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A modified QuEChERS approach for the screening of dioxins and furans in sediments

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Abstract

A rapid extraction and cleanup method for the screening of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in sediments is described which combines a modified QuEChERS extraction with carbon reversed-phase solid phase extraction cleanup. This approach is compared to the classical Soxhlet extraction and multi-column cleanup method in terms of toxic equivalence quotients (TEQs), precision, instrumental chromatography, method detection limits (MDLs), recovery of 13C-labelled quantitation standard, sample preparation time, workload capacity, and sustainability factors. TEQs of 32 sediment samples were found to be well correlated and differed by 16 ± 10 % between the two methods. Certified and standard reference sediments differed by 4.1 and 6.7 %, respectively. Precision and instrumental chromatography were comparable. While the modified QuEChERS method had higher MDLs and lower recoveries, in terms of preparation time and workload capacity, the modified QuEChERS approach can prepare approximately 30 samples per day as compared to 10–20 samples in 3 to 4 days for the classic method. The modified QuEChERS method was also found to be safer and greener. The appreciable improvement in capacity makes the modified QuEChERS approach a suitable alternative to the classical method for applications where turnaround time and the number of samples that can be analyzed are more important than minimal detection limits.

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A bar graph with the structures of dioxins and furans on the x axis shows agreement between two sets of data. A legend labels the first set of data as Soxhlet. The Soxhlet set is illustrated as four days crossed off of a calendar page, a Soxhlet extractor, and several packed chromatography columns. The legend identifies the second set of data as QuEChERS. The QuEChERS set is represented by a clock face marked with twenty four hours, two centrifuge tubes containing the sediment and reagents before and after salting out, and a carbon column attached to a reservoir

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References

  1. Berry RM, Luthe CE, Voss RH. Ubiquitous nature of dioxins: a comparison of the dioxins content of common everyday materials with that of pulps and papers. Environ Sci Technol. 1993;27:1164–8.

    Article  CAS  Google Scholar 

  2. Srogi K. Levels and congener distributions of PCDDs, PCDFs and dioxin-like PCBs in environmental and human samples: a review. Environ Chem Lett. 2008;6:1–28.

    Article  CAS  Google Scholar 

  3. Mandal PK. Dioxin: a review of its environmental effects and its aryl hydrocarbon receptor biology. J Comp Physiol B. 2005;175:221–30.

    Article  CAS  Google Scholar 

  4. The 12 initial POPs under the Stockholm Convention (2008) United Nations Environmental Programme. http://chm.pops.int/TheConvention/ThePOPs/The12InitialPOPs/tabid/296/Default.aspx. Accessed 11 Aug 2014.

  5. Dioxins and Furans Factsheet (2012) Environmental Protection Agency (EPA). http://www.epa.gov/osw/hazard/wastemin/minimize/factshts/dioxfura.pdf. Accessed 10 Dec 2013.

  6. Fernandez-Salguero P, Pineau T, Hilbert DM, McPhail T. Immune system impairment and hepatic fibrosis in mice lacking the dioxin-binding Ah receptor. Science. 1995;268:722–6.

    Article  CAS  Google Scholar 

  7. Bock KW, Köhle C. Ah receptor: dioxin-mediated toxic responses as hints to deregulated physiologic functions. Biochem Pharmacol. 2006;72:393–404.

    Article  CAS  Google Scholar 

  8. Fernandez-Salguero PM, Hilbert DM, Rudikoff S, Ward JM, Gonzalez FJ. Aryl-hydrocarbon receptor-deficient mice are resistant to 2, 3, 7, 8-tetrachlorodibenzo-p-dioxin-induced toxicity. Toxicol Appl Pharmacol. 1996;140:173–9.

    Article  CAS  Google Scholar 

  9. Van den Berg M, Birnbaum LS, Denison M, De Vito M, Farland W, Feeley M, et al. The 2005 World Health Organization reevaluation of human and mammalian toxic equivalency factors for dioxins and dioxin-like compounds. Toxicol Sci. 2006;93:223–41.

