High-resolution measurements of sulphur isotope variations in sedimentpore-waters by laser ablation multicollector inductively coupled plasma mass spectrometry

A novel combination of the technique of diffusive gradients in thin films (DGT) and laser ablation high-resolution multicollector inductively coupled plasma mass spectrometry was developed to study sulphur isotope variations of dissolved pore-water sulphide in freshwater and marine sediments. The technique enables two-dimensional mapping of isotopic variations (δ34S) in dissolved sulphide captured as solid Ag2S in DGT polyacrylamide gels. Measurements can be performed at a spatial resolution (~100 μm) relevant to microbiological processes and formation of individual iron sulphide grains in surface sediments. Values of δ34S measured in BaSO4–DGT gel isotope standards (δ34S=9.28±0.36‰ to 9.33±0.57‰) are within 1‰ of the accepted value determined with conventional analytical techniques (δ34S=10.13±0.29‰). Sulphur isotope measurements were performed in sediments from a eutrophic lake (Esthwaite Water, UK) contained in laboratory mesocosms. Bacterial sulphate reduction and sulphide formation in this sediment are predominantly localized to discrete, mm-sized microniches, where oxidation of labile organic matter such as fresh algae and faecal pellets drives the reduction of sulphate. The results emphasize the importance of microniches as localized, highly dynamic reaction sites in sediments, where significant shifts in δ34S of up to +20‰ relative to the local background were measured across microniches. The improved spatial resolution for pore-water sulphur isotope measurements, compared to that of conventional sampling and analytical techniques, is essential for improving our understanding of the global biogeochemical cycling of sulphur as well as trace metal–sulphide interactions in modern sediments

External carbon addition for enhancing denitrification modifies bacterial community composition and affects CH₄ and N₂O production in sub-arctic mining pond sediments.

Explosives used in mining operations release reactive nitrogen (N) that discharge into surrounding waters. Existing pond systems at mine sites could be used for N removal through denitrification and we investigated capacity in tailings and clarification pond sediments at an iron-ore mine site. Despite differences in microbial community structure in the two ponds, the potential denitrification rates were similar, although carbon limited. Therefore, a microcosm experiment in which we amended sediment from the clarification pond with acetate, cellulose or green algae as possible carbon sources was conducted during 10 weeks under denitrifying conditions. Algae and acetate treatments showed efficient nitrate removal and increased potential denitrification rates, whereas cellulose was not different from the control. Denitrifiers were overall more abundant than bacteria performing dissimilatory nitrate reduction to ammonium (DNRA) or anaerobic ammonium oxidation, although DNRA bacteria increased in the algae treatment and this coincided with accumulation of ammonium. The algae addition also caused higher emissions of methane (CH <sub>4</sub> ) and nitrous oxide (N <sub>2</sub> O). The bacterial community in this treatment had a large proportion of Bacteroidia, sulfate reducing taxa and bacteria known as fermenters. Functional gene abundances indicated an imbalance between organisms that produce N <sub>2</sub> O in relation to those that can reduce it, with the algae treatment showing the lowest relative capacity for N <sub>2</sub> O reduction. These findings show that pond sediments have the potential to contribute to mitigating nitrate levels in water from mining industry, but it is important to consider the type of carbon supply as it affects the community composition, which in turn can lead to unwanted processes and increased greenhouse gas emissions

Early diagenesis and isotopic composition of lead in Lake Laisan, northern Sweden

Water column (dissolved/suspended phase, sediment traps) and sediment data (pore-water, solid-phase sediment) were combined with stable Pb and Pb-210 isotope data to trace the early diagenetic behaviour and geochemical cycling of Pb in Lake Laisan, a lake which has received large quantities of anthropogenic Pb since the early 1940s. Early diagenetic remobilisation of Pb is indicated by a subsurface pore-water Pb maximum (120 mug 1(-1)) in the oxic surface layer of the sediment, where the solid-phase Pb concentration is 3400-4600 mug g(-1). The remobilisation of Pb appears to be caused by a pH-controlled desorption of Pb from solid-phase sediment, which is consistent with a model describing surface complexation of Pb(II) on hydrous goethite surfaces. The diffusive Pb flux from the subsurface pore-water maximum towards the sediment surface (36 mug cm(-2) year(-1)) exceeds the depositional Pb flux (8.6 mug cm(-2) year(-1)) by approximately a factor of four, indicating that Pb is highly mobile in the sediment. Stable Pb isotope data and a mass balance calculation suggest that Pb diffusing upwards is, to a large extent, trapped in the surface sediment. Lead that may diffuse into the slightly alkaline lake water appears to be efficiently sorbed to suspended particulate matter, resulting in low dissolved Pb concentrations in the water column (0.040-0.046 mug 1(-1)). Sorption of Pb to suspended particulate matter is consistent with the elevated suspended particulate Pb concentrations in the hypolimnion (3800-4000 mug g(-1)), and the fact that the stable Pb isotopic compositions of suspended matter and pore-water are similar

Remediation of a marine shore tailings deposit and the importance of water-rock interaction on element cycling in the coastal aquifer

We present the study of the geochemical processes associated with the first successful remediation of a marine shore tailings deposit in a coastal desert environment (Bahia de Ite, in the Atacama Desert of Peru). The remediation approach implemented a wetland on top of the oxidized tailings. The site is characterized by a high hydrauliz gradient produced by agricultural irrigation on upstream gravel terraces that pushed river water (similar to 500 mg/L SO(4)) toward the sea and through the tailings deposit. The geochemical and isotopic (delta(2)H(water) and delta(18)O(water), delta(34)S(sulfate) , delta(18)O(sulfate)) approach applied here revealed that evaporite horizons (anhydrite and halite) in the gravel terraces are the source of increased concentrations of SO(4), Cl, and Na up to similar to 1500 mg/L in the springs at the base of the gravel terraces. Deeper groundwater interacting with underlying marine sequences increased the concentrations of SO(4), Cl, and Na up to 6000 mg/L and increased the alkalinity up to 923 mg/L CaCO(3) eq. in the coastal aquifer. These waters infiltrated into the tailings deposit at the shelf-tailings interface. Nonremediated tailings had a low-pH oxidation zone (pH 1-4) with significant accumulations of efflorescent salts (10-20 cm thick) at the surface because of upward capillary transport of metal cations in the arid climate. Remediated tailings were characterized by neutral pH and reducing conditions (pH similar to 7, Eh similar to 100 mV). As a result, most bivalent metals such as Cu, Zn, and Ni had very low concentrations (around 0.01 mg/L or below detection limit) because of reduction and sorption processes. In contrast, these reducing conditions increased the mobility of iron from two sources in this system: (1) The originally Fe(III)-rich oxidation zone, where Fe(II) was reduced during the remediation process and formed an Fe(II) plume, and (2) reductive dissolution of Fe(III) oxides present in the original shelf lithology formed an Fe-Mn plume at 10-m depth. These two Fe-rich plumes were pushed toward the shoreline where more oxidizing and higher pH conditions triggered the precipitation of Fe(HI)hydroxide coatings on silicates. These coatings acted as a filter for the arsenic, which naturally infiltrated with the river water (similar to 500 mu g/L As natural background) into the tailings deposit