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Arsenic speciation in sulfidic waters : Reconciling contradictory spectroscopic and chromatographic evidence

Title data

Planer-Friedrich, Britta ; Süß, Elke ; Scheinost, Andreas C. ; Wallschläger, Dirk:
Arsenic speciation in sulfidic waters : Reconciling contradictory spectroscopic and chromatographic evidence.
In: Analytical Chemistry. Vol. 82 (2010) Issue 24 . - pp. 10228-10235.
ISSN 1520-6882
DOI: https://doi.org/10.1021/ac1024717

Abstract in another language

In recent years, analytical methods have been developed that have demonstrated that soluble arsenic-sulfur species constitute a major fraction of dissolved arsenic in sulfidic waters. However, an intense debate is going on about the exact chemical nature of these compounds, since X-ray absorption spectroscopy (XAS) data generated at higher (mmol/L) concentrations suggest the presence of (oxy)thioarsenites in such waters, while ion chromatographic (IC) and mass spectroscopic data at lower (μmol/L to nmol/L) concentrations indicate the presence of (oxy)- thioarsenates. In this contribution, we connect and explain these two apparently different types of results. We show by XAS that thioarsenites are the primary reaction products of arsenite and sulfide in geochemical model experiments in the complete absence of oxygen. However, thioarsenites are extremely unstable toward oxidation, and convert rapidly into thioarsenates when exposed to atmospheric oxygen, e.g., while waiting for analysis on the chromatographic autosampler. This problem can only be eliminated when the entire chromatographic process is conducted inside a glovebox. We also show that thioarsenites are unstable toward sample dilution, which is commonly employed prior to chromatographic analysis when ultrasensitive detectors like ICP-MS are used. This instability has two main reasons: if pH changes during dilution, then equilibria between individual arsenic-sulfur species rearrange rapidly due to their different stability regions within the pH range, and if pH is kept constant during dilution, then this changes the ratio between OHand SH- in solution, which in turn shifts the underlying speciation equilibria. This problem is avoided by analyzing samples undiluted. Our studies show that thioarsenites appear as thioarsenates in IC analyses if oxygen is not excluded completely, and as arsenite if samples are diluted in alkaline anoxic medium. This also points out that thioarsenites are necessary intermediates in the formation of thioarsenates.

Further data

Item Type: Article in a journal
Refereed: Yes
Additional notes: BAYCEER88401
Institutions of the University: Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Earth Sciences > Professorship Environmental Geochemistry Group
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Earth Sciences > Professorship Environmental Geochemistry Group > Professorship Environmental Geochemistry - Univ.-Prof. Dr. Britta Planer-Friedrich
Research Institutions > Research Centres > Bayreuth Center of Ecology and Environmental Research- BayCEER
Faculties
Faculties > Faculty of Biology, Chemistry and Earth Sciences
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Earth Sciences
Research Institutions
Research Institutions > Research Centres
Result of work at the UBT: Yes
DDC Subjects: 500 Science
Date Deposited: 05 May 2015 12:10
Last Modified: 05 May 2015 12:10
URI: https://eref.uni-bayreuth.de/id/eprint/12798