Analysis of Suspended Solids in the Muddy River Using XRF Instrumentation
Jesse Fejes, Simmons College, 300 The Fenway, Boston, MA
Amber Indoccio, Simmons College , 300 The Fenway, Boston , MA
Lauren Johnson, Simmons College , 300 The Fenway, Boston , MA
Sarah Rockwell, Simmons College , 300 The Fenway, Boston , MA 
Mei Tan, Simmons College , 300 The Fenway, Boston , MA
Michael Berger, Simmons College , 300 The Fenway, Boston , MA, Tel: 617-521-2722, Email: bergerm@simmons.edu
Martin Mastovich, Thermo Fisher Scientific, 900 Middlesex Turnpike, Building 8, Billerica, MA, 01821, Tel: 978-670-7460, Fax: 978-670-7422, Email: marty.mastovich@thermofisher.com

The Muddy River is the backbone of the Emerald Necklace, a historic landscape and river system surrounding Boston, which over several decades has accumulated sediments with high levels of metals, (especially lead), petroleum hydrocarbons, and decaying vegetation.  In addtion to riverbank erosion, deposition of suspended solids and contaminants in storm water are the major sources of sediment accumulation.  A major remediation of the Muddy River system will include the dredging and disposal of thousands of tons of contaminated sediments.  It will be important to monitor and quantify the changes in the contaminant levels in suspended solids prior to, during, and after the dredging.  Currently the analysis of metal contaminants in surface waters or sediments is accomplished by analytical methods such as atomic absorption and ICP-AES.  While these methods offer excellent sensitivity, considerable sample preparation is required.  The use of the XRF allows direct analysis of sediment particles with little sample preparation or chemical workup.  Analytical resulsts obtained with XRF are compared with traditional analytical methods.

Preparation and Analysis of Total Mercury in Biological Tissue Samples Using Atomic Fluorescence Spectrometry
Leonard C. Pitts. Alpha Analytical, 320 Forbes Blvd., Mansfield, MA 02048,Tel: 508-822-9300, Fax: 508-822-3288, Email: lpitts@alphalab.com  

Atomic fluorescence spectrometry is an extremely sensitive and specific technique for determining total mercury in biological tissue samples. The analytical sensitivity can be adjusted for measurement of elevated mercury levels in tissues, or set for trace levels by adjusting the instrumental gain to calibrate and analyze different ranges. Extremely low concentration samples, or samples where the mass is limited, may be analyzed using gold amalgamation pre-concentration for maximum sensitivity. Clean reagents are necessary to minimize the background contribution to the analytical signal and may require reagent clean-up prior to use. Due to the large variety of biological samples encountered in environmental studies and the desire for whole body as well as specific sub-sample analysis, sample preparation is extremely critical to insure minimal sample contamination. Also, a 1-2 g aliquot that is selected for analysis should be representative of the entire sample. Homogenization techniques using titanium utensils and digestion methods including microwave oven heating in high pressure fluorocarbon vessels were performed. The efficacy of these methods is demonstrated by the analysis of quality control samples such as preparation blanks, matrix spikes, matrix duplicates and standard reference materials.  

Continuous Profiling of Subsurface Pollutants
Albert Robbat and Thomas Considine, Tufts University , Chemistry Department, Center for Field Analytical Studies and Technology, Medford , Massachusetts , 02155, Tel: 617-627-3474, Email: arobbat@tufts.edu  

Our goal is to accelerate the site investigation process and, at the same time, reduce the overall cost of cleanup by developing conceptual models that are information rich in geology, hydrology and chemical data.  Toward this end, we continue to advance dynamic site investigations, consistent with EPA’s TRIAD process, and have developed two different probes capable of extracting organic pollutants from subsurface soil and groundwater.  To accomplish this task, our probes are connected on one end to a 300 ⁰C flexible, heated transfer line and, on the other end, to a heated six-port valve.  Organic vapors are swept from the collection port through the transfer line into a valve that is connected to a photoionization detector (PID) for rapid subsurface profiling. When the PID signal increases over baseline, detector response indicates the magnitude of pollutants present at that location.  When the valve is switched from the PID to an external freeze-trap, organics are trapped inside an empty glass sleeve, which is brought to a thermal desorption gas chromatography/mass spectrometry (GC/MS) instrument for on-site analysis.

When moisture content is < 15%, organics are desorbed from soil and collected directly into the transfer line or through a hydrophobic membrane.  The membrane allows the passage of organics and excludes the passage of water into the transfer line.  For semivolatile organics, extraction efficiencies of 70-90% are achievable with the direct inlet probe because soil temperatures can reach 300 ⁰C.  In contrast, soil only reaches 120 ⁰C with the membrane inlet probe and much lower extraction efficiencies are obtained.  An advantage, however, is that the same technology can be used to profile soil-to-water or water-to-sediment interfaces in a continuum.  Data will be presented from a coal tar site in which polycyclic aromatic hydrocarbons (PAHs) are profiled continuously by PID as the probe is advanced into the subsurface.  PID response is compared against GC/MS results at the same exact location, with the overall correlation coefficient > 0.92.  When the heated transfer line is connected directly to an online freeze trap in series with the GC column, correlation coefficients increase.  We will show low molecular weight, low boiling organics such as benzene, naphthalene and their alkylated analogs are much more efficiently captured than what was obtainable using the external freeze-trap.  To match sample collection and analysis speeds, a 5-min GC/MS analysis was performed using the Ion Signature deconvolution algorithms to quantify target compounds.  Combining these technologies will facilitate onsite sample collection and analysis using modified SW-846 GC/MS methods optimized to meet field conditions.

