthur Chin, Ph.D., ExxonMobil Environmental Remediation, 1900 East Linden Ave, Linden, NJ  07036, Tel: 908-474-7395
Scott Stout, Ph.D., Paul Boehm, Ph.D., Allen Uhler, Ph.D., and Kevin McCarthy, Battelle Memorial Institute, 397 Washington Street, Duxbury, MA 02332, Tel: 781-934-0571

Distinguishing the origin of pyrogenic PAH from multiple sources in sediment presents numerous technical challenges.  Generally, the chemical signatures of natural, point and non-point PAH sources are potentially very similar.  The effects of environmental weathering and matrix interferences in environmental media often confound the signature of various proximate sources.  Consequently, multiple lines of environmental forensic evidence and the creative use of alternative measurement techniques are required to isolate an individual PAH source among others.

Several emerging environmental forensic methodologies have been reviewed and tested for identifying the sources of pyrogenic materials in the environment generated by the manufacture of gas, coke, and tar products in the presence of urban background.  The demonstrated effectiveness of these methods in sediment samples offers similar opportunities for source identification projects involving surface and subsurface soils in the future.  The analytical methods tested include alkylated PAHs (GC/MS), biomarkers (GC/MS), organic petrology, compound-specific isotope ratio mass spectrometry (GC/IRMS) and Fourier transformed ion cyclotron resonance mass spectroscopy (FTICRMS).  The interpretive techniques include chemical fingerprinting, principal components analysis (PCA), diagnostic ratios, organic petrography and fragmentation analysis.

Distribution and Mobility of Lead Contamination in Soils of Florida Shooting Ranges

Ming Chen, University of Florida, Everglades Research and Education Center, 3200 E. Palm Beach Road, Belle Glade, FL, 33430, Tel: 561-993-1527, Fax: 561-993-1528, Email: mchen@mail.ifas.ufl.edu
Lena Q. Ma, Soil and Water Science Department, University of Florida, Gainesville, FL32611-0290, Tel: 352-392-9063, Fax: 352-392-3902
Samira H. Daroub, University of Florida, Everglades Research and Education Center, 3200 E. Palm Beach Road, Belle Glade, FL, 33430, Tel: 561-993-1593, Fax: 561-993-1528
Xinde Cao, Soil and Water Science Department, University of Florida, 2169 McCarty Hall, Gainesville, FL 32611-0290, Tel: 352 392-1951, Fax: 352-392-3902, Email: xcao@mail.ifas.ufl.edu
Willie G. Harris, Soil and Water Science Department, University of Florida, 2169 McCarty Hall, Gainesville, FL , 32611-0290, Tel: 352 392-1951, Fax: 352-392-3902, Email: wghs@gnv.ifas.ufl.edu

Lead is ranked as the No.2 priority hazardous substance on the Agency for Toxic Substances and Disease Registry and the U.S. Environmental Protection Agency (USEPA) priority list of hazardous substances. Lead contamination in soils of several outdoor shooting ranges (rifle, pistol and shotgun) from the use of lead shot/bullets was evaluated by collecting grid soil samples and analyzing total-recoverable (EPA Method 3051a) and Toxicity Characteristics Leaching Procedure (TCLP) Pb in these soils. Preliminary results indicated that high concentrations of Pb were generally present and the soil leached more lead than what is acceptable by the Resource Conservation and Recovery Act (RCRA) and would be characterized as hazardous wastes. The highest Pb contamination (total Pb = 95,388 ppm) was detected in the backstop berm of a 50-yard pistol range that has been in operation for over 30 years. Elevated Pb levels were also determined in plant and surface water samples at those ranges. Sequential fractionation and X-ray diffraction analyses revealed that hydrocerussite (Pb₃(CO₃)₂(OH)₂) was the primary crystal Pb mineral existed in lead contaminated soils at most shooting ranges. Lead phosphate was formed in the soil of a shooting range with high concentration of phosphorous. Soil pH and organic matter are two most important factors affecting Pb weathering and transformation.  Lead did not migrate downward until being solubilized with organic matter at alkaline conditions.  Site-specific distribution and mobility of soil Pb contamination in different shooting ranges indicates a best management practices (BMPs) program needs to be developed, which is critical in assessing potential remedial alternatives.

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