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The quantification of short-chain chlorinated paraffins in sediment samples using comprehensive two-dimensional gas chromatography with μECD detection

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Abstract

The analysis of persistent organic pollutants in environmental samples is a challenge due to the very large number of compounds with varying chemical and physical properties. Chlorinated paraffins (CPs) are complex mixtures of chlorinated n-alkanes with varying chain lengths (C10 to C30) and degree of chlorination (30 to 70% by weight). Their physical-chemical properties make these compounds persistent in the environment and able to bioaccumulate in living organisms. Comprehensive two-dimensional gas chromatography (GC × GC) coupled with micro-electron capture detection (μECD) was used to separate and quantify short-chain chlorinated paraffins (SCCP) in sediment samples. Distinct ordered bands were observed in the GC × GC chromatograms pointing to group separation. Using the Classification function of the ChromaTOF software, summary tables were generated to determine total area counts to set up multilevel-calibration curves for different technical mixes. Fortified sediment samples were analyzed by GC × GC-μECD with minimal extraction and cleanup. Recoveries ranged from 120 to 130%. To further validate the proposed method for the analysis of SCCPs, the laboratory participated in interlaboratory studies for the analysis of standards and sediment samples. The results showed recoveries between 75 and 95% and z-score values <2, demonstrating that the method is suitable for the analysis of SCCPs in soil/sediment samples.

Quantification of SCCPs by 2D-GC-μECD

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References

  1. Muir D. Chlorinated paraffins. In: Paasivirta J, editor. The handbook of environmental chemistry, vol. 3. Berlin: Springer; 2000. p. 203–36.

    Google Scholar 

  2. Tomy GT. Analysis of chlorinated paraffins in environmental matrices: the ultimate challenge for the analytical chemist. In: Boer J, editor. The Handbook of Environmental Chemistry, vol. 10. Berlin: Springer; 2010. p. 83–106.

    Google Scholar 

  3. Muir D. Environmental levels and fate. In: Boer J, editor. The Handbook of Environmental Chemistry, vol. 10. Berlin: Springer; 2010. p. 107–33.

    Google Scholar 

  4. Drouillard KG, Tomy GT, Muir DCG, Friesen KJ. Volatility of chlorinated n‐alkanes (C10 – C12): vapor pressures and Henry’s law constants. Environ Toxicol Chem. 1998;17(7):1252–60.

    CAS  Google Scholar 

  5. Drouillard KG, Hiebert T, Tran P, Tomy GT, Muir DCG, Friesen KJ. Estimating the aqueous solubilities of individual chlorinated n ‐alkanes (C10 – C12) from measurements of chlorinated alkane mixtures. Environ Toxicol Chem. 1998;17(7):1261–7.

    CAS  Google Scholar 

  6. Environment Canada 2008; Chlorinated Paraffins. Accessed 14 Sep 2015. http://www.ec.gc.ca/lcpe-cepa/default.asp?lang=En&n=D7D84872-1&offset=11

  7. Fiedler H. Short-chain chlorinated paraffins: production, use and international regulations. In: Boer J, editor. The Handbook of Environmental Chemistry, vol. 10. Berlin: Springer; 2000. p. 1–40.

    Google Scholar 

  8. Stern GA, Tomy GT. An overview of environmental levels and distribution of polychlorinated paraffins. Organohalog Compd. 2000;47:135–8.

    CAS  Google Scholar 

  9. Geiß S, Schneider M, Donnevert G, Einax J, Lettmann W, Rey N, et al. Validation interlaboratory trial for ISO 12010: water quality—determination of short-chain polychlorinated alkanes (SCCP) in water. Accred Qual Assur. 2012;17(1):15–25.

    Article  Google Scholar 

  10. Geiß S, Lettman N, Rey A, Lepper H, Korner B, Mais S, et al. Preliminary interlaboratory trial for ISO/DIS 12010: determination of short chain polychlorinated alkanes (SCCP) in water. Clean-Soil Air Water. 2011;39(6):537–42.

