X-ray Fluorescence vs Inductively Coupled Plasma for Metals Analysis: Can XRF be a Substitute for ICP?
Jay Clausen, US Army Corps of Engineers, Hanover, NH

Perfluorinated Compounds in Surface Waters of the Pacific Northwest by HPLC/MS/MS Detection
Michael A. Erickson, Columbia Analytical Services, Inc., Kelso, WA

Mass DEP's Evaluation of Laboratory Performance Based on a Large VOC Double-Blind Study
R. Kendall Marra, Massachusetts Department of Environmental Protection, Boston, MA

Obtaining Representative PCB Site Data- Overcoming Common Field and Analytical Pitfalls 
Frank Ricciardi, Weston & Sampson Engineers, Inc., Peabody, MA

Using Quadrupole ICP MS Generated Stable Lead Isotope Ratios in Environmental Risk and Forensic Studies
Leonard Pitts, Alpha Woods Hole Labs, Raynham, MA

Analytical Considerations for Applying EPA Method 1668A for PCB Analysis on Soil and Sediment Investigations

David R. Blye, CEAC, Environmental Standards, Inc., 1140 Valley Forge Road, Valley Forge, PA, 19482-0810, Tel:  610-935-5577, Fax:  610-935-5583, Email: dblye@envstd.com
Rock J. Vitale, CPC, CEAC, Environmental Standards, Inc., 1140 Valley Forge Road, Valley Forge, PA, 19482-0810, Tel:  610-935-5577, Fax:  610-935-5583, Email: rvitale@envstd.com

Numerous groundwater, surface water, soil, and sediment investigations include characterization and subsequent remediation of PCBs in the environment.  Historically, environmental samples have been analyzed for PCB Aroclors using GC/ECD analytical methods.  Comparison of GC/ECD chromatographic patterns of samples to laboratory-generated PCB Aroclor standards has led to a variety of problematic reporting issues because PCBs released to the environment decades ago can undergo weathering, alteration or degradation to varying degrees depending on the environmental conditions.  For example, a common situation has been observed when a laboratory analyst believes PCB congeners are present in a sample but a chromatographic match to an Aroclor standard is not reasonable and the sample result is somewhat “inappropriately” reported as not detected.  Additionally, identification of Aroclor concentrations may not provide the best information for use in human health or ecological risk assessments.

As a result of these misleading Aroclor reporting problems and the need for congener specific information for risk assessment, application of high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) isotope dilution techniques to characterize and quantitate individual PCB congeners is gaining popularity.  Since 1999, significant attention has been focused on use of the US EPA’s Method 1668A for PCB congener analysis. This costly performance-based method is often viewed as the gold standard for PCB congener analysis; however, a number of pitfalls and limitations exist in the method that should be understood at the earliest stages of the project planning phase when US EPA Method 1668A is being considered.  The work presented will summarize the historic development of the US EPA Method 1668A, including the results of US EPA’s inter-laboratory validation study to validate the method, as well as the ramifications and current limitations of this analytical technique.

X-ray Fluorescence vs Inductively Coupled Plasma for Metals Analysis: Can XRF be a Substitute for ICP?

Jay Clausen, US Army Corps of Engineers, Environmental Research and Development Center, Cold Regions Research and Engineering Laboratory, 72 Lyme Road, Hanover, NH 03755-1290, Tel: 603-646-4597, Email: Jay.L.Clausen@erdc.usace.army.mil
Susan Taylor, US Army Corps of Engineers, Environmental Research and Development Center, Cold Regions Research and Engineering Laboratory, 72 Lyme Road, Hanover, NH 03755-1290, Tel: 603-646-4388, Email: Susan.Taylor@erdc.usace.army.mil
Alan Hewitt, US Army Corps of Engineers, Environmental Research and Development Center, Cold Regions Research and Engineering Laboratory, 72 Lyme Road, Hanover, NH 03755-1290, Tel: 603-646-4597, Email: Alan.D.Hewitt@erdc.usace.army.mil
Steve Larson, US Army Corps of Engineers, Environmental Research and Development Center, Environmental Laboratory, 3909 Halls Ferry Road, Vicksburg, MS 39180-2802, Tel: 601-634-3431, Email: Steven.L.Larson@erdc.usace.army.mil
Chuck Ramsey, Envirostat Inc., P. O. Box 636, Fort Collins, CO 80522, Tel: 970-229-9977, Email: chuck@envirostat.org
Bonnie Packer, US Army Environmental Center, 5179 Hoadley Road, Aberdeen Proving Ground, MD 21010, Tel: 410-436-6846, Email: Bonnie.Packer@aec.apgea.army.mil
Kim Watts, US Army Environmental Center, 5179 Hoadley Road, Aberdeen Proving Ground, MD 21010, Tel: 410-436-6843, Email: Kimberly.Watts@aec.apgea.army.mil

