Redox characterization of the Fe(II)-catalyzed transformation of ferrihydrite to goethite

Jones, Adele M.; Collins, Richard N.; Waite, T. David

doi:10.1016/j.gca.2017.09.024

Cited by 67 publications

(60 citation statements)

References 65 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Extensive microbial dissimilatory iron reduction by Fe(III)-reducing bacteria in dysoxic to anoxic conditions results in low δ 56 Fe values (Beard et al 1999), consistent with results presented by Table 1. Recent research on the reactive nature between aqueous Fe(II) and Fe (III) goethite is of interest for fluvial-lacustrine sediments because of interactions resulting from dissolution/re-precipitation redox-driven processes (Handler et al 2009;Beard et al 2010;Jones et al 2017). Low ambient temperatures with near neutral pH of fluvial-lacustrine environments result in sediment depositional environments in which Fe isotope variations as much as 4‰ can occur.…”

Section: Biomineralizationmentioning

confidence: 99%

Ferruginous casts of bromalites in kaolin beds: microbial ferrihydrite‐goethite transformation as early stage taphonomy in lacustrine and riparian sediments

Broughton

2021

LET

View full text Add to dashboard Cite

Section: Biomineralizationmentioning

confidence: 99%

Ferruginous casts of bromalites in kaolin beds: microbial ferrihydrite‐goethite transformation as early stage taphonomy in lacustrine and riparian sediments

Broughton

2021

LET

View full text Add to dashboard Cite

“…Ferrihydrite transformation to more crystalline phases can be rapidly induced by dissolved Fe(II). At ambient temperatures, this process yields lepidocrocite, goethite, and, at elevated Fe(II) concentrations, magnetite (Tronc et al, 1992;Hansel et al, 2003;Hansel et al, 2005;Pedersen et al, 2005;Yee et al, 2006;Liu et al, 2007;Yang et al, 2010;Hansel et al, 2011;Boland et al, 2013;Boland et al, 2014;Liu et al, 2016;Tomaszewski et al, 2016;Jones et al, 2017). Hematite also occurs when ferrihydrite reacts with dissolved Fe(II) at elevated temperature, typically 60 °C or greater (Hansel et al, 2005;Liu et al, 2005;Pedersen et al, 2005;Liu et al, 2008;Wang et al, 2015).…”

Section: Introductionmentioning

confidence: 99%

Impact of Zn Substitution on Fe(II)-induced Ferrihydrite Transformation Pathways

Yan¹,

Frierdich²,

Catalano³

2022

Preprint

View full text Add to dashboard Cite

Iron oxide minerals are ubiquitous in soils, sediments, and aquatic systems and influence the fate and availability of trace metals. Ferrihydrite is a common iron oxide of nanoparticulate size and poor crystallinity, serving as a thermodynamically unstable precursor to more crystalline phases. While aging induces such phase transformations, these are accelerated by the presence of dissolved Fe(II). However, the impact of trace metals on Fe(II)-catalyzed ferrihydrite phase transformations at ambient temperatures and the associated effects on trace metal speciation has seen limited study. In the present work, phase transformations of ferrihydrite that contains the trace metal zinc in its structure were investigated during aging at ambient temperature in the presence of two different Fe(II) concentrations at pH 7. X-ray diffraction reveals that low Fe(II) concentration (0.2 mM) generates hematite plus minor lepidocrocite, whereas high Fe(II) concentration (1.0 mM) promotes the production of a magnetite-lepidocrocite mixture. In both cases, a substantial fraction of ferrihydrite remains after 12 days. In contrast, Zn-free ferrihydrite forms primarily lepidocrocite and goethite in the presence of 0.2 mM Fe(II), with minor hematite and a trace of ferrihydrite remaining. For 1.0 mM Fe(II), magnetite, goethite, and lepidocrocite form when Zn is absent, leaving no residual ferrihydrite. Transformations of Zn-ferrihydrite produce a transient release of zinc to solution, but this is nearly quantitatively removed into the mineral products after 1 hour. Extended X-ray absorption fine structure spectroscopy suggests that zinc partitions into the newly formed phases, with a shift from tetrahedral to a mixture of tetrahedral and octahedral coordination in the 0.2 mM Fe(II) system and taking on a spinel-like local structure in the 1.0 mM Fe(II) reaction products. This work indicates that substituting elements in ferrihydrite may play a key role in promoting the formation of hematite in low temperature systems, such as soils or sediments. In addition, the retention of zinc in the products of ferrihydrite phase transformation shows that trace metal micronutrients and contaminants may not be mobilized under circumneutral conditions despite the formation of more crystalline iron oxides. Furthermore, mass balance requires that the abundance and isotopic composition of iron oxide-associated zinc, and possibly other trace metals, in the rock record may be retained during diagenetic phase transformations of ferrihydrite if catalyzed by dissolved Fe(II).

