Michael Berger, Simmons College, 300 The Fenway, Boston, MA 02115, Tel: 617-521-2722, Email: bergerm@simmons.edu
Laura Stupi, Thermo Fisher Scientific, 900 Middlesex Turnpike, Building 8, Billerica, MA, 01821, Tel: 978-670-7460, Fax: 978-670-7422, Email: laura.stupi@thermofisher.com
Robert Schleicher, Thermo Fisher Scientific, 900 Middlesex Turnpike, Building 8, Billerica, MA 01821, Tel: 978-670-7460, Fax: 978-670-7422, Email: robert.schleicher@thermofisher.com

Copper Basin , located near the junction of Tennessee , Georgia , and North Carolina and the Muddy River in Boston , Massachusetts both present elevated levels of sulfur (S) in soils and sediments. The Copper Basin was once an active mining site and the elevated sulfur presence there is a result of pollution from the mining activities. One of the first steps is the identification and removal of S rich soils (greater than 2%) which are thought to have the greatest potential for acid mine drainage. The Muddy River is the backbone of the Emerald Necklace and the historic landscape surrounding Boston which has accumulated sediments with high levels of metals, petroleum hydrocarbons and decaying vegetation.  The selection of a remediation strategy that minimizes sulfur volatile emissions during sediment dredging operations could be aided by a sulfur analysis of Muddy River sediments.

Previously, sulfur (S) has been considered too light an element to be detected with portable X-ray Fluorescence (XRF). However, with recent technological advances it is now a possibility to detect and sometimes quantify sulfur. The detection limit of sulfur had previously been established at approximately 1%, but new He-purge capabilities are pushing that number down to one-third of that value. Data will be presented from investigations of Copper Basin soils and Muddy River sediments to demonstrate the capabilities and effectiveness of the analyzer for site characterization and remediation activities.  Analytical results obtained with XRF are compared to traditional Sulfur analytical methods.

Analysis Method for Congener Isomer by Series of Polar and Non-polar Column GC Combination

Jong-Heub Jung, Seoul Metropolitan Government research Institute of Public Health and Environment, 202-3 Yangjae-dong Sucho-gu, Seoul 137-130 Korea, Tel : 82-2-570-3130, Fax: 82-2-570-3134
Seok-Won Eom, Seoul Metropolitan Government research Institute of Public Health and Environment, 202-3 Yangjae-dong Sucho-gu, Seoul 137-130 Korea, Tel: 82-2-570-3221, Fax: 82-2-570-3134
Seung-Gu Ahn, School of Environmental Engineering and Science, University of Seoul, 90 Jeonnong-dong, Dongdaemun-gu, Seoul 130-743 Korea, Tel : 82-2-2210-2432, Fax : 82-2-2244-2245

In the environment, there are so many substances related with human health that should be known whether present or not and how much. Current analysis methods for complicate environment samples such as dioxin, PCB, VOC etc, have had some problem. In case of dioxin analysis methods, the problem is that not all of 17 toxic isomers could separate with single column. Therefore, 7 of dioxins and 10 of furans should be separated and quantified with polar and non-polar column one by one exactly. To resolve these problem pre-treated samples should be analyzed with more than 2 columns, which needs much more time and causes increasing cost due to readjustment of sensitivity and calibration curve. This study  was to find out the method that can separate toxic 2,3,7,8-chlorinated dioxin with one time analysis quickly by combination with 2 different columns without the problem of existing single column method, which is difficult to separate isomers exactly. Polar SP-2331 column and non-polar DB-5MS column were connected in-line using 2 units of GC, maintaining the optimum temperature for each polar and non-polar column, 350℃ and 275℃ respectively. With one shot of sample, after first GC with relatively higher temperature separated substances from low chloride to high chloride using 60m non-polar DB-5MS column, second GC with relatively lower temperature separated substances using polar SP-2331 column, which had various length of 1m, 2m, 3m, 4m, 5m, 6m and 10m to see the change of resolution degree. The resolution degree of specific isomer from 2, 3, 7, 8-chlorinated dioxin could be improved by changing the elution characteristics.

Congener Specific Analysis of PCBs By High Resolution GC with Low Resolution MS – The Need For a Standardized Method

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

PCB manufacture and distribution was banned in the USA in 1977, but to this day they remain a ubiquitous contaminate. PCBs are the focus of remediation efforts and are intensely monitored in natural resources such as groundwater, surface water, sediments, soils, fish, wildlife, and air.

PCBs were manufactured as AroclorÒ formulations in the United States. The AroclorsÒ were produced to contain a fixed weight percent of chlorinated biphenyl to yield fluids that were useful in applications such as transformers, capacitors, heat transfer systems, hydraulic systems, and sealants. The PCB congener patterns exhibited by the original AroclorsÒ can be accurately and routinely measured by traditional analytical techniques (GC/ECD), with pattern matching the key tool in all routine methods of analysis.

