Mechanism of Vanadium Leaching during Surface Weathering of Basic Oxygen Furnace Steel Slag Blocks: A Microfocus X-ray Absorption Spectroscopy and Electron Microscopy Study

Basic oxygen furnace (BOF) steelmaking slag is enriched in potentially toxic V which may become mobilized in high pH leachate during weathering. BOF slag was weathered under aerated and air-excluded conditions for 6 months prior to SEM/EDS and μXANES analysis to determine V host phases and speciation in both primary and secondary phases. Leached blocks show development of an altered region in which free lime and dicalcium silicate phases were absent and Ca–Si–H was precipitated (CaCO₃ was also present under aerated conditions). μXANES analyses show that V was released to solution as V(V) during dicalcium silicate dissolution and some V was incorporated into neo-formed Ca–Si–H. Higher V concentrations were observed in leachate under aerated conditions than in the air-excluded leaching experiment. Aqueous V concentrations were controlled by Ca₃(VO₄)₂ solubility, which demonstrate an inverse relationship between Ca and V concentrations. Under air-excluded conditions Ca concentrations were controlled by dicalcium silicate dissolution and Ca–Si–H precipitation, leading to relatively high Ca and correspondingly low V concentrations. Formation of CaCO₃ under aerated conditions provided a sink for aqueous Ca, allowing higher V concentrations limited by kinetic dissolution rates of dicalcium silicate. Thus, V release may be slowed by the precipitation of secondary phases in the altered region, improving the prospects for slag reuse

Dynamic characteristics of sulfur, iron and phosphorus in coastal polluted sediments, north China

The cycling of sulfur (S), iron (Fe) and phosphorus (P) in sediments and pore water can impact the water quality of overlying water. In a heavily polluted river estuary (Yantai, China), vertical profiles of fluxes of dissolved sulfide, Fe2+ and dissolved reactive phosphorus (DRP) in sediment pore water were investigated by the Diffusive Gradients in Thin films technique (DGT). Vertical fluxes of S, Fe, P in intertidal sediment showed the availability of DRP increased while the sulfide decreased with depth in surface sediment, indicating that sulfide accumulation could enhance P release in anoxic sediment. In sites with contrasting salinity, the relative dominance of iron and sulfate reduction was different, with iron reduction dominant over sulfate reduction in the upper sediment at an intertidal site but the reverse true in a freshwater site, with the other process dominating at depth in each case. Phosphate release was largely controlled by iron reduction

Mobilisation of arsenic from bauxite residue (red mud) affected soils: effect of pH and redox conditions

The tailings dam breach at the Ajka alumina plant, western Hungary in 2010 introduced ~1 million m3 of red mud suspension into the surrounding area. Red mud (fine fraction bauxite residue) has a characteristically alkaline pH and contains several potentially toxic elements, including arsenic. Aerobic and anaerobic batch experiments were prepared using soils from near Ajka in order to investigate the effects of red mud addition on soil biogeochemistry and arsenic mobility in soil–water experiments representative of land affected by the red mud spill. XAS analysis showed that As was present in the red mud as As(V) in the form of arsenate. The remobilisation of red mud associated arsenate was highly pH dependent and the addition of phosphate to red mud suspensions greatly enhanced As release to solution. In aerobic batch experiments, where red mud was mixed with soils, As release to solution was highly dependent on pH. Carbonation of these alkaline solutions by dissolution of atmospheric CO2 reduced pH, which resulted in a decrease of aqueous As concentrations over time. However, this did not result in complete removal of aqueous As in any of the experiments. Carbonation did not occur in anaerobic experiments and pH remained high. Aqueous As concentrations initially increased in all the anaerobic red mud amended experiments, and then remained relatively constant as the systems became more reducing, both XANES and HPLC–ICP-MS showed that no As reduction processes occurred and that only As(V) species were present. These experiments show that there is the potential for increased As mobility in soil–water systems affected by red mud addition under both aerobic and anaerobic conditions

Habitat use by the endangered white-clawed crayfish Austropotamobius species complex: a systematic review

Understanding habitat requirements is a key part of conserving declining species, particularly when reintroductions are planned as part of the recovery strategy. The white-clawed crayfish (Austropotamobius pallipes) has undergone severe declines across its range and is now classified by the International Union for Conservation of Nature (IUCN) as ‘endangered’. Translocation of threatened A. pallipes populations to isolated ‘Ark sites’ where threats are minimised is an increasingly used conservation tool. A full feasibility assessment of potential Ark sites, including an assessment of habitat suitability, is recommended within translocation guidelines developed by the IUCN. This literature review employed a systematic search and ‘vote counting’ approach to identify and assess the relative importance of physical habitat requirements of A. pallipes. Many habitat features were positively associated with crayfish presence, in particular: boulder substrate, trees/shading, woody debris, exposed roots, and undercut banks; and habitat use patterns varied among crayfish sexes and size classes. Ark sites should incorporate heterogeneous habitat, with as many of these features as possible, to provide both ample refugia and rich foraging areas

Stream-bed phosphorus in paired catchments with different agricultural land use intensity