    Article  Google Scholar 

  10. Birnbaum LS, DeVito MJ. Use of toxic equivalency factors for risk assessment for dioxins and related compounds. J Toxicol. 1995;105:391–401.

    Article  CAS  Google Scholar 

  11. Whitlock Jr JP. Mechanistic aspects of dioxin action. Chem Res Toxicol. 1993;6:754–63.

    Article  CAS  Google Scholar 

  12. Wan Y, Hu J, Yang M, An L, An W, Jin X, et al. Characterization of trophic transfer for polychlorinated dibenzo-p-dioxins, dibenzofurans, non-and mono-ortho polychlorinated biphenyls in the marine food web of Bohai Bay. North China Environ Sci Technol. 2005;39:2417–25.

    Article  CAS  Google Scholar 

  13. Pickard SW, Clarke JU. Benthic bioaccumulation and bioavailability of polychlorinated dibenzo-p-dioxins/dibenzofurans from surficial Lake Ontario sediments. Great Lake Res. 2008;34:418–33.

    Article  CAS  Google Scholar 

  14. Gutenmann WH, Ebel Jr JG, Kuntz HT, Yourstone KS, Lisk DJ. Residues of p, p’-DDE and mercury in lake trout as a function of age. Arch Environ Contam Toxicol. 1992;22:452–5.

    Article  CAS  Google Scholar 

  15. Djien Liem AK, Furst P, Rappe C. Exposure of populations to dioxins and related compounds. Food Addit Contam. 2000;17:241–59.

    Article  Google Scholar 

  16. Svensson BG, Nilsson A, Hansson M, Rappe C, Åkesson B, Skerfving S. Exposure to dioxins and dibenzofurans through the consumption of fish. N Engl J Med. 1991;324:8–12.

    Article  CAS  Google Scholar 

  17. Larsson P. Contaminated sediments of lakes and oceans act as sources of chlorinated hydrocarbons for release to water and atmosphere. Nature. 1985; 347–349.

  18. Oliver BG. Uptake of chlorinated organics from anthropogenically contaminated sediments by oligochaete worms. Fish Aquat Sci. 1984;41:878–83.

    Article  CAS  Google Scholar 

  19. Burton GA. Assessing the toxicity of freshwater sediments. Environ Toxicol Chem. 1991;10:1585–627.

    Article  CAS  Google Scholar 

  20. Foster GD, Baksi SM, Means JC. Bioaccumulation of trace organic contaminants from sediment by baltic clams (Macoma balthica) and soft‐shell clams (Mya arenaria). Environ Toxicol Chem. 1987;6:969–76.

    Article  CAS  Google Scholar 

  21. Cook A, Kuehl DW, Walker MK, Peterson RE. In: Gallow MA, Scheuplein RJ, VanDerHeijden K, editors. Biological basis for risk assessment of dioxins and related compounds, Banbury Report 35. Cold Spring Harbor: Cold Spring Harbor Laboratory Press; 1991.

  22. Bhavsar SP, Gewurtz SB, Helm PA, Labencki TL, Marvin CH, Fletcher R, et al. Estimating sediment quality thresholds to prevent restrictions on fish consumption: application to polychlorinated biphenyls and dioxins–furans in the Canadian Great Lakes. Integr Environ Assess Manag. 2010;6:641–52.

    Article  CAS  Google Scholar 

  23. Lau SS. The significance of temporal variability in sediment quality for contamination assessment in a coastal wetland. Water Res. 2000;34:387–94.

    Article  CAS  Google Scholar 

  24. Tam NF, Wong YS. Spatial and temporal variations of heavy metal contamination in sediments of a mangrove swamp in Hong Kong. Mar Pollut Bull. 1995;31:254–61.

    Article  CAS  Google Scholar 

  25. Perelo LW. Review: in situ and bioremediation of organic pollutants in aquatic sediments. J Hazard Mater. 2010;177:81–9.