show abstract

“…A number of studies have evaluated the impact of Si addition to iron (oxyhydr)oxides (including Fh) on transformation from less to more stable crystalline phases. ,,− In general, Si incorporation into Fh has been shown to inhibit transformation to more stable goethite (Gt) and lepidocrocite (Lp) minerals. , This transformation has been attributed to reductive dissolution of Fe(III) at the Fh surface by sorbed Fe(II), resulting in recrystallization of a more stable mineral phase; , Sheng et al presented evidence that this was related to the formation of a more labile and reactive intermediate-Fe(III) species. Isotope exchange studies indicated that the exchange of sorbed Fe(II) with structural Fe(III) occurred at similar or faster rates for Si-containing versus pure Fh, suggesting that Si inhibited Fh polymerization during recrystallization.…”

Section: Introductionmentioning

confidence: 99%

Biological Reduction of Ferrihydrite with Silica Addition: Rates and Controlling Mechanisms

Gong

Zhang

et al. 2021

ACS Earth Space Chem.

View full text Add to dashboard Cite

Si-incorporated ferrihydrite (SiFh) is ubiquitous in nature, and Fe(III) reactivity within such minerals is relevant to a number of important biogeochemical reactions, including soil organic carbon turnover and pollutant oxidation. Herein, reduction of SiFh with varying Si/Fe molar ratios was investigated and rates and controlling mechanisms were explored. Results showed that SiFh first-order reduction rates increased from 0.038 to 0.113 day–1 as the Si/Fe ratio increases from 0 to 0.444, respectively. As expected, the reduction rate constant increases with decreasing SiFh crystallinty. However, it increases with decreasing SiFh surface area (304.7–188.9 m2 g–1) and standard reduction potential (0.897–0.829 V). The lack of correlation with surface areas or thermodynamic favorability motivated measurement of electron transfer rate constants using mediated electrochemical reduction (MER), and these values increased with Si/Fe ratios of SiFh. This suggests that electron transfer rates to SiFh surfaces may limit SiFh reduction rates by Shewanella oneidensisMR-1 and that electron transfer rates increase with decreasing SiFh crystallinity. The results have implications for understanding rates of metal oxide reduction and associated rates of organic carbon, nutrient, and pollutant oxidation in natural environments where silica is common.

show abstract

Redox characterization of the Fe(II)-catalyzed transformation of ferrihydrite to goethite

Cited by 67 publications

References 65 publications

Ferruginous casts of bromalites in kaolin beds: microbial ferrihydrite‐goethite transformation as early stage taphonomy in lacustrine and riparian sediments

Ferruginous casts of bromalites in kaolin beds: microbial ferrihydrite‐goethite transformation as early stage taphonomy in lacustrine and riparian sediments

Impact of Zn Substitution on Fe(II)-induced Ferrihydrite Transformation Pathways

Biological Reduction of Ferrihydrite with Silica Addition: Rates and Controlling Mechanisms

Contact Info

Product

Resources

About