Antimony and arsenic behaviour in lead/zinc mine tailings during storage under vegetation cover

The high-volume, fine grained tailings produced from Pb/Zn ore processing need to be carefully managed. Metalloid elements, As and Sb, are present in tailings at ∼800 and ∼80 mg kg−1 respectively, and in neutral pH leachates at 5–50 μg L−1. Despite these relatively low leachate concentrations, As and Sb can cause regulatory concern due to their high toxicity and propensity for bioaccumulation. As and Sb mobility in tailings are controlled by their chemical speciation and associations with mineral phases. Changes in As and Sb speciation were, therefore, determined in depth profile samples taken from an active tailings management facility during waste storage up to 8 years since deposition. At this site, primarily to prevent dust formation, a vegetation cover was established by addition of organic compost to surface layers and seeding grasses. Over time a robust vegetation cover was established consisting of perennial grasses, clovers, and after 8 years, small trees and shrubs. The surface layer of the tailings also became progressively more oxidised over time producing a substrate more suitable for plant growth enabling the establishment of beneficial vegetation cover and the development of a thin soil-like surface layer. As and Sb were both present in predominately reduced 3+ forms in freshly deposited tailings but were converted to oxidised 5+ forms in older samples. Oxidation of Fe(II) in pyrite also occurred, producing increased amounts of weak acid leachable Fe(III)-oxides in the tailings. Sorption of As to neoformed iron oxides in leachate drains reduced concentrations in leachates to below regulatory limits, but Sb sorption was relatively ineffective resulting in higher Sb concentration in site drainage waters, which may require specific treatments to reduce Sb concentrations prior to discharge

Role of an organic carbon-rich soil and Fe(III) reduction in reducing the toxicity and environmental mobility of chromium(VI) at a COPR disposal site

Cr(VI) is an important contaminant found at sites where chromium ore processing residue (COPR) is deposited. No low cost treatment exists for Cr(VI) leaching from such sites. This study investigated the mechanism of interaction of alkaline Cr(VI)-containing leachate with an Fe(II)-containing organic matter rich soil beneath the waste. The soil currently contains 0.8% Cr, shown to be present as Cr(III)(OH)3 in EXAFS analysis. Lab tests confirmed that the reaction of Cr(VI) in site leachate with Fe(II) present in the soil was stoichiometrically correct for a reductive mechanism of Cr accumulation. However, the amount of Fe(II) present in the soil was insufficient to maintain long term Cr(VI) reduction at historic infiltration rates. The soil contains a population of bacteria dominated by a Mangroviflexus-like species, that is closely related to known fermentative bacteria, and a community capable of sustaining Fe(III) reduction in alkaline culture. It is therefore likely that in situ fermentative metabolism supported by organic matter in the soil produces more labile organic substrates (lactate was detected) that support microbial Fe(III) reduction. It is therefore suggested that addition of solid phase organic matter to soils adjacent to COPR may reduce the long term spread of Cr(VI) in the environment

Prehospital ambulance 12-lead electrocardiograms reduce door to needle time for thrombolysis in the emergency room

Digitalitzat per Artypla

Evolution of Cu and Zn speciation in agricultural soil amended by digested sludge over time and repeated crop growth

Metals such as Zn and Cu present in sewage sludge applied to agricultural land can accumulate in soils and potentially mobilise into crops. Sequential extractions and X-ray absorption spectroscopy results are presented that show the speciation changes of Cu and Zn sorbed to anaerobic digestion sludge after mixing with soils over three consecutive 6-week cropping cycles, with and without spring barley (Hordeum vulgare). Cu and Zn in digested sewage sludge are primarily in metal sulphide phases formed during anaerobic digestion. When Cu and Zn spiked sludge was mixed with the soil, about 40% of Cu(I)-S phases and all Zn(II)-S phases in the amended sludge were converted to other phases (mainly Cu(I)-O and outer sphere Zn(II)-O phases). Further transformations occurred over time, and with crop growth. After 18 weeks of crop growth, about 60% of Cu added as Cu(I)-S phases was converted to other phases, with an increase in organo-Cu(II) phases. As a result, Cu and Zn extractability in the sludge-amended soil decreased with time and crop growth. Over 18 weeks, the proportions of Cu and Zn in the exchangeable fraction decreased from 36% and 70%, respectively, in freshly amended soil, to 28% and 59% without crop growth, and to 24% and 53% with crop growth. Overall, while sewage sludge application to land will probably increase the overall metal concentrations, metal bioavailability tends to reduce over time. Therefore, safety assessments for sludge application in agriculture should be based on both metal concentrations present and their specific binding strength within the amended soil

Assessing metal contamination and speciation in sewage sludge: implications for soil application and environmental risk

Based on the most recently published data, we definitively estimated that the annual global production of sewage sludge may rise from ~ 53 million tons dry solids currently to ~ 160 million tons if global wastewater were to be treated to a similar level as in the 27 European Union countries/UK. It is widely accepted that the agricultural application is a beneficial way to recycle the abundant organic matter and plant nutrients in sewage sludge. However, land application may need to be limited due to the presence of metals. This work presents a meticulous and systematic review of the sources, concentrations, partitioning, and speciation of metals in sewage sludge in order to determine the impacts of sludge application on metal behavior in soils. It identifies that industrial wastewater, domestic wastewater and urban runoff are main sources of metals in sludge. It shows conventional treatment processes generally result in the partitioning of over 70% of metals from wastewater into primary and secondary sludge. Typically, the order of metal concentrations in sewage sludge is Zn > Cu > Cr ≈ Pb ≈ Ni > Cd. The proportion of these metals that are easily mobilised is highest for Zn and Ni, followed by Cd and Cu, then Pb and Cr. Sludge application to land will lead to elevated metal concentrations, and potentially to short-term changes to the dominant metal species in soils. However, the speciation of sludge-associated metals will change over time due to interactions with plant roots and soil minerals and as organic matter is mineralised by rhizo-microbiome

