High-throughput analysis of emerging and historical pollutants in biological matrices.


The Deepwater Horizon Gulf Spill highlighted key deficiencies associated with our ability to analyze contaminants in biological tissue in a timely manner. These deficiencies in laboratory capacity and preparedness demonstrated a critical need to develop and validate high-throughput analytical methods capable of rapid and accurate quantification of organic pollutants in biological tissue from aquatic environments. High-throughput methods offer distinct advantages over historical methods, namely a reduction in the intrinsic costs associated with the sample preparation: time, solvents, labor, laboratory space, training, and potential loss of analytes. Sample preparation steps for the analysis of organic pollutants represent ~2/3 of the analytical cost, and are often the logistical bottleneck for laboratory capacity and preparedness.
An enhanced pressurized liquid extraction (ePLE) method was developed for simultaneous analysis of pharmaceuticals and personal care products (PPCPs) in fish tissue and was utilized in a nationwide PPCP study conducted in Germany. The developed high-throughput method incorporated silica gel cleanup with PLE and improved the method sensitivity by optimizing resonant collision induced dissociation energy through ion-trap mass analyzer. The nationwide PPCP study found that the proximity of sampling locations to the upstream wastewater treatment plant discharging point and mean annual flow at the sampling locations were found to significantly powerful predictor of galaxolide and tonalide fish tissue concentrations (galaxolide: r2 = 0.79, p = 0.021 and tonalide: r2 = 0.81, p = 0.037) in Germany. Galaxolide and tonalide, both polycyclic musk fragrance materials, in German fish tissues were ~19 and ~28× lower, respectively, as compared to similar nationwide PPCP study in the United States. Similarly, a high-throughput ePLE method was developed for polychlorodibenzo-p-dioxins/furans (PCDD/Fs) and dioxin-like polychlorobiphenyls (dl-PCBs) by incorporating pressurized liquid extraction and multiple cleanup techniques. Sample preparation time and solvents were reduced as much as 95% and 65%, respectively, as compared to a conventional USEPA Method 1613. ePLE extracts were sufficiently clean for high resolution mass spectrometry analysis of PCDD/Fs and dl-PCBs in fish tissues from San Jacinto River Waste Pits, a Superfund site in Houston, TX.



Enhanced pressurized liquid extraction technique., High-throughout analytical techniques., German environment specimen bank samples., Houston shipping channel, a superfund site., Chlorinated dioxins, furans, and biphenyls., Fate and transport of organic contaminant., Pharmaceuticals and personal care products.


Subedi, B., Mottaleb, M. A., Chambliss, C. K., Usenko, S. "Simultaneous analysis of select pharmaceuticals and personal care products in fish tissue using pressurized liquid extraction combined with silica gel cleanup." J. Chromatogr. A 1218, 37 (2011): 6278-6284.
Subedi, B., Du, B., Chambliss, C. K., Koschorreck, J., Rüdel, H., Quack, M., Brooks, B. W., Usenko, S. "Occurrence of pharmaceuticals and personal care products in German fish tissue : a national study." Environ. Sci. Technol. 46, 16 (2012): 9047-9054.
Subedi, B., Usenko, S. "Enhanced pressurized liquid extraction technique capable of analyzing polychlorodibenzo-p-dioxins, polychlorodibenzofurans, and polychlorobiphenyls in fish tissue." J. Chromatogr. A 1238 (2012): 30-37.