Stream-bed sediments from three paired catchments, each draining a lower agricultural intensity system and a higher agricultural intensity system, were analysed for (a) total P (TP), (b) bioavailable-P (Resin-P), (c) equilibrium phosphorus concentration (EPC0), and (d) degree of phosphorus saturation (DPS). The influence of agriculture on sediment P was explored within the context of other key variables that may control the sediment P concentrations such as particle size, Fe, Ca and organic matter content, and in terms of potential implications of sediment P to in-stream biota. TP concentrations, EPC0, and the proportion of fine sediment were highest at the sites with the greater agricultural impact. Higher concentrations of bioavailable-P were also found in higher intensity agricultural systems. However, the highest concentrations of bioavailable-P were found at sites with point source inputs. Sites with high Fe concentrations had higher TP concentrations relative to agricultural intensity, but also had lower DPS values, illustrating that the sediment still had the capacity to take up P in a strongly bound form. The results from this study show that higher risk agricultural practices (intensive arable production and dairy and beef production) can lead either directly, or indirectly through increased inputs of fine sediment, to increased sediment TP concentrations. The importance of geochemical and physical controls on the bed sediments’ capacity to mitigate high P inputs in headwater lowland streams, especially under low flows and times of eutrophication risk in spring and summer is illustrated

Phosphorus dynamics and productivity in sewage-impacted lowland chalk stream

Hourly in situ phosphorus, conductivity, turbidity, dissolved oxygen, pH, and chlorophyll measurements were collected from January 2004 to November 2006 for the River Kennet, 2 km downstream of a sewage effluent inlet. Excess carbon dioxide pressure (EpCO2) was calculated from continuous pH and spot alkalinity measurements. EpCO2 and dissolved oxygen were used to estimate rates of photosynthesis and respiration. These parameters were examined alongside flow, water temperature and solar radiation to explore controls on phosphorus dynamics and in-stream productivity. Diurnal, event and seasonal patterns were observed in phosphorus concentrations. The diurnal and seasonal variations appeared to be related to the upstream sewage treatment works. The event patterns coincided with periods of high flow, and were attributed to diffuse sources. Chlorophyll behaved independently of phosphorus concentration and returned to baseline levels before photosynthesis rate. This indicated that, during the period of study, in-stream productivity was primarily controlled by aquatic plants other than phytoplankton

Internal loading of phosphorus in a sedimentation pond of a treatment wetland: Effect of a phytoplankton crash

Sedimentation ponds are widely believed to act as a primary removal process for phosphorus (P) in nutrient treatment wetlands. High frequency in-situ P, ammonium (NH4+) and dissolved oxygen measurements, alongside occasional water quality measurements, assessed changes in nutrient concentrations and productivity in the sedimentation pond of a treatment wetland between March and June. Diffusive equilibrium in thin films (DET) probes were used to measure in-situ nutrient and chemistry pore-water profiles. Diffusive fluxes across the sediment–water interface were calculated from the pore-water profiles, and dissolved oxygen was used to calculate rates of primary productivity and respiration. The sedimentation pond was a net sink for total P (TP), soluble reactive P (SRP) and NH4+ in March, but became subject to a net internal loading of TP, SRP and NH4+ in May, with SRP concentrations increasing by up to 41 μM (1300 μl− 1). Reductions in chlorophyll a and dissolved oxygen concentrations also occurred at this time. The sediment changed from a small net sink of SRP in March (average diffusive flux: − 8.2 μmol m− 2 day− 1) to a net source of SRP in June (average diffusive flux: + 1324 μmol m− 2 day− 1). A diurnal pattern in water column P concentrations, with maxima in the early hours of the morning, and minima in the afternoon, occurred during May. The diurnal pattern and release of SRP from the sediment were attributed to microbial degradation of diatom biomass, causing reduction of the dissolved oxygen concentration and leading to redox-dependent release of P from the sediment. In June, 2.7 mol-P day− 1 were removed by photosynthesis and 23 mol-P day− 1 were supplied by respiration in the lake volume. SRP was also released through microbial respiration within the water column, including the decomposition of algal matter. It is imperative that consideration to internal recycling is given when maintaining sedimentation ponds, and before the installation of new ponds designed to treat nutrient waste

Studies on synthesis and characteristics of zeolite prepared from Indian fly ash

In the present study, samples of coal fly ash were obtained from seven major Indian thermal power plants. These samples were transformed into fly ash zeolite (FAZ) using hydrothermal activation by treatment with NaOH. All experiments were carried out at 100 °C, but with different solid:liquid ratios, different concentrations of alkali and different incubation times. The chemical composition, mineralogy and morphology of the fly ash and FAZ were determined by wet chemical method after Na2CO3 fusion, x-ray diffraction and scanning electron microscopy. The cation exchange capacity of fly ash and FAZ was determined using the ammonium acetate method (IS:2720). The ammonium exchange capacity was determined by the titrimetric method. The experiments demonstrate that zeolite can be synthesized at 100 °C using alkali. The cation exchange capacity and ammonium adsorption capacity of FAZ (up to 250 meq/100 g and 22.93 mg NH4 +/g respectively) indicate that the FAZ may be potentially useful to reduce heavy metals and other pollutants from contaminated environments. Therefore, zeolitization at low temperature potentially allows waste fly ash to be used in an economically advantageous way