Metals in small arms range soils were evaluated on-site using hand-held X-ray fluorescence (XRF) instruments and in a laboratory by inductively coupled plasma (ICP) analysis.  The evaluation consisted of testing of two different types of XRF units (X-ray tube and radioactive isotopes technologies) and equipment from two different manufacturers.  Comparisons between real-time field measurements and laboratory post-processed samples (air-dried only or air-dried and ground) are in progress.  Finally, the XRF field results were compared with those obtained utilizing modified versions of the US Environmental Protection Agency (EPA) SW-846 Methods 3050B, 3051, 6010B, and 6020.  Replicate XRF analysis of soil samples and soil standards in the field indicates good agreement between the two different types of XRF instruments as well as the two equipment manufacturers.  Preliminary analysis of the data suggests good reproducibility between XRF measurements in the field (wet soil samples) and laboratory ICP analysis following air-drying and digestion of ground soil samples.  The advantage of using a field instrument such as an XRF instrument is the generation of real-time data allowing for decision-making in the field and the maximum utilization of time and resources.  In addition, if the quality of the data with the XRF can be demonstrated to be as accurate as the ICP then it may be possible to reduce sampling and analytical costs.

Perfluorinated Compounds in Surface Waters of the Pacific Northwest by HPLC/MS/MS Detection

Michael A. Erickson, Columbia Analytical Services, 1317 S. 13^th Ave., Kelso, WA, 98626, Tel: 360-577-7222, Fax: 360-636-1068, Email: merickson@kelso.caslab.com
Thomas L. Fillmore, Columbia Analytical Services, 1317 S. 13^th Ave., Kelso, WA, 98626, Tel: 360-577-7222, Fax: 360-636-1068, Email: tfillmore@kelso.caslab.com  

Perfluorinated compounds are widely used in manufacturing throughout the world for application of coatings on textiles and plastics, as surfactants and for insecticide applications.  These compounds have been shown to be persistent in the environment and bioaccumulate.  An HPLC electrospray-tandem mass spectrometry method has been developed to investigate the level of contamination of a number of perfluorinated compounds.  Eight compounds including perfluorooctanoic acid (PFOA) and perfluorooctanesulfonate (PFOS) were included to investigate the extent of contamination in surface waters throughout the Pacific Northwest.  Sixty sites were chosen from five different regions of the Pacific Northwest. This allowed for comparison of areas with various levels of manufacturing and commercial activities.  A range of sources from lakes, small streams and large rivers were also included for comparison.  By utilizing liquid-liquid extraction coupled with HPLC/MS/MS, ultra-low detection limits have been obtained.  The limit of quantitation was 1.0ng/L for all reported compounds.  This was the first study that examined the extent of contamination by perfluorinated compounds in waters of the Pacific Northwest of the United States.

Mass DEP’s Evaluation of Laboratory Performance based on a Large VOC Double-Blind Study

R. Kendall Marra, P.E., Massachusetts Department of Environmental Protection, Bureau of Waste Site Cleanup, 1 Winter Street, Boston, MA  02180, Tel: 617-292-5966, Fax: 617-292-5530, Email: kendall.marra@state.ma.us
John J. Fitzgerald, P.E., Massachusetts Department of Environmental Protection, Bureau of Waste Site Cleanup, 1 Winter Street, Boston, MA  02180, Tel: 617-292-5767, Fax: 617-292-5530, Email: john.j.Fitzgerald@state.ma.us

The Massachusetts Department of Environmental Protection (MassDEP) regulates the cleanup of contaminated sites in the state under a privatized program begun in 1993.  In the past 12 years, over 20,000 sites have been assessed and cleaned up under this system.  However, assessment and cleanup decisions are based upon test data from labs that are not specifically approved or monitored for this work.  That has lead to concerns over the quality of the analytical data used to support site cleanup decisions.  To address these concerns, MassDEP conducted a large double-blind laboratory evaluation study, involving 19 commercial laboratories located throughout New England that provide the majority of analytical support services to parties assessing and cleaning up hazardous waste sites in Massachusetts.  A “double-blind” study is one in which a laboratory is unaware that they have been sent samples that contain known concentrations of contaminants.  This study, believed to be one of the largest “undercover” investigations of analytical testing laboratories ever conducted in the United States, was undertaken by MassDEP as part of a multi-year/multi-component data enhancement effort, in order to obtain a direct, real world sense of data quality and reliability in its waste site cleanup program.

