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Laboratory Focus April/May 2014
Online SPE HPLC/MS/MS has also been used to analyze a variety of trace organics in water. These include herbicides, pesticides, pharmaceuticals, estrogens, and glyphosate in potable water. Sarah Gledhill of SouthEast Water (UK) reports on a validated online SPE LC/MS/MS method for detection of 17 chlorinated phenoxy acid herbicides and pentachlorophenol (PCP) in surface and treated water, using only 1.5 mL of sample.9 This method delivers <10 ng/L (ppt) limits of detection (LODs), as well as recoveries >95 per cent for most of the compounds. In addition to a reduction in sample volume, this method provides faster results at lower cost. The solid phase extraction cartridges are reusable, and less solvent is used for extraction of the sample. Finally, the results are more reproducible than their older method based on manual SPE, because the system is fully automated and less prone to operator error. This method meets the performance requirements set by the UK Drinking Water Inspectorate for standard deviation, bias, recovery, and total error and is accredited by the United Kingdom Accreditation Service (UKAS).
Q-TOF Accurate Mass analysis enables highly sensitive and untargeted screening of pharmaceuticals in water Mike Thurman and Imma Ferrer at the University of Colorado demonstrated that a quadrupole time-offlight mass spectrometer (Q-TOF MS) can provide high confidence identification and quantitation of pharmaceuticals, enabling an untargeted LC/ MS screening method that has been used to characterize more than 100 pharmaceuticals and their metabolites in water sources at concentrations as low as parts per trillion10 (Table 2). Sophisticated software tools for molecular feature extraction, formula generation, molecular structure correlation, and accurate mass database matching are key to the success of the method. This approach is particularly useful for separating and identifying isobaric and isomeric compounds that can be difficult to analyze using other methods.
Mobile analysis can be used effectively to rapidly assess drinking water quality Circumstances can often dictate the need for onsite analysis to immediately confirm the safety of surface and drinking water. Such a need arose after a recent earthquake in China. Agilent Technologies was requested to provide onsite water quality monitoring, as rapid and reliable lab-quality results in the field were necessary in order to make decisions to avoid a national emergency from contaminated drinking water. The Agilent 5975T LTM GC/MSD, a mobile combination gas chromato-
graph/mass selective detector (GC/ MSD) configured with a purge and trap concentrator and low thermal mass technology, was used as a testing station in this crisis.11 Although portable, it provided the accuracy and sensitivity required to assure compliance with regulatory standards for drinking water safety (Figure 2). A method was developed on this portable system to rapidly analyze for 22 trace volatile organic pollutants that are regulated in drinking water. While routine cycle time was reduced to five to 10 minutes, compared to more than 30 minutes with traditional laboratory methods, the minimum detection limits varied between 0.090.14 μg/l (ppb) for all 22 compounds These levels are below the acceptable detection limits for these compounds in drinking water in China. This method provides results with high sensitivity, accuracy, sensitivity, and reproducibility similar to results that can be obtained in a stationary lab, providing the versatility for analyses in remote disaster locations.
Conclusion Modern society generates a plethora of waste products containing a wide range of organic chemicals that are clearly making their way into surface and drinking water. These compounds are often present in trace amounts, even parts per trillion, and their impact on the environment and human health are unknown. Regulatory agencies worldwide are making efforts to characterize the nature and concentrations of these compounds so that their threat to the environment and human health can be accurately assessed. These efforts require new technologies and methods to assure success in a meaningful timeframe. Recent advances in automated online sample enrichment, more sensitive and faster scanning mass spectrometers, Q-TOF and accurate mass software tools, and mobile analysis systems are helping to meet this challenge. Together they can reduce the time and sample volume needed to assess water sources, while providing accurate and reproducible detection of >200 trace organic contaminants simultaneously, at parts per trillion (ng/L) concentrations.
References 1. Anumol T., Merel S., Clarke B. O., Snyder S. A. Ultra high performance liquid chromatography tandem mass spectrometry for rapid analysis of trace organic contaminants in water. Chem Cent J. Jun 18;7(1):104 (2013). 2. Kidd K. A., Blanchfield P. J., Mills K. H., Palace V. P., Evans R. E., Lazorchak J. M., Flick R. W. Collapse of a fish population after exposure to a synthetic estrogen. Proc Natl Acad Sci U S A. 104, 8897-8901 (2007). 3. Drugs in the drinking water, an
Associated Press Investigation: http://hosted.ap.org/specials/interactives/pharmawater_site/. 4. Arvai A., Flecka G., Jasim, S. Melcer H., Laitta M. T. Protecting our great lakes: assessing the effectiveness of wastewater treatments for the removal of chemicals of emerging concern. Water Qual Res J Can In Press, doi:10.216/wgrjc 2013.104. 5. Blair B. D., Crago J. P., Hedman C. J., Klaper R. D., Pharmaceuticals and personal care products found in the Great Lakes above concentrations of environmental concern. Chemosphere 93, 2116-2123 (2013). 6. Unregulated Contaminant Monitoring Rule 3 (UCMR3),http:// water.epa.gov/lawsregs/relesreg/ sdwa/ucmr/ucmr3/index.cfm 7. Pollutants in Urban Waste Water and Sewage Sludge, http://ec.europa.eu/environment/ waste/sludge/pdf/sludge_pollutants_xsum.pdf 8. Anumol T., Snyder S., Mohsin S. B. Sensitive LC/MS Quantitation of Trace Organic Contaminants in Water with Online SPE Enrichment. Agilent Technologies Application Note 5991-1849EN (2013). 9. Gledhill, S. High Sensitivity Detection of Pesticides in Water Using Online SPE Enrichment.
feature Agilent Technologies Application Note 5991-0871EN (2012). 10. Ferrer I., Thurman E. M. High Resolution Mass Spectrometry (LC/Q-TOF/MS) for the Detection of Pharmaceuticals in Water. Agilent Technologies Application Note 5991-3261 (2013). 11. Cooperation with the China Academy of Urban Planning and Design for Field VOC Measurement of Drinking Water Sources with the Agilent 5875T LTM GC/ MSD. Agilent Technologies Application Note 5991-3140EN (2013).
Mr. Weitzel is the Agilent Global Environmental Market Development Manager. Before being employed by Agilent, Joe had been employed as a municipal water utility chemist and the lab manager for an environmental contract testing laboratory. Joe has been with Agilent since 1984 in various sales and marketing positions.
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