Reduction Pathway-Dependent Formation of Reactive Fe(II) Sites in Clay Minerals.

Structural Fe in clay minerals is an important, potentially renewable source of electron equivalents for contaminant reduction, yet our knowledge of how clay mineral Fe reduction pathways and Fe reduction extent affect clay mineral Fe(II) reactivity is limited. Here, we used a nitroaromatic compound (NAC) as a reactive probe molecule to assess the reactivity of chemically reduced (dithionite) and Fe(II)-reduced nontronite across a range of reduction extents. We observed biphasic transformation kinetics for all nontronite reduction extents of ≥5% Fe(II)/Fe(total) regardless of the reduction pathway, indicating that two Fe(II) sites of different reactivities form in nontronite at environmentally relevant reduction extents. At even lower reduction extents, Fe(II)-reduced nontronite completely reduced the NAC whereas dithionite-reduced nontronite could not. Our 57Fe Mössbauer spectroscopy, ultraviolet-visible spectroscopy, and kinetic modeling results suggest that the highly reactive Fe(II) entities likely comprise di/trioctahedral Fe(II) domains in the nontronite structure regardless of the reduction mechanism. However, the second Fe(II) species, of lower reactivity, varies and for Fe(II)-reacted NAu-1 likely comprises Fe(II) associated with an Fe-bearing precipitate formed during electron transfer from aqueous to nontronite Fe. Both our observation of biphasic reduction kinetics and the nonlinear relationship of rate constant and clay mineral reduction potential EH have major implications for contaminant fate and remediation.

A New Approach for Investigating Iron Mineral Transformations in Soils and Sediments Using 57Fe-Labeled Minerals and 57Fe Mössbauer Spectroscopy.

Iron minerals in soils and sediments play important roles in many biogeochemical processes and therefore influence the cycling of major and trace elements and the fate of pollutants in the environment. However, the kinetics and pathways of Fe mineral recrystallization and transformation processes under environmentally relevant conditions are still elusive. Here, we present a novel approach enabling us to follow the transformations of Fe minerals added to soils or sediments in close spatial association with complex solid matrices including other minerals, organic matter, and microorganisms. Minerals enriched with the stable isotope 57Fe are mixed with soil or sediment, and changes in Fe speciation are subsequently studied by 57Fe Mössbauer spectroscopy, which exclusively detects 57Fe. In this study, 57Fe-labeled ferrihydrite was synthesized, mixed with four soils differing in chemical and physical properties, and incubated for 12+ weeks under anoxic conditions. Our results reveal that the formation of crystalline Fe(III)(oxyhydr)oxides such as lepidocrocite and goethite was strongly suppressed, and instead formation of a green rust-like phase was observed in all soils. These results contrast those from Fe(II)-catalyzed ferrihydrite transformation experiments, where formation of lepidocrocite, goethite, and/or magnetite often occurs. The presented approach allows control over the composition and crystallinity of the initial Fe mineral, and it can be easily adapted to other experimental setups or Fe minerals. It thus offers great potential for future investigations of Fe mineral transformations in situ under environmentally relevant conditions, in both the laboratory and the field.

Ferrihydrite transformations in flooded paddy soils: rates, pathways, and product spatial distributions.

Complex interactions between redox-driven element cycles in soils influence iron mineral transformation processes. The rates and pathways of iron mineral transformation processes have been studied intensely in model systems such as mixed suspensions, but transformation in complex heterogeneous porous media is not well understood. Here, mesh bags containing 0.5 g of ferrihydrite were incubated in five water-saturated paddy soils with contrasting microbial iron-reduction potential for up to twelve weeks. Using X-ray diffraction analysis, we show near-complete transformation of the ferrihydrite to lepidocrocite and goethite within six weeks in the soil with the highest iron(II) release, and slower transformation with higher ratios of goethite to lepidocrocite in soils with lower iron(II) release. In the least reduced soil, no mineral transformations were observed. In soils where ferrihydrite transformation occurred, the transformation rate was one to three orders of magnitude slower than transformation in comparable mixed-suspension studies. To interpret the spatial distribution of ferrihydrite and its transformation products, we developed a novel application of confocal micro-Raman spectroscopy in which we identified and mapped minerals on selected cross sections of mesh bag contents. After two weeks of flooded incubation, ferrihydrite was still abundant in the core of some mesh bags, and as a rim at the mineral-soil interface. The reacted outer core contained unevenly mixed ferrihydrite, goethite and lepidocrocite on the micrometre scale. The slower rate of transformation and uneven distribution of product minerals highlight the influence of biogeochemically complex matrices and diffusion processes on the transformation of minerals, and the importance of studying iron mineral transformation in environmental media.

A comparison of methods used to calculate normal background concentrations of potentially toxic elements for urban soil.

To meet the requirements of regulation and to provide realistic remedial targets there is a need for the background concentration of potentially toxic elements (PTEs) in soils to be considered when assessing contaminated land. In England, normal background concentrations (NBCs) have been published for several priority contaminants for a number of spatial domains however updated regulatory guidance places the responsibility on Local Authorities to set NBCs for their jurisdiction. Due to the unique geochemical nature of urban areas, Local Authorities need to define NBC values specific to their area, which the national data is unable to provide. This study aims to calculate NBC levels for Gateshead, an urban Metropolitan Borough in the North East of England, using freely available data. The 'median + 2MAD', boxplot upper whisker and English NBC (according to the method adopted by the British Geological Survey) methods were compared for test PTEs lead, arsenic and cadmium. Due to the lack of systematically collected data for Gateshead in the national soil chemistry database, the use of site investigation (SI) data collected during the planning process was investigated. 12,087 SI soil chemistry data points were incorporated into a database and 27 comparison samples were taken from undisturbed locations across Gateshead. The SI data gave high resolution coverage of the area and Mann-Whitney tests confirmed statistical similarity for the undisturbed comparison samples and the SI data. SI data was successfully used to calculate NBCs for Gateshead and the median+2MAD method was selected as most appropriate by the Local Authority according to the precautionary principle as it consistently provided the most conservative NBC values. The use of this data set provides a freely available, high resolution source of data that can be used for a range of environmental applications.