    Article  Google Scholar 

  11. Nicholls CR, Allchin CR, Law RJ. Levels of short and medium chain length polychlorinated n-alkanes in environmental samples from selected industrial areas in England and Wales. Environ Pollut. 2001;114(3):415.

    Article  CAS  Google Scholar 

  12. Zeng L, Li H, Wang T, Gao Y, Xiao K, Du Y, et al. Behavior, fate, and mass loading of short chain chlorinated paraffins in an advanced municipal sewage treatment plant. Environ Sci Technol. 2013;47(2):732.

    Article  CAS  Google Scholar 

  13. Tomy GT, Stern GA, Lockhart WL, Muir D. Occurrence of C10-C13 polychlorinated n-alkanes in Canadian midlatitude and Arctic lake sediments. Environ Sci Technol. 1999;33(17):2858–63.

    Article  CAS  Google Scholar 

  14. Marvin CH, Painte S, Tomy GT, Stern GA, Braekevelt E, Muir DCG. Spatial and temporal trends in short-chain chlorinated paraffins in Lake Ontario sediments. Environ Sci Technol. 2003;37(20):4561.

    Article  CAS  Google Scholar 

  15. Tomy GT, Muir DCG, Stern GA, Westmore JB. Levels of C10-C13 polychloro-n-alkanes in marine mammals from the Arctic and the St. Lawrence River Estuary. Environ Sci Technol. 2000;34(9):1615–9.

  16. Tomy G, Stern G, Muir D, Fisk A, Cymbalisty CD, Westmore J. Quantifying C10-C13 polychloroalkanes in environmental samples by high-resolution gas chromatography electron capture negative ion high resolution mass spectrometry. Anal Chem. 1997;69(14):2762–71.

    Article  CAS  Google Scholar 

  17. Zeng L, Chen R, Zhao Z, Wang T, Gao Y, Li A, et al. Spatial distributions and deposition chronology of short chain chlorinated paraffins in marine sediments across the Chinese Bohai and Yellow Seas. Environ Sci Technol. 2013;47(20):11449–56.

    Article  CAS  Google Scholar 

  18. Reth M, Zencak Z, Oehme M. First study of congener group patterns and concentrations of short- and medium-chain chlorinated paraffins in fish from the North and Baltic Sea. Chemosphere. 2005;58(7):847–54.

    Article  CAS  Google Scholar 

  19. Saborido Basconcillo L, Backus SM, McGoldrick DJ, Zaruk D, Sverko E, Muir DCG. Current status of short- and medium chain polychlorinated n-alkanes in top predatory fish across Canada. Chemosphere. 2015;127:93–100.

    Article  CAS  Google Scholar 

  20. Nilsson M, Waldebäck M, Liljegren G, Kylin H, Markides KE. Pressurized-fluid extraction (PFE) of chlorinated paraffins from the biodegradable fraction of source-separated household waste. Fresenius J Anal Chem. 2001;370(7):913–8.

    Article  CAS  Google Scholar 

  21. Nilsson M, Bengtsson S, Kylin H. Identification and determination of chlorinated paraffins using multivariate evaluation of gas chromatographic data. Environ Pollut. 2012;163:142–8.

  22. Stockholm Convention on Persistent Organic Pollutants (2009). http://chm.pops.int

  23. Canadian Environmental Protection Act. 1999 (S.C. 1999, c. 33) http://laws-lois.justice.gc.ca/eng/acts/C-15.31/section-93.html

  24. Sverko E, Tomy GT, Marvi CH, Muir DCG. Improving the quality of environmental measurements on short chain chlorinated paraffins to support global regulatory efforts. Environ Sci Technol. 2012;46:4697–8.

