Sponsored by Northeast Analytical

Interlaboratory Study on PCB Analysis of Natural Waters by Method 1668A
David R. Blye,  Environmental Standards, Inc., Valley Forge, PA

An Assessment and Overview of PCB and Congener Specific PCB Testing Methodologies
Jason Homrighaus, Northeast Analytical, Inc., Schenectady, NY

Compliant Analysis of Water, Wastes and Related Solid Environmental Samples Using Inductively Coupled Plasma Atomic Emission and Mass Spectrometry - A Critical Comparison of QA/QC Requirements of EPA and Standard Method Procedures
I.B. Brenner, Environmental Analytical Services, Jerusalem, Israel

The Nylon Plasticizer, N-(n-butyl)benzenesulfonamide, Misidentified as Diesel Contamination in Groundwater 
Steven D. Gregory, Lawrence Livermore National Laboratory, Livermore, CA

Low Thermal Mass Gas Chromatography – Analysis at MACH Speed          
Ann C. Casey, Northeast Analytical, Inc., Schenectady, NY

Lessons Learned on the Implementation of CRREL Multi-Increment Sampling (MIS) and Analysis by SW-846 Method 8330B   
Mark R. Koenig, USACE Project Chemist, Concord, MA

Risk-Based Characterization of Extractable Petroleum Hydrocarbon Contamination Using Comprehensive Two-Dimensional Gas Chromatography with Dean's-Switch Modulation
Robert G. Brown, Lancaster Laboratories, Lancaster, PA

Interlaboratory Study on PCB Analysis of Natural Waters by Method 1668A   

Julio A. Zimbron, GE Global Research, Environmental Technologies Lab, One Research Circle, Niskayuna NY 12302, Tel: 518 387-4309, Fax: 518 387-7563, Email: zimbron@research.ge.com
David R. Blye,  Environmental Standards, Inc., 1140 Valley Forge Road, PO Box 810, Valley Forge, PA 19482-0810, Tel: 610 935-5577, Fax: 610 935-5583, Email: dblye@envstd.com

Method 1668, Revision A (1668A) for polychlorinated biphenyl (PCB) single congener analysis uses high resolution gas chromatography combined with high resolution mass spectrometry.  Method 1668A includes estimated method detection limits as low as 4 pg/L for individual PCB congeners.  Despite the reported increased sensitivity of Method 1668A with respect to previous PCB analytical methods, test results using independent laboratories are not available.  The objective of this interlaboratory study is to provide estimates of measurement error for PCB analysis in natural waters using Method 1668A.  Due to the widespread use of solid-phase-extraction (SPE) for field-concentrating high volumes of natural waters, the study included two applications: (a) analysis of grab samples, and (b) high volume field sampling using SPE with XAD resin.  Samples were taken at two locations, where previously measured PCB concentrations differed by approximately two orders of magnitude.  Grab-low volume (4L) and SPE-high volume (~1000 L water) samples were taken at the location where a higher concentration previously had been reported, while a SPE-high volume sample (~1000 L) was taken at the location where a lower concentration previously had been reported.  Grab and SPE-high volume extract splits triplicates were sent to three commercial labs for analysis.  Analysis of variance indicated that results by the three labs on the “higher concentration site” samples (both grab samples and split extracts) were significantly different (C.L. = 95%), while results for the “lower concentration site” split extracts were not.   Reported lab-specific detection limits were different than those included in the method and varied widely among labs.  None of the three labs met all the QA/QC method provisions (i.e., chromatographic resolution, internal standard recoveries, spikes recoveries).  Laboratory and field blanks showed concentrations higher than the method detection limits.

An Assessment and Overview of PCB and Congener Specific PCB Testing Methodologies 

Jason Homrighaus, Northeast Analytical, Inc., 2190 Technology Drive, Schenectady, NY  12308, Tel: 518-346-4592, Fax: 518-381-6055
Robert E. Wagner, Northeast Analytical, Inc., 2190 Technology Drive, Schenectady, NY  12308, Tel: 518-346-4592, Fax: 518-381-6055
Ann C. Casey, Northeast Analytical, Inc., 2190 Technology Drive, Schenectady, NY  12308, Tel: 518-346-4592, Fax: 518-381-6055

As the public health and ecological concerns surrounding PCBs in the environment grow and, as the extent of the problem becomes more apparent, efforts to identify and remediate sources of contamination take on greater significance.  Both health and environmental professionals face a daunting array of situations in which proper identification of sources of contamination is critical to evaluating environmental impact and determining the appropriate cleanup and protection measures.  The wide array of analytical tests available for PCB determination is not immediately apparent as many are not part of the formal EPA method system or are not widely used outside of specific regions or applications. 