Obtaining Representative PCB Site Data – Overcoming Common Field and Analytical Pitfalls

Frank Ricciardi, P.E., Weston & Sampson Engineers, Inc, 5 Centennial Drive, Peabody, MA, 01960, Tel: 978-532-1900, Fax: 978-977-0100, email: ricciarf@wseinc.com
Thomas Veratti, Jr., ConTest Analytical Laboratories, 39 Spruce Street, East Longmeadow, MA, 01028, Tel: 413-525-2332, Fax: 413-525-6405, tveratti@contestlabs.com

The Toxic Substance Control Act (TSCA -40 CFR 761) contains stringent regulations for assessing and remediating sites contaminated with polychlorinated biphenyls (PCBs). These regulations include very detailed requirements for the collection and analysis of PCB samples. This paper will discuss common field and laboratory errors that could be detrimental to the goals of the assessment/remedial program and the usability of the analytical data including the following:

Field Sampling issues:

• Improper investigation sequence causing cross contamination

• Mismanagement of vehicular or heavy equipment traffic across the Site

• Improper decontamination methods

• Missing information on laboratory Chain of Custody such as field observation of odor (e.g. sulfur, petroleum, organic) sheen, or staining, concentration range assessed from previous Site data, and the required detection limits

• Lack of field Quality Assurance/Quality Control (QA/QC) samples such as field duplicates, MS/MSDs, and temperature, field and equipment blanks

• Failure to obtain the required approvals from USEPA

• Incorrect grid alignment for cleanup verification

Laboratory issues:

• Improper extraction methods (Sonication not allowed by TSCA)

• Interferences caused by sulfur or naturally occurring organics

• Excess water in sample requiring additional cleanup

• Unresolved mixtures of Aroclors and estimation of PCB concentrations

• Inability to meet project required data turn-around times (TAT) due to instrument down time, sample interferences, or unexpected high PCB concentrations

• Inability to meet required detection limits

• Poor batch QA/QC results including surrogate recoveries

We will present chromatograms from active TSCA-regulated cleanup sites that illustrate key issues presented above and discuss how proper field planning can result in the attainment of data quality objectives, regulatory compliance, and site closure.

Using Quadrupole ICP MS Generated Stable Lead Isotope Ratios in Environmental Risk and Forensic Studies

Leonard C. Pitts, Alpha Woods Hole Laboratories, 375 Paramount Dr., Raynham, MA 02767, Tel: 508-822-9300, Fax: 508-822-3288, Email: lpitts@alphalab.com

Stable lead isotope ratios can be used to identify sources of environmental contamination because the isotopic composition of lead varies depending on where it was obtained. Decay of naturally occurring radionuclides to the stable lead isotopes Pb-206, Pb-207 and Pb-208 over geologic time scales changes the abundance of these isotopes in the ore from which the lead was processed. A source of environmental lead contamination can be characterized based on these differences in isotopic ratios and used to identify contributions to far field sites. Thermal Ionization Mass Spectrometry (TIMS) has typically been used to determine isotope ratios, however, Quadrupole ICP MS is becoming increasingly more common in environmental laboratories and can also be used to generate isotope ratios, though the precision may not be as good. Two case studies are presented using quadrupole ICP MS generated isotope ratios to identify sources of lead contamination or using lead as a tracer associated with other contaminants. In the first case, two sea water samples, an effluent and far field sample, were shown to have different isotope ratios indicating that the effluent was either not the source of lead to the far field sample or significantly diluted. In the second case study, sediment cores were collected to examine the extent of contamination from a source containing high concentrations of lead, copper and zinc. Isotope ratios from the source lead were characterized and used to indicate the contribution to a far field core with high lead concentrations in the surface layer and periodic depositions at lower depths.

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