Sulfidization of Organic Freshwater Flocs from a Minerotrophic Peatland: Speciation Changes of Iron, Sulfur, and Arsenic

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• 作者：Laurel K. ThomasArrigo ; Christian Mikutta ; Regina Lohmayer ; Britta Planer-Friedrich ; Ruben Kretzschmar
• 刊名：Environmental Science & Technology
• 出版年：2016
• 出版时间：April 5, 2016
• 年：2016
• 卷：50
• 期：7
• 页码：3607-3616
• 全文大小：722K
• ISSN：1520-5851

文摘

Iron-rich organic flocs are frequently observed in surface waters of wetlands and show a high affinity for trace metal(loid)s. Under low-flow stream conditions, flocs may settle, become buried, and eventually be subjected to reducing conditions facilitating trace metal(loid) release. In this study, we reacted freshwater flocs (704–1280 mg As/kg) from a minerotrophic peatland (Gola di Lago, Switzerland) with sulfide (5.2 mM, S(-II)_spike/Fe = 0.75–1.62 mol/mol) at neutral pH and studied the speciation changes of Fe, S, and As at 25 ± 1 °C over 1 week through a combination of synchrotron X-ray techniques and wet-chemical analyses. Sulfidization of floc ferrihydrite and nanocrystalline lepidocrocite caused the rapid formation of mackinawite (52–81% of Fe_solid at day 7) as well as solid-phase associated S(0) and polysulfides. Ferrihydrite was preferentially reduced over lepidocrocite, although neoformation of lepidocrocite from ferrihydrite could not be excluded. Sulfide-reacted flocs contained primarily arsenate (47–72%) which preferentially adsorbed to Fe(III)-(oxyhydr)oxides, despite abundant mackinawite precipitation. At higher S(-II)_spike/Fe molar ratios (≥1.0), the formation of an orpiment-like phase accounted for up to 35% of solid-phase As. Despite Fe and As sulfide precipitation and the presence of residual Fe(III)-(oxyhydr)oxides, mobilization of As was recorded in all samples (As_aq = 0.45–7.0 μM at 7 days). Aqueous As speciation analyses documented the formation of thioarsenates contributing up to 33% of As_aq. Our findings show that freshwater flocs from the Gola di Lago peatland may become a source of As under sulfate-reducing conditions and emphasize the pivotal role Fe-rich organic freshwater flocs play in trace metal(loid) cycling in S-rich wetlands characterized by oscillating redox conditions.