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Stability of ferrous-iron-rich bridgmanite under reducing midmantle conditions.

ABSTRACT: Our current understanding of the electronic state of iron in lower-mantle minerals leads to a considerable disagreement in bulk sound speed with seismic measurements if the lower mantle has the same composition as the upper mantle (pyrolite). In the modeling studies, the content and oxidation state of Fe in the minerals have been assumed to be constant throughout the lower mantle. Here, we report high-pressure experimental results in which Fe becomes dominantly Fe²⁺ in bridgmanite synthesized at 40-70 GPa and 2,000 K, while it is in mixed oxidation state (Fe³⁺/∑Fe = 60%) in the samples synthesized below and above the pressure range. Little Fe³⁺ in bridgmanite combined with the strong partitioning of Fe²⁺ into ferropericlase will alter the Fe content for these minerals at 1,100- to 1,700-km depths. Our calculations show that the change in iron content harmonizes the bulk sound speed of pyrolite with the seismic values in this region. Our experiments support no significant changes in bulk composition for most of the mantle, but possible changes in physical properties and processes (such as viscosity and mantle flow patterns) in the midmantle.

SUBMITTER: Shim SH

PROVIDER: S-EPMC5488914 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:High levels of arsenic in groundwater and drinking water are a major health problem. Although the processes controlling the release of As are still not well known, the reductive dissolution of As-rich Fe oxyhydroxides has so far been a favorite hypothesis. Decoupling between arsenic and iron redox transformations has been experimentally demonstrated, but not quantitatively interpreted. Here, we report on incubation batch experiments run with As(V) sorbed on, or co-precipitated with, 2-line ferrihydrite. The biotic and abiotic processes of As release were investigated by using wet chemistry, X-ray diffraction, X-ray absorption and genomic techniques. The incubation experiments were carried out with a phosphate-rich growth medium and a community of Fe(III)-reducing bacteria under strict anoxic conditions for two months. During the first month, the release of Fe(II) in the aqueous phase amounted to only 3% to 10% of the total initial solid Fe concentration, whilst the total aqueous As remained almost constant after an initial exchange with phosphate ions. During the second month, the aqueous Fe(II) concentration remained constant, or even decreased, whereas the total quantity of As released to the solution accounted for 14% to 45% of the total initial solid As concentration. At the end of the incubation, the aqueous-phase arsenic was present predominately as As(III) whilst X-ray absorption spectroscopy indicated that more than 70% of the solid-phase arsenic was present as As(V). X-ray diffraction revealed vivianite Fe(II)3(PO4)2.8H2O in some of the experiments. A biogeochemical model was then developed to simulate these aqueous- and solid-phase results. The two main conclusions drawn from the model are that (1) As(V) is not reduced during the first incubation month with high Eh values, but rather re-adsorbed onto the ferrihydrite surface, and this state remains until arsenic reduction is energetically more favorable than iron reduction, and (2) the release of As during the second month is due to its reduction to the more weakly adsorbed As(III) which cannot compete against carbonate ions for sorption onto ferrihydrite. The model was also successfully applied to recent experimental results on the release of arsenic from Bengal delta sediments.

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Stability of ferrous-iron-rich bridgmanite under reducing midmantle conditions.

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