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Feasibility of gas chromatography-atmospheric pressure photoionization–high-resolution mass spectrometry for the analysis of polychlorinated dibenzo-p-dioxins, dibenzofurans, and dioxin-like polychlorinated biphenyls in environmental and feed samples

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Abstract

In this work, the suitability of atmospheric pressure photoionization (APPI) has been assessed for the determination of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) by gas chromatography–high-resolution mass spectrometry (GC-HRMS). The APPI of target compounds has been tested in both positive and negative ion modes. Under positive ion mode, the analytes generated the molecular ion, which was favoured using dopants that promote charge exchange gas-phase reactions (i.e., benzene), while in negative ion mode, the ion [M−Cl+O]− for PCDFs and dl-PCBs were mainly formed, providing the best results using benzene and diethyl ether as dopants, respectively. Concerning PCDDs, highly chlorinated congeners were mainly ionized by means of the [M−Cl]− ion, whereas [M−Cl+O2]− was the base peak for tetraCDD and [M−Cl+O]− for penta- and hexaCDDs. Method quality parameters, in accordance with the current EU Regulation guidelines for food and feed analysis, showed the good performance of the two GC-APPI-HRMS (Orbitrap) methods since they provided high detection capability (low fg levels), good linearity, and satisfactory precision (RSD% < 9%). In addition, the GC-APPI-HRMS (Orbitrap) methods were validated by analysing selected environmental and feed samples and the results were compared to those obtained using conventional GC-EI-HRMS, demonstrating the good performance in the analysis of the target compounds. Hence, the GC-APPI-HRMS technique can be proposed as alternative to the conventional methods for the determination of PCDD/Fs and dl-PCBs in environmental and feed matrices.

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Funding

The authors thank the financial support received from the Spanish Ministry of Science, Innovation and Universities (project codes: PGC2018-095013-B-I00 and CEX2018-000794-S) and from the Generalitat of Catalonia (project code: 2017–SGR–310). Juan F. Ayala-Cabrera acknowledges the Spanish Ministry of Education, Culture and Sports for the PhD FPU fellowship (code: FPU14/05539).

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Authors and Affiliations

  1. Department of Chemical Engineering and Analytical Chemistry, University of Barcelona, Av. Diagonal 645, 08028, Barcelona, Spain

    J. F. Ayala-Cabrera, E. Moyano & F. J. Santos

  2. Laboratory of Dioxins, Institute of Environmental Assessment and Water Research (IDAEA-CSIC), C/Jordi Girona, 18-26, 08034, Barcelona, Spain

    M. Ábalos & E. Abad

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  1. J. F. Ayala-Cabrera
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  2. M. Ábalos
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Correspondence to F. J. Santos.

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Ayala-Cabrera, J.F., Ábalos, M., Abad, E. et al. Feasibility of gas chromatography-atmospheric pressure photoionization–high-resolution mass spectrometry for the analysis of polychlorinated dibenzo-p-dioxins, dibenzofurans, and dioxin-like polychlorinated biphenyls in environmental and feed samples. Anal Bioanal Chem 412, 3703–3716 (2020). https://doi.org/10.1007/s00216-020-02615-7

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