    Article  CAS  Google Scholar 

  26. Ontario Ministry of the Environment. The determination of polychlorinated dibenzo-p-dioxins, polychlorinated furans and dioxin-like PCBs in environmental matrices by GC–HRMS. Ontario Laboratory Services Branch Method DFPCB-E3418. Ontario Ministry of the Environment, Toronto, ON, Canada. 2004.

  27. Reiner EJ. The analysis of dioxins and related compounds. Mass Spectrom Rev. 2010;29:526–59.

    CAS  Google Scholar 

  28. Canadian Council of Ministers of the Environment. Canadian soil quality guidelines for the protection of environmental and human health: Dioxins and Furans. Canadian environmental quality guidelines. Canadian Council of Ministers of the Environment, Winnipeg, MB, Canada. 2002.

  29. European Commission. Commission Regulation (EC) No 1881/2006 of 19 December 2006 setting maximum levels for certain contaminants in foodstuffs. Off J Eur Union. 2006;364:5–24.

    Google Scholar 

  30. Behnisch PA, Hosoe K, Sakai SI. Bioanalytical screening methods for dioxins and dioxin-like compounds—a review of bioassay/biomarker technology. Environ Int. 2001;27:413–39.

    Article  CAS  Google Scholar 

  31. Nichkova M, Park EK, Koivunen ME, Kamita SG, Gee SJ, Chuang J, et al. Immunochemical determination of dioxins in sediment and serum samples. Talanta. 2004;63:1213–23.

    Article  CAS  Google Scholar 

  32. Roy S, Mysior P, Brzezinski R. Comparison of dioxin and furan TEQ determination in contaminated soil using chemical, micro-EROD, and immunoassay analysis. Chemosphere. 2002;48:833–42.

    Article  CAS  Google Scholar 

  33. Reiner EJ, Clement RE, Okey AB, Marvin CH. Advances in analytical techniques for polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and dioxin-like PCBs. Anal Bioanal. 2006;386:791–806.

    Article  CAS  Google Scholar 

  34. Schrock M, Dindal A, Billets S. Evaluation of alternative approaches for screening contaminated sediments and soils for polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans. J Environ Manag. 2009;90:1289–95.

    Article  CAS  Google Scholar 

  35. Chuang JC, Van Emon JM, Schrock ME. High-throughput screening of dioxins in sediment and soil using selective pressurized liquid extraction with immunochemical detection. Chemosphere. 2009;77:1217–23.

    Article  CAS  Google Scholar 

  36. Onuska FI, Terry KA. Extraction of pesticides from sediments using a microwave technique. Chromatographia. 1993;36:191–4.

    Article  CAS  Google Scholar 

  37. US EPA. Method 1613, Revision B: Tetra- through octachlorinated dioxins and furans by isotope dilution HRGC/HRMS, EPA 821-B94-0059. Office of Water, US Environmental Protection Agency, Washington, DC, USA. 1994.

  38. Sporstøl S, Gjøs N, Carlberg GE. Extraction efficiencies for organic compounds found in aquatic sediments. Anal Chim Acta. 1983;151:231–5.

    Article  Google Scholar 

  39. Tobiszewski M, Mechlińska A, Namieśnik J. Green analytical chemistry—theory and practice. Chem Soc Rev. 2010;39:2869–78.

    Article  CAS  Google Scholar 

  40. Gałuszka A, Migaszewski Z, Namieśnik J. The 12 principles of green analytical chemistry and the SIGNIFICANCE mnemonic of green analytical practices. Trends Anal Chem. 2013;50:78–84.

    Article  Google Scholar 

  41. Melnyk A, Wolska L, Namieśnik J. Coacervative extraction as a green technique for sample preparation for the analysis of organic compounds. J Chromatogr A. 2014;1339:1–12.

    Article  CAS  Google Scholar 

  42. Armenta S, Garrigues S, de la Guardia M. The role of green extraction techniques in Green Analytical Chemistry. Trends Anal Chem. 2015;71:2–8.