As PCB entered the environment changes occurred to the original PCB patterns that make routine determinative methods ineffective in accurately identifying and quantifying PCB concentrations. Changes to the original PCB congener patterns have been mediated by; (1) physical changes such as mixing and evaporation, (2) extensive biotransformation by bacteria, and (3) alteration in the food web by bioaccumulation and enzymatic metabolism. Also, in many situations, PCBs exist with other environmental contaminates such as pesticides, Chlordane, Toxaphene, PCTs, and PCNs that will interfere with measurement by routine techniques.

This presentation will describe and present information on development of a gas chromatographic low resolution mass spectrometry method. Data will be presented on samples that have proven to be difficult to analyze by traditional GC/ECD techniques. Information will also be provided on certified standard reference materials (SRMs) and the accuracy of this method in quantifying PCB congeners. Lastly, we will demonstrate the sensitivity of the method by employing large volume injection (LVI) techniques to analyze low concentration samples.

1,4-Dioxane:  The Impact of Analytical Method – A Case Study

P. James Linton, Blasland, Bouck and Lee, Inc., 3350 Buschwood Park Drive #100, Tampa, Florida 33618, Tel: 813-933-0697, Fax: 813-932-9514, Email: pjl@bbl-inc.com
Tina Armstrong, Lockheed Martin Company, Bethesda , MD
John Alonso, Blasland, Bouck and Lee, Inc., 3350 Buschwood Park Drive #100, Tampa, Florida 33618, Tel: 813-933-0697, Fax: 813-932-9514, Email: jca@bbl-inc.com
Ben Foster, Blasland, Bouck and Lee, Inc., 3350 Buschwood Park Drive #100, Tampa, Florida 33618, Tel: 813-933-0697, Fax: 813-932-9514, bfoster@bbl-inc.com

1,4-Dioxane (C4H8O2, CAS No. 123-91-1) often has been used with chlorinated solvents, particularly 1,1,1-trichloroethane (TCA), as a stabilizer and corrosion inhibitor.  In recent years, evaluation of the presence of this compound where chlorinated solvent contamination exists has become of increasing concern because of the low regulatory concentration, resistance to biodegradation, and water solubility that limits treatment effectiveness by methods normally employed for volatile organic compounds.

Commercial laboratories commonly analyze for 1,4-dioxane in groundwater by either EPA Method 8260 or 8270, though the latter method does not list 1,4-dioxane.  Method 8260 does not generally achieve reporting limits that meet regulatory concentrations.  Determination of 1,4-dioxane in water at low detection levels may also be accomplished using a modified approach to Method 8270 with isotope dilution.  Because of time and sample volume concerns, many laboratories have begun analyzing for 1,4-dioxane using a modified Method 8260 with Specific Ion Monitoring (SIM) GC-MS to improve the detection limits. 

During a recent characterization sampling at a central Florida site with groundwater impacted by chlorinated volatile organic compounds and 1,4-dioxane, split samples of groundwater were collected and analyzed by both Method 8270 and 8260 SIM.  The difference in reported concentrations of 1,4-dioxane by the two methods was significant, sometimes by orders of magnitude, creating a potentially severe regulatory impact.  A study was initiated to evaluate the effect of the different analytical methods on reported concentrations.

This paper presents an evaluation of the comparison of Method 8260 SIM, Method 8270, and Method 8270 with isotope dilution using native samples, multiple-level spike addition, and multiple-concentration laboratory control sample analysis to evaluate the overall accuracy and precision of the three methods.  Potential interference by other compounds that may effect the reported concentration by Method 8260 SIM was also evaluated.

Determination of Acidic Pharmaceutically Active Compounds in Seawater by on Field Solid Phase Extraction and Liquid Chromatography ― Tandem Mass Spectrometry

Yen Ling Tan, Jie Zhang,Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543 and Tropical Marine Science Institute, National University of Singapore, 14 Kent Ridge Road, Singapore 119223, Email: g0403421@nus.edu.sg
Hian Kee Lee, Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543
Jeffrey Philip Obbard, Tropical Marine Science Institute, National University of Singapore, 14 Kent Ridge Road, Singapore 119223

An in-field, solid phase extraction (SPE) procedure for the determination of pharmaceutically active compounds in large volume of seawater has been developed.  In this study, ≥1L of seawater sample was collected using an on-vessel pump.   An HLB polymeric SPE catridge (1g) was used directly for extraction of the sample. In the laboratory, SPE extract is analyzed by using Liquid Chromatography- Electrospray Ionization tandem mass spectrometry (LC-ESI-MS-MS). . The API 4000 tandem mass equipped with an atmospheric pressure chemical ionization source and operated in multiple reaction monitoring (MRM) mode. An Agilent 1100 equipped with a phenyl-hexyl column is used to introduce the sample to the MS. A 2 mM ammonium acetate buffer solution (pH 5.5) in a methanol gradient was used. The method has been used to determine several pharmaceutically active compounds in seawater samples from Singapore with good recoveries (greater than 80% in most cases). Among these target analytes, ketoprofen, naproxen and clofibric acid have been detected in the lower ng/l range. Data are presented for Singapore coastal seawaters and compared to available international data sets.  

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