Publications

An automated gas chromatography was used to analyze water samples contaminated with trace (parts-per-billion) concentrations of organic analytes. A custom interface introduced the liquid sample to the chromatography. This was followed by rapid chromatographic analysis. Characteristics of the analysis include response times less than one minute and automated data processing. Analytes were chosen based on their known presence in the recycle water streams of semiconductor manufacturers and their potential to reduce process yield. These include acetone, isopropanol, butyl acetate, ethyl benzene, p-xylene, methyl ethyl ketone and 2-ethoxy ethyl acetate. Detection limits below 20 ppb were demonstrated for all analytes and quantitative analysis with limited speciation was shown for multianalyte mixtures. Results are discussed with respect to the potential for on-line liquid process monitoring by this method.

Linear chemometric algorithms were used to model the quantitative response of an evanescent fiber optic chemical sensor in aqueous mixtures with concentrations between 20 and 300 ppm. Four data sets were examined with two different experimental arrangements. Two data sets contained trichloroethene, 1,1,2 trichloroethane, and toluene. Partial Least Squares, PLS, and Principal Component Regression, PCR, algorithms performed comparably on these calibration sets with cross-validated root mean squared errors of prediction (RMSEP) for trichloroethene, 1,1,1 trichloroethane, and toluene of approximately 26, 29 and 22 ppm, respectively. The third data set contained trichloroethene, 1,1,2 trichloroethane, toluene, and chloroform and the fourth contained these four analytes as well as tetrachloroethene. Again, both chemometric algorithms performed comparably on a given data set with RMSEP for trichloroethene, 1,1,2 trichloroethane, toluene, and chloroform of approximately 6, 6, 9, and 16 ppm from the first set, and 7, 11, 13, and 31 ppm from the second set with tetrachloroethene RMSEP of 31 ppm. The decrease in the quantitative performance of the sensor for modeling toluene and chloroform upon addition of tetrachloroethene to the sample solutions is due to increased cladding absorption features in the spectral response matrix. These features overlap with the analyte absorption features of toluene and chloroform. These results suggest one of the limitations with this type of sensing format.

The AQUASCAN, a commercially available, fully automated purge-and-trap gas chromatograph from Sentex Systems Inc., was implemented and evaluated as an in-field, automated monitoring system of contaminated groundwater at an active DOE remediation site in Pinellas, FL. Though the AQUASCAN is designed as a stand alone process analytical unit, implementation at this site required additional hardware. The hardware included a sample dilution system and a method for delivering standard solution to the gas chromatograph for automated calibration. As a result of the evaluation the system was determined to be a reliable and accurate instrument. The AQUASCAN reported concentration values for methylene chloride, trichloroethylene, and toluene in the Pinellas ground water were within 20% of reference laboratory values.

Traditionally, pyrolysis combined with infrared, IR, detection of the decomposition products for the analysis of small (<1 mg) samples has been limited due to the size and geometry of commercially available pyrolysis chambers. To reduce the sample size requirements for pyrolysis-IR a system has been designed and built that allows various microgram sized polymer samples to be examined. The design incorporates a commercial pyrolysis system with a small chamber built from readily available parts. Minimal modifications of these components are required to build the system. The micropyrolyzer has been used to successfully identify various filled epoxy samples, such as three Epon 828 samples: 0.46 mg of alumina filled; 0.15 mg of mica filled; and 0.28 mg of glass microballoon, GMB, filled. 7 refs., 6 figs.