To help clarify the scope of methods available, an evaluation of all current PCB testing methodologies was undertaken.  Specific attention was given to the following areas of interest; detection level capabilities, applicable matrices, ruggedness, cost, complexity, turnaround time, data format, data consistency, historical usage, current applications and regulatory considerations. 

A brief overview of all current methodologies as well as the history of PCBs and PCB method development will be presented.  The remaining discussion will delve into greater detail on the currently available PCB Congener methods.  These represent the current state of the art and are some of the least understood of the methods available.  Specific information will be presented on HRGC/HRMS (USEPA 1668/1668a), HRGC/ECD (USEPA 8082, Green Bay Congener) and HRGC/LRMS (USEPA 680, Lab Specific).   

Compliant Analysis of Water, Wastes and Related Solid Environmental Samples Using Inductively Coupled Plasma Atomic Emission and Mass Spectrometry - a critical comparison of QA/QC requirements of EPA and Standard Method Procedures

I.B.Brenner, Environmental Analytical Services, 9 Dishon Street , Malkha, Jerusalem , Israel , 96956, Email: Brenner@cc.huji.ac.il

Inductively coupled plasma atomic emission and mass spectrometry (ICP-AES and ICP-MS) is widely employed for compliant determination of trace, minor, and major element constituents in all types of water, liquid and solid wastes - from natural surface and ground water to acid mine waters, to industrial effluents and hazardous solid wastes. As a result of their excellent analytical characteristics, these instrumental technologies and compliant and performance-based methods have been specified by regulatory agencies and adopted in commercial accredited and research laboratories.

However, there are several critical differences in QA/QC requirements for these analytical tasks using EPA 200.7, EPA 200.8, EPA 200.5 and SW 846 ( 6010C and 6020A) and SM ICP-AES and MS procedures. In this presentation, a comparison will be made of the contrasting differences in terms of sample throughput and accuracy. For example the following figures of merit will be addressed: range of elements, instrument and method limits of detection, minimum limits of determination, multielement calibration and calibration stabilities (CCV, ICV) linear dynamic ranges, compensation of spectroscopic and non spectroscopic interferences), and QA/QC and ISO 17025 requirements.

The Nylon Plasticizer, N-(n-butyl)benzenesulfonamide, Misidentified as Diesel Contamination in Groundwater 

Steven D. Gregory, B.S. Biology, Lawrence Livermore National Laboratory, P.O. Box 808, L-528, Livermore, CA 94551, Tel: 925-422-9904, Email: gregory2@llnl.gov
Harry R. Beller, Ph.D. Civil and Environmental Engineering, Lawrence Livermore National Laboratory, P.O. Box 808, L-542, Livermore, CA 94551, Tel: 925-422-0081, Email: beller2@llnl.gov
Victor Madrid, M.S. Geology, Lawrence Livermore National Laboratory, P.O. Box 808 , L-530, Livermore, CA 94551, Tel: 925-422-9930, Email: madrid2@llnl.gov

During groundwater investigations at Lawrence Livermore National Laboratory (LLNL) Site 300, a previously unidentified chemical was discovered.  Diesel range organic compounds were identified in 22 wells using EPA Method 8015.  However, such widespread diesel contamination was not consistent with site data.  Upon detailed examination of gas chromatograms and analyses using EPA Method 8270, it was determined that what had been interpreted as diesel fuel was predominantly N-(n-butyl)benzenesulfonamide (BBSA).  BBSA, a plasticizer used in the manufacture of nylon tubing, has a retention time that overlaps with diesel range compounds.  All wells in which BBSA was identified were equipped with dedicated pumps and nylon discharge/air-supply tubing.  Following the discovery of BBSA, a new analytical method involving liquid chromatography/ tandem mass spectrometry (LC/MS/MS) was developed at LLNL to confidently identify and accurately quantify the BBSA in groundwater.  The LC/MS/MS method allows direct injection of samples into the instrument and has a detection limit of <1 µg/L.  Using the 8270 method, BBSA could be positively identified, but concentrations only estimated.  All wells equipped with nylon tubing were re-sampled and analyzed by LC/MS/MS.  BBSA concentrations ranged from 800 to 531,000 µg/L.  Experiments conducted to determine the origin of the BBSA included: (1) time series sampling of two wells, and (2) recirculation testing to evaluate BBSA leaching potential.  Both experiments indicated that the BBSA was indeed related to the equipment and was not a groundwater contaminant.  The equipment supplier confirmed the nylon was the source of the BBSA through a leach test.  Thus, we observed that non-diesel compounds can be erroneously identified as diesel fuel in routine analyses, and chemicals leaching from equipment may be incorrectly interpreted as groundwater contaminants. 