Why New Coal Tar and Petroleum Forensic Environmental Methods Are Needed
Albert Robbat and Christian Zeigler, Tufts University, Chemistry Department, Center for Field Analytical Studies and Technology, Medford, MA, 02155, Tel: 617-627-3474, Email: arobbat@tufts.edu

Forensic environmental studies rely on quantitative measurements of specific chemicals or families of chemically related compounds.  For coal tar, petroleum, explosion, and fire-related investigations, gas chromatography/mass spectrometry (GC/MS) data of benzothiophenes, polycyclic aromatic hydrocarbons (PAH), and their alkylated analogs (the C1-C4, saturated side chains) are used to distinguish contaminant source(s), assign blame, and proportionate liability as well as degradation, evaporation, and washing rates due to interactions with the environment.

Quantitative identification by GC/MS is only possible when target compound mass spectra are unencumbered by coeluting compounds, which is not the case.  Chemical noise from the matrix masks target compound spectra making full scan (sample vs library) spectral matching impossible to validate.  Selected ion monitoring (SIM), whether by molecular or multiple ions per homolog, has evolved into the technique of choice based on the false presumption that matrix interferences are minimized. 

Research will be presented illustrating how easy it is to wrongly identify and, therefore, incorrectly quantify alkylated PAH by SIM or full scan MS using standard data analysis software.  We will show why SIM, based on a single ion, yields much higher alkylated PAH concentrations than it should and why analyses, based on single homolog patterns, produce larger than expected underestimations of homolog concentrations.  In contrast, we will show that the Ion Signature deconvolution software, which is based on the algorithms developed at Tufts, lead to more accurate estimates of concentration when multiple fragmentation patterns per homolog are used.  We will show how to use the algorithms to validate the presence of C1-C4 PAH through a combinatorial library building process for isomers whose mass spec are not in standard reference libraries.  Based on this work, we propose a new forensic method for the analysis of alkylated PAH in complex environmental samples.

Environmental Analysis and Water Quality Monitoring of Environmental Waters using an In Vitro Bioassay System in Nara
Akiyoshi Sawabe, Department of Applied Biological Chemistry, Faculty of Agriculture, Kinki University, 3327-204, Nakamachi, Nara, 631-8505, Japan, Tel: +81-742-43-7092, Fax: +81-742-43-1445, E-mail: sawabe@nara.kindai.ac.jp
Kazuki Ikushima, Department of Agricultural Chemistry, Faculty of Agriculture, Kinki University , 3327-204, Nakamachi, Nara , 631-8505, Japan
Ryuji Takeda, Department of Applied Biological Chemistry, Graduate School of Agriculture, Kinki University , 3327-204, Nakamachi, Nara , 631-8505, Japan
Shingen Matsushima, Department of Agricultural Chemistry, Faculty of Agriculture, Kinki University , 3327-204, Nakamachi, Nara , 631-8505, Japan
Yousuke Kouchi, Department of Agricultural Chemistry, Faculty of Agriculture, Kinki University , 3327-204, Nakamachi, Nara , 631-8505, Japan
Shiho Kageyama, Research Center for Environmental Risk, National Institute for Environmental Studies, 16-2, Onogawa, Tsukuba, Ibaraki , 305-3506, Japan
Ryo Kamata, Research Center for Environmental Risk, National Institute for Environmental Studies, 16-2, Onogawa, Tsukuba, Ibaraki , 305-3506, Japan
Daisuke Nakajima, Research Center for Environmental Risk, National Institute for Environmental Studies, 16-2, Onogawa, Tsukuba, Ibaraki , 305-3506, Japan
Fujio Shiraishi, Research Center for Environmental Risk, National Institute for Environmental Studies, 16-2, Onogawa, Tsukuba, Ibaraki, 305-3506, Japan, Tel: +81-29-850-2454, Fax: +81-29-850-2870
Sadao Komemushi, Department of Environmental Management, Faculty of Agriculture, Kinki University , 3327-204, Nakamachi, Nara , 631-8505, Japan

In recent years influence of human body by an internal secretion disturbance chemical compound (environmental endocrine disrupter) becomes a terrible problem.  It is mainly concerned about a cause of hypospadias, thyroid gland aberration and sperm count decrease.

In the Yamato River water system which is one of a Japanese city river, we investigated heavy metal, TOC, anion, T-N and estrogen activity evaluation by yeast Two-Hybrid method from 2005.  As a result, in the upper reaches, there was the point majority who exceeded Japanese environmental quality standard value, and that effect of pollution in domestic wasted water was massive.  In addition, the tendency that a nitric acid ion and a sulfate ion became high concentration in a specific spot was shown.  Furthermore, in estrogenic activity, there are many points more than 10% of the greatest activity value of 17-b-estradiol, thus presence of alkyl phenols such as nonyl phenol is considered.  In Yamato River water system, PFOS and PFOA were present in the surface water which we obtained from a place and confluence spot with much domestic wasted water.