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Iron and arsenic speciation in marine sediments undergoing a resuspension event: the impact of biotic activity

  • SEDIMENTS, SEC 2 • PHYSICAL AND BIOGEOCHEMICAL PROCESSES • RESEARCH ARTICLE
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Abstract

Purpose

Changes in the chemical conditions of sediment following a resuspension event might lead to release of sequestered pollutants. In the present study, arsenic (As) and iron (Fe) speciation were investigated before and after such an event, in sediment from L'Estaque marina (France). This marina is located near an industrial plant which processed As-bearing ores for several decades.

Materials and methods

Cores (0–60 cm) and surface sediment (0–10 cm) were collected by a diver. Sediment properties along the length of the core were determined by coupling chemical extractions, and diffraction (i.e., X-ray diffraction) and spectroscopic techniques (i.e., micro-X-ray fluorescence, scanning electron microscopy coupled with energy dispersive spectroscopy, Raman spectroscopy, and X-ray absorption near-edge spectroscopy). Laboratory experiments mimicking resuspension and resettlement events were conducted over a period of 3 months in both biotic and abiotic (autoclaved) conditions. In both cases, oxidation proceeded by oxygen diffusion from the top to the bottom of the sediment.

Results and discussion

It was demonstrated that the unperturbed sediment was anoxic. Arsenic, almost fully under its trivalent As(III) form, had a concentration between 194 and 473 μg g−1, and its main carrier phase was the Fe-monosulfide mackinawite; this mineral originated from in situ transformation of Fe oxides, partly emitted by the industrial plant. The observed progressive pyritisation of mackinawite was not accompanied by further reduction of As which means that As remained bound to mackinawite, as incorporation into the pyrite lattice would require that it reduced to its (−I) oxidation state.

After oxidation during the resuspension event, and in abiotic conditions, As was fully pentavalent As(V) in the oxidized zone of the re-settled sediment. On the contrary, in the biotic experiment, the development of a bacterial mat, which consumed oxygen for respiration processes, preserved the sediment from total oxidation. Consequently, As was present under both As(III) and As(V) forms, the first one being minor (∼20 % of total As) in the top of the sediment. The diversity of aioA genes was large, and was similar in the oxidized layer and the deeper black-colored sediment.

Conclusions

These results indicate that biological processes partly control the in situ geochemical system by inducing low redox areas in theoretically oxidized sediments.

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Acknowledgments

This study was part of the ASEDMAR project, supported by the French National Research Agency, under reference“2008 CESA-003”. It was performed within the framework of the research network “Arsenic metabolism in Prokaryotes” (GDR2909-CNRS). The authors thank Gaboreau S. for the preparation of the thin sections, and Jean-Prost V. and Ruffier V. for their help during XRD measurements. M. Alleki is thanked for his help during sample preparation. Dr. C. Tournassat is thanked for fruitful discussions. Diamond Light Source is thanked for providing beamtime under award 6841.

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  1. BRGM, 3 avenue Claude Guillemin, 45060, Orléans Cedex 02, France

    Philippe Bataillard, Sylvain Grangeon, Abdeltif Lahfid, Guillaume Wille, Catherine Joulian & Fabienne Battaglia-Brunet

  2. Diamond Light Source, Diamond House, Harwell Science and Innovation Campus, Didcot, Oxfordshire, OX11 0DE, UK

    Paul Quinn & Fred Mosselmans

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  1. Philippe Bataillard
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  2. Sylvain Grangeon
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Bataillard, P., Grangeon, S., Quinn, P. et al. Iron and arsenic speciation in marine sediments undergoing a resuspension event: the impact of biotic activity. J Soils Sediments 14, 615–629 (2014). https://doi.org/10.1007/s11368-013-0829-5

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