    Article  CAS  Google Scholar 

  25. International Chlorinated Alkanes Industry Association; Newsletters http://www.eurochlor.org/chlorinated-alkanes-(casg)/international-cooperation.aspx

  26. Zencak Z, Oehme M. Recent developments in the analysis of chlorinated paraffins. Trends Anal Chem. 2006;25(4):310–7.

    Article  CAS  Google Scholar 

  27. Van Mourik LM, Leonards PE, Gaus C, De Boer. Recent developments in capabilities for analysing chlorinated paraffins in environmental matrices: a review. Chemosphere. 2015;136:259.

    Article  Google Scholar 

  28. Phillips J, Liu Z. Comprehensive two-dimensional gas chromatography using an on-column thermal modulator interface. J Chromatogr Sci. 1991;29:227–31.

  29. Muscalu AM, Reiner EJ, Liss SN, Chen T, Ladwig G, Morse D. A routine accredited method for the analysis of polychlorinated biphenyls, organochlorine pesticides, chlorobenzenes and screening of other halogenated organics in soil, sediment and sludge by GCxGC-μECD. Anal Bioanal Chem. 2011;401:2403–13.

    Article  CAS  Google Scholar 

  30. Ontario Ministry of the Environment and Climate Change. Method E3487 (2010).

  31. Korytár P, Leonards PEG, de Boer J, Brinkman UAT. Group separation of organohalogenated compounds by means of comprehensive two-dimensional gas chromatography. J Chromatogr A. 2005;1086(1-2):29–44.

    Article  Google Scholar 

  32. Korytár P, Parera J, Leonards PEG, Santos FJ, de Boer J, Brinkman UAT. Characterization of polychlorinated n-alkanes using comprehensive two-dimensional gas chromatography–electron-capture negative ionisation time-of-flight mass spectrometry. J Chromatogr A. 2005;1086(1):71–82.

    Article  Google Scholar 

  33. Xia D, Gao L, Zhu S, Zheng M. Separation and screening of short-chain chlorinated paraffins in environmental samples using comprehensive two-dimensional gas chromatography with micro electron capture detection. Anal Bioanal Chem. 2014;406(29):7561–70.

    Article  CAS  Google Scholar 

  34. van der Veen I, Cofino W, Crum S, De Boer J. Interlaboratory study on the analysis of chlorinated paraffins in environmental matrices, phase 1. IVM Institute for Environmental Studies, Amsterdam, 2012, QUASIMEME Report W-12/11.

  35. van Mourik L, van der Veen I, Crum S, De Boer J. Interlaboratory study on the analysis of chlorinated paraffins in environmental matrices, phase 3. IVM Institute for Environmental Studies, Amsterdam. 2014; QUASIMEME Report R-15/10.

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Acknowledgments

The authors would like to thank Sean Backus and Libia Saborido Basconcillo of the Environment Canada for providing valuable information and support for this study. We would also like to thank Vedrana Pantelic of the Ontario Ministry of the Environment and Climate Change for the support during the study.

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Authors and Affiliations

  1. Ministry of the Environment and Climate Change (MOECC), Toronto, ON, M9P 3V6, Canada

    Alina M. Muscalu, Dave Morse & Eric J. Reiner

  2. Department of Chemistry, University of Waterloo, Waterloo, ON, N2L 3G1, Canada

    Alina M. Muscalu & Tadeusz Górecki

Authors
  1. Alina M. Muscalu
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  2. Dave Morse
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  3. Eric J. Reiner
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  4. Tadeusz Górecki
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Correspondence to Eric J. Reiner.

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Muscalu, A.M., Morse, D., Reiner, E.J. et al. The quantification of short-chain chlorinated paraffins in sediment samples using comprehensive two-dimensional gas chromatography with μECD detection. Anal Bioanal Chem 409, 2065–2074 (2017). https://doi.org/10.1007/s00216-016-0153-1

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  • DOI: https://doi.org/10.1007/s00216-016-0153-1

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