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Appears in Collections:Biological and Environmental Sciences Journal Articles
Peer Review Status: Refereed
Title: Structure and composition of Fe-OM co-precipitates that form in soil-derived solutions
Authors: Fritzsche, Andreas
Schröder, Christian
Wieczorek, Arkadiusz
Handel, Matthias
Ritschel, Thomas
Totsche, Kai U
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Issue Date: 15-Nov-2015
Publisher: Elsevier
Citation: Fritzsche A, Schröder C, Wieczorek A, Handel M, Ritschel T & Totsche KU (2015) Structure and composition of Fe-OM co-precipitates that form in soil-derived solutions, Geochimica et Cosmochimica Acta, 169, pp. 167-183.
Abstract: Iron oxides represent a substantial fraction of secondary minerals and particularly affect the reactive properties of natural systems in which they formed, e.g. in soils and sediments. Yet, it is still obscure how transient conditions in the solution will affect the properties of in situ precipitated Fe oxides. Transient compositions, i.e. compositions that change with time, arise due to predominant non-equilibrium states in natural systems, e.g. between liquid and solid phases in soils. In this study, we characterize Fe-OM co-precipitates that formed in pH-neutral exfiltrates from anoxic topsoils under transient conditions. We applied soil column outflow experiments, in which Fe 2+was discharged with the effluent from anoxic soil and subsequently oxidized in the effluent due to contact with air. Our study features three novel aspects being unconsidered so far: i) the transient composition of soil-derived solutions, ii) that pedogenic Fe oxides instead of Fe salts serve as major source for Fe2+ in soil solution and iii) the presence of exclusively soil-derived organic and inorganic compounds during precipitation. The experiments were carried out with two topsoil materials that differed in composition, texture and land use. Derived from Mössbauer spectroscopy, broad distributions in quadrupole splittings (0 - 2 mm s-1) and magnetic hyperfine fields (35 - 53 T) indicated the presence of low-crystalline ferrihydrite and even lower crystalline Fe phases in all Fe-OM co-precipitates. There was no unequivocal evidence for other Fe oxides, i.e. lepidocrocite and (nano)goethite. The Fe-OM co-precipitates contained inorganic (P, sulfate, silicate, Al, As) and organic compounds (proteins, polysaccharides), which were concurrently discharged from the soils. Their content in the Fe-OM co-precipitates was controlled by their respective concentration in the soil-derived solution. On a molar basis, OC and Fe were the main components in the Fe-OM co-precipitates (OC/Fe ratio = 0.5 - 2). The elemental composition of the Fe-OM co-precipitates was in accordance with the sequential precipitation of Fe(III)phosphates/arsenates prior to the formation of ferrihydrite. This explains decreasing Si contents in the Fe-OM co-precipitates with increasing availability of P. With respect to constant mean quadrupole splittings and slightly decreasing mean magnetic hyperfine fields, increasing contents of OC, P and Al in the Fe-OM co-precipitates did not further increase the structural disorder of the Fe polyhedra, while the crystallite interactions slightly decreased. Scanning electron microscopy and dynamic light scattering revealed the coincidental presence of variably sized aggregates and a considerable amount of Fe-OM co-precipitates, which remained dispersed in solution for months. Thus, variably composed Fe-OM co-precipitates with highly diverse aggregate sizes and comparably constant poor crystallinity can be expected after the oxidation of Fe2+ in transient, soil-derived solutions.
Type: Journal Article
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Rights: This item has been embargoed for a period. During the embargo please use the Request a Copy feature at the foot of the Repository record to request a copy directly from the author. You can only request a copy if you wish to use this work for your own research or private study. Accepted refereed manuscript of: Fritzsche A, Schröder C, Wieczorek A, Handel M, Ritschel T & Totsche KU (2015) Structure and composition of Fe-OM coprecipitates that form in soil-derived solutions, Geochimica et Cosmochimica Acta, 169, pp. 167-183. DOI: 10.1016/j.gca.2015.07.041 © 2015, Elsevier. Licensed under the Creative Commons Attribution- NonCommercial-NoDerivatives 4.0 International
Affiliation: Friedrich Schiller University of Jena
Biological and Environmental Sciences
Friedrich Schiller University of Jena
Friedrich-Schiller-Universität, Germany
Friedrich Schiller University of Jena
Friedrich-Schiller-Universität, Germany

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