This document was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor the University of California nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or the University of California. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or the University of California, and shall not be used for advertising or product endorsement purposes.
UCRL-ABS-227147  

Low Thermal Mass Gas Chromatography – Analysis at MACH Speed

Robert E. Wagner, Northeast Analytical, Inc., 2190 Technology Drive, Schenectady , NY 12308, Tel: 518-346-4592, Fax: 518-381-6055
Ann C. Casey, Northeast Analytical, Inc., 2190 Technology Drive, Schenectady , NY 12308, Tel: 518-346-4592, Fax: 518-381-6055
Inga Hotaling, Northeast Analytical, Inc., 2190 Technology Drive, Schenectady , NY 12308, Tel: 518-346-4592, Fax: 518-381-6055

Gas Chromatography (GC and GC/MS) analysis has been the mainstay for the analysis of regulated organic contaminates in the environmental field. Numerous advancements have occurred in GC instrumentation that include improvements for injectors, detectors, automation, software, and GC column choices. Although many advancements have been made in GC technology, very little has changed for column oven design and operation. Traditionally, GC column ovens are still large, with huge power requirements, limited temperature programming rates and long cool down times, dictating the overall speed of analysis.

Recently Low Thermal Mass (LTMÔ) technology, developed by RVM Scientific, has become commercially available from Gerstel as the Modular Accelerated Column Heater (MACHÔ). This new technology has dramatically increased the speed of analysis while still maintaining chromatographic resolution. Key to this new technology is that LTMÔ hardware can be retrofitted to GCs currently in use, providing ultra fast temperature programming with unprecedented cool down time and extremely low power consumption.

This presentation will discuss data obtained from the MACHÔ and lessons learned for dual column PCB and Pesticide analysis, column selection and optimization, and retrofitting MACHÔ hardware to instrumentation not currently supported by the manufacturer. Several case studies will be discussed on how fast GC analysis can provide benefit to the contract lab industry as well as the environmental professional who utilizes lab services.

Lessons Learned on the Implementation of CRREL Multi-Increment Sampling (MIS) and Analysis by SW-846 Method 8330B

Mark R. Koenig, USACE Project Chemist, New England District, 696 Virginia Road, Concord, MA  01742-2751, Tel: 978-318-8312, Fax: 978-318-8614, Email: mark.r.koenig@usace.army.mil
Laurie Ekes, Project Chemist, Environmental Chemical Corporation, PB 519 Otis ANGB, MA  02542, Phone; 508-968-5620, Email, lekes@ecc.net
Brad Chrigwin, HPLC Chemist, STL-Burlington, VT, 30 Community Drive, Suite 11, South Burlington, VT  05403, Tel: 802-660-1990, Fax: 802-660-1919, Email: bchrigwin@stl-inc.com
Alan Hewitt, Research Scientist, US Army Engineer Research and Development Center, Cold Regions Research Engineering Laboratory (CRREL), 72 Lyme Road, Hanover, NH 03755-1290, Tel: 603-646-4388, Fax: 603-646-4785, Email: Alan.D.hewitt@erdc.usace.army.mil
Thomas F. Jenkins, Research Scientist, US Army Engineer Research and Development Center, Cold Regions Research Engineering Laboratory (CRREL), 72 Lyme Road, Hanover, NH 03755-1290, Tel: 603-646-4385, Fax: 603-646-4785
Marrianne Walsh, Research Scientist, US Army Engineer Research and Development Center, Cold Regions Research Engineering Laboratory (CRREL), 72 Lyme Road, Hanover, NH 03755-1290, Tel: 603-646-4666, Fax: 603-646-4785