Microbially-mediated chromate reduction in highly alkaline groundwater systems

Chromium ore processing residue (COPR) has been deposited at a site in the North of England, probably at the end of the nineteenth century. The site covers an area of approximately 2.2 ha, and is situated between a canal and a river that are about 150m apart. It is in a glacial valley underlain by millstone grit and in-filled with alluvial deposits (silt, clay and sand). The original surface deposit is a thin layer of sandy clay that was probably deposited during over-bank flow of the river. COPR has been tipped onto the hillside between the river and canal (which is ~7m above the river), possibly to support the canal bank. At some time in the past top-soil has been placed over the COPR, and the site is now covered with grass. Ground level on the tip is about 1.5m higher than the canal towpath. Currently the site is a cause for environmental concern because groundwater emerging from the waste is alkaline, visibly yellow and has an elevated Cr(VI) concentration. This paper reports an investigation into the possible fate of any Cr(VI) that migrates downwards from the waste into the underlying soils. Sandy clay from immediately beneath the waste (assumed to be the topsoil layer prior to waste tipping) contains 30-70% acid extractable iron as reduced Fe(II), and between about 3,000 and 600 mg.kg 1 of Cr decreasing with depth. DNA fragments from soil bacteria were extracted from this soil, and microcosm experiments with this soil where the pH was reduced showed that it contains a viable bacterial population capable of iron-reduction. This sandy clay layer, despite a pH value of 10.5, appears to be acting as a natural reactive zone beneath the waste as it is accumulating chromium. It is thought that the mechanism of Cr(VI) reduction is most likely to be an abiotic reaction with the Fe(II) present in the soil, and that Fe(II) in the soil is being replenished by microbial iron reduction (albeit probably at a slow rate)

Ocean-climate processes recorded in holocene laminated sediments from the Gotland Deep, Baltic Sea

Available from British Library Document Supply Centre-DSC:DXN050843 / BLDSC - British Library Document Supply CentreSIGLEGBUnited Kingdo

Microfabric study of diatomaceous and lithogenic deposition in laminated sediments from the Gotland Deep, Baltic Sea

The deep basins of the Baltic Sea are commonly anoxic, and finely laminated diatomaceous sediments have been deposited at intervals throughout the last 8000 yr. The origin and composition of individual laminae in Gotland Deep sediments have often proved difficult to characterise using traditional micropalaeontological and sedimentological studies. Here, we present a scanning electron microscope study in which lamina down to 30 m in thickness with distinct mineralogical or micropalaeontological composition have been identified and described. Depositional laminae sequences in the form of couplets, triplets and quadruplets of diatomaceous and lithogenic laminae are observed with an average thickness of approximately 700 m. Diagenetic Ca-rhodochrosite laminae also occur within these depositional sequences. Examination of the diatom assemblages suggests that these bundles of laminae represent annual deposits, or varves. Varves are relatively uncommon, and typically occur in small intervals of two to five varves, which are interrupted by more diffusely laminated and homogenous sediments. The origin of these more massive sediments probably relates to periodic re-oxygenation of the basin on inter-annual time scales and destruction of varves by bioturbation

Metagenomes from microbial populations beneath a chromium waste tip give insight into the mechanism of Cr (VI) reduction

Dumped Chromium Ore Processing Residue (COPR) at legacy sites poses a threat to health through leaching of toxic Cr(VI) into groundwater. Previous work implicates microbial activity in reducing Cr(VI) to less mobile and toxic Cr(III), but the mechanism has not been explored. To address this question a combined metagenomic and geochemical study was undertaken. Soil samples from below the COPR waste were used to establish anaerobic microcosms which were challenged with Cr(VI), with or without acetate as an electron donor, and incubated for 70 days. Cr was rapidly reduced in both systems, which also reduced nitrate, nitrite then sulfate, but this sequence was accelerated in the acetate amended microcosms. 16S rRNA gene sequencing revealed that the original soil sample was diverse but both microcosm systems became less diverse by the end of the experiment. A high proportion of 16S rRNA gene reads and metagenome-assembled genomes (MAGs) with high completeness could not be taxonomically classified, highlighting the distinctiveness of these alkaline Cr impacted systems. Examination of the coding capacity revealed widespread capability for metal tolerance and Fe uptake and storage, and both populations possessed metabolic capability to degrade a wide range of organic molecules. The relative abundance of genes for fatty acid degradation was 4× higher in the unamended compared to the acetate amended system, whereas the capacity for dissimilatory sulfate metabolism was 3× higher in the acetate amended system. We demonstrate that naturally occurring in situ bacterial populations have the metabolic capability to couple acetate oxidation to sequential reduction of electron acceptors which can reduce Cr(VI) to less mobile and toxic Cr(III), and that microbially produced sulfide may be important in reductive precipitation of chromate. This capability could be harnessed to create a Cr(VI) trap-zone beneath COPR tips without the need to disturb the waste