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Analytical and Bioanalytical Chemistry

, Volume 397, Issue 1, pp 43–54 | Cite as

Application of the novel 5-chloro-2,2,3,3,4,4,5,5-octafluoro-1-pentyl chloroformate derivatizing agent for the direct determination of highly polar water disinfection byproducts

  • Marco Vincenti
  • Francesca Fasano
  • Maria Carmen Valsania
  • Pierantonio Guarda
  • Susan D. Richardson
Paper in Forefront

Abstract

A novel derivatizing agent, 5-chloro-2,2,3,3,4,4,5,5-octafluoropentyl chloroformate (ClOFPCF), was synthesized and tested as a reagent for direct water derivatization of highly polar and hydrophilic analytes. Its analytical performance satisfactorily compared to a perfluorinated chloroformate previously described, namely 2,2,3,3,4,4,5,5-octafluoropentyl chloroformate (OFPCF). The chemical properties (reactivity, selectivity, derivatization products, and their chromatographic and spectral features) for ClOFPCF were investigated using a set of 39 highly polar standard analytes, including, among others, hydroxylamine, malic and succinic acids, resorcinol, hydroxybenzaldehyde, and dihydroxybenzoic acid. Upon derivatization, the analytes were extracted from the aqueous solvent and analyzed by gas chromatography (GC)-mass spectrometry (MS) in the electron-capture negative ionization (ECNI) mode. Positive chemical ionization (PCI)-MS was used for confirming the molecular ions, which were virtually absent in the ECNI mass spectra. ClOFPCF showed good reaction efficiency, good chromatographic and spectroscopic properties (better than with OFPCF), good linearity in calibration curves, and low detection limits (0.3–1 µg/L). A unique feature of the derivatizations with ClOFPCF, and, in general, highly fluorinated chloroformates, is their effectiveness in reacting with carboxylic, hydroxylic, and aminic groups at once, forming multiply-substituted non-polar derivatives that can be easily extracted from the aqueous phase and determined by GC-ECNI-MS. The entire procedure from raw aqueous sample to ready-to-inject hexane solution of the derivatives requires less than 10 min. Another benefit of this procedure is that it produced stable derivatives, with optimal volatility for GC separation, and high electron affinity, which allows their detection as negative ions at trace level. In addition, their mass spectra exhibits chlorine isotopic patterns that clearly indicate how many polar hydrogens of the analyte undergo derivatization. Finally, derivatization with ClOFPCF was used successfully to identify 13 unknown highly polar disinfection byproducts (DBPs) in ozonated fulvic and humic acid aqueous solutions and in real ozonated drinking water.

Figure

The derivatization of hydroxylamine with 5-chloro-2,2,3,3,4,4,5,5-octafluoropentyl chloroformate yields optimal gas chromatographic separation despite a 27-fold molecular weight increment.

Keywords

Humic substances Water disinfection byproducts Derivatization Chloroformate Hydrophilic compounds ECNI 

Notes

Acknowledgments

Financial support from the U.S. Environmental Protection Agency (U.S.-EPA; Cooperative Agreement No. R-82795101-1), from M.I.U.R. and Regione Piemonte is gratefully acknowledged. This paper has been reviewed in accordance with the U.S. EPA’s peer and administrative review policies and approved for publication. Mention of trade names or commercial products does not constitute endorsement or recommendation for use by the U.S. EPA.

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Copyright information

© Springer-Verlag 2010

Authors and Affiliations

  • Marco Vincenti
    • 1
  • Francesca Fasano
    • 1
  • Maria Carmen Valsania
    • 2
  • Pierantonio Guarda
    • 3
  • Susan D. Richardson
    • 4
  1. 1.Dipartimento di Chimica AnaliticaUniversità degli Studi di TorinoTorinoItaly
  2. 2.Dipartimento di Traumatologia, Ortopedia e Medicina del LavoroUniversità degli Studi di TorinoTorinoItaly
  3. 3.Solvay Solexis S.p.A.MilanItaly
  4. 4.National Exposure Research LaboratoryU.S. Environmental Protection AgencyAthensUSA

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