title: Quantification of methylated selenium, sulfur, and arsenic in the environment.
abstract: Biomethylation and volatilization of trace elements may contribute to their redistribution in the environment. However, quantification of volatile, methylated species in the environment is complicated by a lack of straightforward and field-deployable air sampling methods that preserve element speciation. This paper presents a robust and versatile gas trapping method for the simultaneous preconcentration of volatile selenium (Se), sulfur (S), and arsenic (As) species. Using HPLC-HR-ICP-MS and ESI-MS/MS analyses, we demonstrate that volatile Se and S species efficiently transform into specific non-volatile compounds during trapping, which enables the deduction of the original gaseous speciation. With minor adaptations, the presented HPLC-HR-ICP-MS method also allows for the quantification of 13 non-volatile methylated species and oxyanions of Se, S, and As in natural waters. Application of these methods in a peatland indicated that, at the selected sites, fluxes varied between 190-210 ng Se·m(-2)·d(-1), 90-270 ng As·m(-2)·d(-1), and 4-14 µg S·m(-2)·d(-1), and contained at least 70% methylated Se and S species. In the surface water, methylated species were particularly abundant for As (>50% of total As). Our results indicate that methylation plays a significant role in the biogeochemical cycles of these elements.
authors.affiliation: Department of Water Resources and Drinking Water, Swiss Federal Institute of Aquatic Science and Technology, Dübendorf, Switzerland; Institute of Biogeochemistry and Pollutant Dynamics, Swiss Federal Institute of Technology, Zürich, Switzerland.
authors.forename: Bas
authors.initials: B
authors.lastname: Vriens
authors.affiliation: Department of Environmental Toxicology, Swiss Federal Institute of Aquatic Science and Technology, Dübendorf, Switzerland.
authors.forename: Adrian A
authors.initials: AA
authors.lastname: Ammann
authors.affiliation: Department of Thin Films and Photovoltaics, Swiss Federal Institute for Material Science and Technology, Dübendorf, Switzerland.
authors.forename: Harald
authors.initials: H
authors.lastname: Hagendorfer
authors.affiliation: Institute for Ecopreneurship, School of Life Science, University of Applied Sciences and Arts Northwestern Switzerland, Muttenz, Switzerland; Department of Environmental Technology, Wageningen University, Wageningen, The Netherlands.
authors.forename: Markus
authors.initials: M
authors.lastname: Lenz
authors.affiliation: Department of Water Resources and Drinking Water, Swiss Federal Institute of Aquatic Science and Technology, Dübendorf, Switzerland.
authors.forename: Michael
authors.initials: M
authors.lastname: Berg
authors.affiliation: Department of Water Resources and Drinking Water, Swiss Federal Institute of Aquatic Science and Technology, Dübendorf, Switzerland; Institute of Biogeochemistry and Pollutant Dynamics, Swiss Federal Institute of Technology, Zürich, Switzerland.
authors.forename: Lenny H E
authors.initials: LH
authors.lastname: Winkel
mesh_terms: D001151:Arsenic / Q000032:analysis*; D002851:Chromatography, High Pressure Liquid; D004777:Environment; D012643:Selenium / Q000032:analysis*; D013455:Sulfur / Q000032:analysis*; D053719:Tandem Mass Spectrometry; D014131:Trace Elements / Q000032:analysis*; D014835:Volatilization
chemical_list: D014131:Trace Elements; D013455:Sulfur; D012643:Selenium; D001151:Arsenic