Iron and Arsenic Speciation and Distribution in Organic Flocs from Streambeds of an Arsenic-Enriched Peatland

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• 作者：Laurel K. ThomasArrigo ; Christian Mikutta ; James Byrne ; Kurt Barmettler ; Andreas Kappler ; Ruben Kretzschmar
• 刊名：Environmental Science & Technology
• 出版年：2014
• 出版时间：November 18, 2014
• 年：2014
• 卷：48
• 期：22
• 页码：13218-13228
• 全文大小：603K
• 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. To date, spectroscopic speciation analyses of Fe and trace elements in these mineral-organic matter (OM) associations are missing. In this study, we investigated the speciation and distribution of Fe and As in flocs collected from low-flow streams (pH 5.3鈥?.3) of the naturally As-enriched peatland Gola di Lago (Switzerland) using ⁵⁷Fe M枚ssbauer spectroscopy and synchrotron X-ray techniques. The flocs were rich in acid carbohydrates and contained up to 22.1 wt % Fe, 34.9 wt % C, and 2620 mg/kg As. M枚ssbauer analyses revealed small quantities (<5%) of Fe(II) and Fe(III)-OM complexes and the predominance of ferrihydrite (鈭糉e₅HO₈路4H₂O, 51鈥?9%) and lepidocrocite (纬-FeOOH, 34鈥?6%). The latter was not observed by synchrotron X-ray diffraction, implying a coherent scattering domain size of <10 nm. Iron X-ray absorption spectroscopy (XAS) confirmed the M枚ssbauer results, and bulk As XAS indicated the prevalence of arsenate (71鈥?4%) in the flocs. Shell-fit analyses showed that As was entirely sorbed to Fe(III)-(oxyhydr)oxides and that both arsenate and arsenite exclusively formed monodentate-binuclear (鈥渂ridging鈥? complexes (R_As鈥揊e = 3.31鈥?.34 脜). Microfocused X-ray fluorescence spectrometry documented a strong correlation between As and Fe in the flocs. These analyses also revealed intense As hotspots coinciding with abundant freshwater green algae (Closterium spp.). Microfocused As X-ray absorption near-edge structure spectra collected at algae-specific points identified up to 29% As(III), which, in combination with 鈭?% As(III) detected at Fe-rich points, suggests As(V) bioreduction in the algae. Our findings imply that floc (bio)organics serve primarily as nucleation sites for the precipitation of nanocrystalline Fe(III)-(oxyhydr)oxides, rendering flocs effective sorbents for trace metal(loid)s. Thus, Fe-rich freshwater flocs likely play a pivotal role for the speciation and cycling of trace elements in wetlands.