title: Electrochemistry coupled to (LC-)MS for the simulation of oxidative biotransformation reactions of PAHs.
abstract: Electrochemistry coupled to liquid chromatography and mass spectrometry was used for simulating the biological and environmental fate of polycyclic aromatic hydrocarbons (PAHs) as well as for studying the PAH degradation behavior during electrochemical remediation. Pyrene and benzo[a]pyrene were selected as model compounds and oxidized within an electrochemical thin-layer cell equipped with boron-doped diamond electrode. At potentials of 1.2 and 1.6 V vs. Pd/H2, quinones were found to be the major oxidation products for both investigated PAHs. These quinones belong to a large group of PAH derivatives referred to as oxygenated PAHs, which have gained increasing attention in recent years due to their high abundance in the environment and their significant toxicity. Separation of oxidation products allowed the identification of two pyrene quinone and three benzo[a]pyrene quinone isomers, all of which are known to be formed via photooxidation and during mammalian metabolism. The good correlation between electrochemically generated PAH quinones and those formed in natural processes was also confirmed by UV irradiation experiments and microsomal incubations. At potentials higher than 2.0 V, further degradation of the initial oxidation products was observed which highlights the capability of electrochemistry to be used as remediation technique.
authors.affiliation: Institute of Inorganic and Analytical Chemistry, Westfälische Wilhelms-Universität Münster, Corrensstraße 30, 48149, Münster, Germany; NRW Graduate School of Chemistry, Westfälische Wilhelms-Universität Münster, Wilhelm-Klemm-Strasse 10, 48149, Münster, Germany.
authors.forename: Tina
authors.initials: T
authors.lastname: Wigger
authors.affiliation: Biochemical Institute for Environmental Carcinogens, Lurup 4, 22927, Grosshansdorf, Germany.
authors.forename: Albrecht
authors.initials: A
authors.lastname: Seidel
authors.affiliation: Institute of Inorganic and Analytical Chemistry, Westfälische Wilhelms-Universität Münster, Corrensstraße 30, 48149, Münster, Germany; NRW Graduate School of Chemistry, Westfälische Wilhelms-Universität Münster, Wilhelm-Klemm-Strasse 10, 48149, Münster, Germany. Electronic address: uk@uni-muenster.de.
authors.forename: Uwe
authors.initials: U
authors.lastname: Karst
mesh_terms: D001564:Benzo(a)pyrene / Q000378:metabolism; D001711:Biotransformation; D002853:Chromatography, Liquid / Q000379:methods; D004563:Electrochemistry / Q000379:methods*; D004785:Environmental Pollutants / Q000737:chemistry; D052918:Environmental Restoration and Remediation / Q000379:methods*; D006801:Humans; D013058:Mass Spectrometry; D008862:Microsomes, Liver / Q000378:metabolism; D010084:Oxidation-Reduction; D011084:Polycyclic Aromatic Hydrocarbons / Q000737:chemistry*; D011721:Pyrenes / Q000378:metabolism; D011809:Quinones / Q000378:metabolism
chemical_list: D004785:Environmental Pollutants; D011084:Polycyclic Aromatic Hydrocarbons; D011721:Pyrenes; D011809:Quinones; D001564:Benzo(a)pyrene; C030984:pyrene
keywords: Electrochemistry; Mass spectrometry; Metabolism simulation; PAHs; Photooxidation