    Article  CAS  Google Scholar 

  43. Anastassiades M, Lehotay SJ, Štajnbaher D, Schenck FJ. Fast and easy multiresidue method employing acetonitrile extraction/partitioning and “dispersive solid-phase extraction” for the determination of pesticide residues in produce. J AOAC Int. 2003;86:412–31.

    CAS  Google Scholar 

  44. João Ramalhosa M, Paíga P, Morais S, Delerue‐Matos C. Prior Pinto Oliveira MB. Analysis of polycyclic aromatic hydrocarbons in fish: evaluation of a quick, easy, cheap, effective, rugged, and safe extraction method. J Sep Sci. 2009;32:3529–38.

    Article  Google Scholar 

  45. Smoker M, Tran K, Smith RE. Determination of polycyclic aromatic hydrocarbons (PAHs) in shrimp. J Agric Food Chem. 2010;58:12101–4.

    Article  CAS  Google Scholar 

  46. Gratz SR, Ciolino LA, Mohrhaus AS, Gamble BM, Gracie JM, Jackson DS, et al. Screening and determination of polycyclic aromatic hydrocarbons in seafoods using QuEChERS-based extraction and high-performance liquid chromatography with fluorescence detection. J AOAC Int. 2011;94:1601–16.

    Article  CAS  Google Scholar 

  47. Albinet A, Tomaz S, Lestremau F. A really quick easy cheap effective rugged and safe (QuEChERS) extraction procedure for the analysis of particle-bound PAHs in ambient air and emission samples. Sci Total Environ. 2013;450:31–8.

    Article  Google Scholar 

  48. Asensio-Ramos M, Hernández-Borges J, Ravelo-Pérez LM, Rodríguez-Delgado MA. Evaluation of a modified QuEChERS method for the extraction of pesticides from agricultural, ornamental and forestal soils. Anal Bioanal Chem. 2010;396:2307–19.

    Article  CAS  Google Scholar 

  49. Pinto CG, Martín SH, Pavón JL, Cordero BM. A simplified Quick, Easy, Cheap, Effective, Rugged and Safe approach for the determination of trihalomethanes and benzene, toluene, ethylbenzene and xylenes in soil matrices by fast gas chromatography with mass spectrometry detection. Anal Chim Acta. 2011;689:129–36.

    Article  Google Scholar 

  50. Bragança I, Plácido A, Paíga P, Domingues VF, Delerue-Matos C. QuEChERS: a new sample preparation approach for the determination of ibuprofen and its metabolites in soils. Sci Total Environ. 2012;433:281–9.

    Article  Google Scholar 

  51. Anastassiades M, Tasdelen B, Scherbaum E, Stajnbaher D. Recent developments in QuEChERS methodology for pesticide multiresidue analysis. In: Ohkawa H, Miyagawa H, Lee PW, editors. Pesticide chemistry: crop protection, public health, environmental safety. New York: Wiley; 2007. p. 439–58.

    Chapter  Google Scholar 

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Acknowledgments

The authors thank Manish Amin of Agilent Technologies Inc. for assistance with the QuEChERS extraction and dispersive cleanup kits. We also thank Lisa Richman of the Ontario Ministry of Environment and Climate Change for the sediment samples.

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  1. Ontario Ministry of the Environment and Climate Change, 125 Resources Rd., Toronto, ON, M9P 3V6, Canada

    Liad Haimovici, Eric J. Reiner, Sladjana Besevic, Karl J. Jobst, Matthew Robson, Terry Kolic & Karen MacPherson

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  1. Liad Haimovici
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Correspondence to Liad Haimovici.

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Haimovici, L., Reiner, E.J., Besevic, S. et al. A modified QuEChERS approach for the screening of dioxins and furans in sediments. Anal Bioanal Chem 408, 4043–4054 (2016). https://doi.org/10.1007/s00216-016-9493-0

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