A Multi-Increment Sampling (MIS) approach and modified analytical method 8330B have been recommended for sampling and analysis of explosive compounds by the U.S. Army Corps of Engineers Cold Regions Research and Engineering Laboratory (CRREL).  This method was recently adopted by EPA in their Small Arms Range (SAR) Work Plans. The U.S. Army Corps of Engineers, New England District (NAE) has been working closely with CRREL, the Army Environmental Command Impact Area Groundwater Study Program (IAGWSP), MassDEP, EPA, Environmental Chemical Corporation (ECC), and TAL VTB (formerly STL-VT) on implementing the Multi-Increment Sampling (MIS) approach and modified analytical method at the Massachusetts Military Reservation (MMR), Camp Edwards , MA. 

The MIS and Method 8330B have been implemented at Small Arms Ranges (SARs) and Gun and Motar (G&M) firing positions and target locations.  The MIS approach has mainly been applied to explosives. The several different multi-increment sampling (MIS) and grinding techniques that were evaluated during implementation will be discussed.

Specific MMR project requirements were developed based on the MMR Program DQO’s required. These DQO’s included dual column confirmation using the Phenyl Hexyl confirmatory column, an extended target analyte list including NG, PETN, 2,4-DANT, 2,6-DANT, picric acid, as well as the RDX degradation by products, MNX, DNX and TNX. All 22 Target explosives and propellants have been resolved in one analysis run on both the primary C-18 and confirmatory phenyl hexyl analytical HPLC columns. STL-VT has also been using the Photo Diode Array (PDA) detector or UV spectral detection method for an additional level of confirmation. The closest matching concentration standard PDA spectra are compared to the sample PDA UV spectra for any dual column confirmed explosive target analyte HPLC peak.

The main focus on this presentation will be on the lesson learned during the implementation of the CRREL Multi-increment Sampling and analysis by SW-846 Method 8330B. The analytical method development used to meet the MMR project specific DQO’s will be discussed in detail. Also, the successes of the multi-increment sampling will be highlighted by review of actual SAR sampling and analysis data. The pros and cons encountered will be evaluated throughout the presentation.  

Risk-Based Characterization of Extractable Petroleum Hydrocarbon Contamination Using Comprehensive Two-Dimensional Gas Chromatography with Dean's-Switch Modulation

Robert G. Brown, Lancaster Laboratories, 2425 New Holland Pike, Lancaster, PA 17605, Tel: 717-656-2300, Fax: 717-656-2681, Email: rbrown@lancasterlabs.com
John V. Seeley, Dept. of Chemistry, Oakland University, 2200 Squirrel Rd, Rochester, MI 48309, Tel: 248-370-2329,  Fax: 248-370-2321, Email: seeley@oakland.edu
James D. McCurry, Ph.D., Agilent Technologies,  2850 Centerville Rd, Wilmington, DE 19808, Tel: 302-633-7375, Email: james_mccurry@agilent.com
Stacy K. Seeley, Kettering University , Department of Science and Mathematics, Flint , MI 48504 , Email: sseeley@kettering.edu
Steve V. Bandurski, (graduate student), Oakland University ; 2200 Squirrel Rd , Rochester , MI 48309

Approximately ten years have passed since the first generation of risk-based petroleum methods was developed and put into production in the environmental laboratory. However, the precise amounts of the several different solvents needed, in addition to variables affecting the fractionation medium often result in “breakthrough” of target compounds into the wrong fraction(s) and/or contamination of the final extract(s). Advances in gas chromatographic and flow control technologies can now be used to replace the tedious sample preparation techniques previously required to obtain the separate sample extracts (“fractions”) used for site characterization/assessment. 

Soil/wastewater samples are extracted using methylene chloride.  Extracts are dried with sodium sulfate, concentrated and treated with silica gel to remove polar, non-petroleum related compounds.  The final extract is then analyzed using a two-dimensional gas chromatograph (2-D GC; GC x GC) designed to separate the aliphatic and aromatic species present in the extract using flame ionization detection (FID). 

This new approach meets the original intent of the Massachusetts state and TPH Working Group methods to measure and quantitate collective aliphatic and aromatic hydrocarbon concentrations, as well as target polynuclear aromatic hydrocarbons (PAHs).

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