Uptake and incorporation of Al, Cr, V, Zn and Mo in hematite: Competition, synergies and influence on structural properties.

This study investigated multiple (di-, tri- and tetra-)incorporation of selected minor and trace elements (Al3+, Cr3+, V3-5+, Zn2+, Mo6+ and As5+) into hematite. The purpose was to improve understanding of how hematite may control trace element mobility in the environment, and how physical and chemical properties of hematite are impacted by multi-element incorporation at x/Fe molar ratios of up to 10%. Simultaneous structural incorporation of Al±Cr±V±Zn into hematite was achieved, with both synergistic and antagonistic effects occurring between certain element combinations. Cr+Al had synergistic effects on their co-incorporation, while V negatively affected Al incorporation, and both V and Zn negatively affected Cr incorporation. In contrast, Mo was minimally associated with hematite, and As prevented hematite formation completely. X-ray diffraction indicated contraction and expansion of the hematite unit-cell upon substitution was related to the ionic radius of the substituting element in single-element samples, while V predominantly controlled the direction of deviation in multi-element samples. X-ray absorption near-edge structure spectroscopy indicated V was present as a mixture of V3+-V5+, with a higher average V oxidation state associated with multi-element samples. Results provide new insights into trace element geochemistry within hematite, and highlight the importance of multi-element studies to better understand natural and anthropogenic systems.

Monosulfidic black ooze accumulations in sediments of the Geographe Bay area, Western Australia.

Mobilisation of sedimentary monosulfidic black ooze (MBO) may result in rapid deoxygenation and acidification of surface waters, and release of potentially toxic metals. This study examines the extent and nature of MBO accumulation in the Geographe Bay area, Western Australia. MBO accumulations were found to be widespread in benthic sediments of the Geographe Bay area with acid-volatile sulfide (AVS) contents as high as 320 µmol g(-1). The MBO materials often had unusually high dissolved sulfide (S(-II)) concentrations in their pore-waters (up to 610 mg L(-1)) and elevated elemental sulfur (S(0)) contents (up to 51 µmol g(-1)). Dissolved S(-II) is able to accumulate due to limited iron availability and S(0) is largely its partial oxidation product. The availability of organic carbon and Fe limited MBO accumulation at many sites. A comparison of AVS and simultaneously extracted metal (SEM) concentrations has shown that metals are likely to be bound in sulfide complexes.

Iron-monosulfide oxidation in natural sediments: resolving microbially mediated S transformations using XANES, electron microscopy, and selective extractions.

Iron-monosulfide oxidation and associated S transformations in a natural sediment were examined by combining selective extractions, electron microscopy and S K-edge X-ray absorption near-edge structure (XANES) spectroscopy, The sediment examined in this study was collected from a waterway receiving acid-sulfate soil drainage. It contained a high acid-volatile sulfide content (1031 micromol g(-1)), reflecting an abundance of iron-monosulfide. The iron-monosulfide speciation in the initial sediment sample was dominated by nanocrystalline mackinawite (tetragonal FeS). At near-neutral pH and an 02 partial pressure of approximately 0.2 atm, the mackinawite was found to oxidize rapidly, with a half-time of 29 +/- 2 min. This oxidation rate did not differ significantly (P < 0.05) between abiotic versus biotic conditions, demonstrating that oxidation of nanocrystalline mackinawite was not microbially mediated. The extraction results suggested that elemental S (S8(0)) was a key intermediate S oxidation product Transmission electron microscopy showed the S8(0) to be amorphous nanoglobules, 100-200 nm in diameter. The quantitative importance of S8(0) was confirmed by linear combination XANES spectroscopy, after accounting for the inherent effect of the nanoscale S8(0) particle-size on the corresponding XANES spectrum. Both the selective extraction and XANES data showed that oxidation of S8(0) to SO4(2-) was mediated by microbial activity. In addition to directly revealing important S transformations, the XANES results support the accuracy of the selective extraction scheme employed here.

Estimating sludge loadings to land based on trace metal sorption in soil: effect of dissolved organo-metallic complexes.

This paper describes the results of research examining the effect of dissolved organo-metallic complexes of copper (Cu) and zinc (Zn) from sewage sludge leachate on sorption by a humic-gley soil A-horizon, and the influence of such complexes on resultant sludge loading estimates. Sorption was described with Linear, Freundlich or Langmuir equations, and compared between a sample of sludge leachate (containing 97.4% of Cu and 63.2% of Zn as dissolved organo-metallic complexes) and a reference solution (which mimicked the leachate, except for a lack of dissolved organic material). This comparison revealed that dissolved organo-metallic complexes significantly depressed Cu and Zn sorption in the study soil. The isotherm equations were then used to estimate sludge-derived Cu and Zn loadings to soil in order to result in an "allowable" output concentration from the soil solution to the surrounding environment. These loadings, together with soil bulk density and "availability" of sludge Cu and Zn, were incorporated in a preliminary model to estimate sludge application rates which are acceptable in terms of off-site movement of these metals through leaching losses. In the absence of dissolved organo-metallic complexes (sorption from the reference solution), levels of Cu and Zn sorption in the study soil indicated a sludge application rate of approximately 3500 kg/ha. However, when Cu and Zn sorption from the sludge leachate with dissolved organo-metallic complexes was considered, calculated loading rates were reduced to approximately 690 kg-sludge/ha. This suggests that for sludge loading estimates based on soil sorption characteristics to be relevant to environmental protection, the sorption depressing effect of dissolved organo-metallic complexes should be quantitatively considered.