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Lepidocrocite Formation Kinetics from Schwertmannite in Fe(II)-Rich Anoxic Alkaline Medium

Kinetik der Lepidokrokitbildung aus Schwertmannit in Fe(II)-reichen anoxischen Medien

Cinética de formación de epidocrocita a partir de schwertmannita en un medio alcalino anóxico rico en Fe(II)

无氧、碱性、富铁(FeII)条件下施氏矿生成纤铁矿的动力学特征

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Abstract

Effect of dissolved ferrous iron [Fe(II)aq = 0–1.0 mM] on stability of schwertmannite containing ≈40 wt% Fe(III) and 15 wt% SO4 2− [with and without 0.92 wt% sorbed As(III)] was investigated in anoxic alkaline conditions at pH 8 for 154 h. New product formation, sulfate, iron, and arsenic release kinetics were examined using diffractogram, microscopic, spectroscopic and geochemical techniques. Both schwertmannite types were incompletely transformed to lepidocrocite with a platy tabular morphometry. Product formation was accelerated with increased Fe(II)aq, while sorbed As(III) markedly hindered lepidocrocite formation. Almost 50–57 % of the SO4 2− was released from schwertmannite within 154 h in the absence of Fe(II)aq, while its presence inhibited its release. Some of the sorbed As(III) was released during lepidocrocite formation with a maximum in the presence of 1.0 mM Fe(II)aq (0.02 %, 21 µg L−1), presumably due to catalytic action of Fe(II)aq on schwertmannite dissolution, which likely re-precipitated as lepidocrocite with considerable surface-adsorbed SO4 2−.

Zusammenfassung

In Versuchen wurde der Effekt von gelöstem zweiwertigem Eisen (Fe(II)aq = 0-1,0 mM) auf die Stabilität von Schwertmannit mit 40 Ma.- % Fe(III) und 15 Ma.- % SO 2-4 (mit und ohne 0,93 Ma.- % sorbiertes As(III)) unter anoxischen Bedinungen bei pH-Werten um 8 über 154 h untersucht. Die Bildung neuer Reaktionsprodukte sowie die Kinetik der Freisetzung von Sulfat, Eisen und Arsen wurde mit Hilfe von diffraktometrischen, mikroskopischen, spektroskopischen und geochemischen Methoden untersucht. Beide Schwertmannittypen wurden unvollständig in Lepidokrokit umgewandelt. Die Umwandlung wurde durch eine erhöhte Fe(II)aq-Konzentration beschleunigt. Dagegen wurde die Bildung von Lepidokrokit durch sorbiertes As(III) stark behindert. Bei Abwesenheit von Fe(II)aq wurden etwa 50 % bis 57 % des SO 2-4 innerhalb von 154 h freigesetzt, während die Anwesenheit die Freisetzung hemmt. Ein Teil des sorbierten As(III) wurde während der Lepidokrokitbildung freigesetzt. Die maximale Freisetzung erfolgte bei Anwesenheit von 1,0 mM Fe(II)aq (0,02 %, 21 µg/L), vermutlich durch die katalytische Wirkung des Fe(II)aq auf die Lösung von Schwertmannit. An der Oberfläche des gebildeten Lepidokrokits adsorbiert überwiegend SO4 2−.

Resumen

Se investigó el efecto de hierro ferroso disuelto (Fe(II)ac = 0-1,0 mM) sobre la estabilidad de schwertmannita con un contenido de ≈ 40 % p/p de Fe(III) y 15 % p/p de SO42- (con y sin 0,92 % p/p de As(III) adsorbido) bajo condiciones alcalinas anóxicas, a pH 8, durante 154 h. La formación de nuevos productos y las cinéticas de disolución de sulfato, hierro y arsénico se examinaron usando técnicas microscópicas, espectroscópicas, geoquímicas y de difracción. Ambos tipos de schwertmannita fueron transformados incompletamente en lepidocrocita con una morfometría tipo tableta. La formación de producto fue acelerada por el incremento de la concentración de Fe(II)ac mientras que el As(III) sorbido dificultó marcadamente la formación de lepidocrocita. Casi 50-57 % de SO42- fue liberado de la schwertmannita dentro de las 154 h en ausencia de Fe(II)ac aunque su presencia inhibió esa liberación. Parte del As(III) sorbido fue liberado durante la formación de lepidocrocita con un máximo en la presencia de 1,0 mM de Fe(II)ac (0,02 %, 21 µg L-1), probablemente debido a la acción catalítica de Fe(II)ac sobre la disolución de la schwertmannita dissolution, que reprecipitó como lepidocrocita con una considerable adsorción superficial de SO42-.

摘要

本文研究了在无氧和碱性(pH=8)条件下,可溶亚铁离子〈Fe(II)aq=0-1.0 mM〉在154小时反应时间内对施氏矿〈40%的Fe(III)、15%的SO 2-4 、含或不含0.92%的吸附As(III)〉的稳定性作用。通过衍射试验、显微技术、分光光谱学和地球化学技术研究了该反应过程中新生成物、硫酸根离子、铁离子、砷释放规律的动力学特征。施氏矿不完全地转化为扁平状纤铁矿。新生成物由于可溶亚铁离子增多而增大,而吸附的As(III)却阻碍了纤铁矿生成。在可溶亚铁离子不足时,几乎50-57%的SO 2-4 在154小时内从施氏矿中释放出来; 而当亚铁离子充足时,抑制了SO 2-4 释出。当亚铁离子浓度达最大量时(1.0 mM,或0.02%, 21 µg L−1),部分吸附As(III)也同时释放出来。推测原因是:可溶Fe(II)aq对施氏矿的溶解具有催化化用,再沉淀成的纤铁矿具有更大的表面积来吸附SO 2-4 。

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Acknowledgments

This work was supported by the German Academic Exchange Service (DAAD) and the Geotechnologien programme (BMBF, No-03G0714A) and was performed at the University of Bayreuth, Germany. Dr. Janneck (GEOS, Freiburg) provided the schwertmannite sample. We thank the reviewers for their suggestions on how to improve the data presentation.

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  1. Department of Hydrology, University of Bayreuth, 95440, Bayreuth, Germany

    Susanta Paikaray & Stefan Peiffer

  2. Department of Earth and Environmental Sciences, Indian Institute of Science Education and Research Bhopal, Bhopal, India

    Susanta Paikaray & Stefan Peiffer

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  1. Susanta Paikaray
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Correspondence to Susanta Paikaray.

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Paikaray, S., Peiffer, S. Lepidocrocite Formation Kinetics from Schwertmannite in Fe(II)-Rich Anoxic Alkaline Medium. Mine Water Environ 34, 213–222 (2015). https://doi.org/10.1007/s10230-014-0309-1

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