ABSTRACT
Pb soil pollution poses a serious health risk to both the environment and humans. Immobilization is the most common strategy for remediation of heavy metal polluted soil. In this study, municipal sewage sludge was used as an amendment for rehabilitation of Pb-contaminated soils, for agricultural use, near a lead-acid battery factory. The passivation effect was further improved by the addition of phosphate fertilizer. It was found that the leachable Pb content in soils was decreased from 49.6 mg kg-1 to 16.1-36.6 mg kg-1 after remediation of sludge for 45 d at applied dosage of municipal sewage sludge of 4-16 wt%, and further decreased to 14.3-34.3 mg kg-1 upon extension of the remediation period to 180 d. The addition of phosphate fertilizer greatly enhanced the Pb immobilization, with leachable Pb content decreased to 2.0-23.6 mg kg-1 with increasing dosage of phosphate fertilizer in range of 0.8-16 wt% after 180 d remediation. Plant assays showed that the bioavailability of Pb was significantly reduced by the soil remediation, with the content of absorbed Pb in mung bean roots decreased by as much as 87.0%. The decrease in mobility and biotoxicity of the soil Pb is mainly attributed to the speciation transformation of carbonate, Fe-Mn oxides and organic matter bound Pb to residue Pb under the synergism of reduction effect of sludge and acid dissolution and precipitation effect of phosphate fertilizer. This study suggests a new method for remediation of Pb-contaminated soil and utilization of municipal sewage sludge resources.
ABSTRACT
Chalcopyrite, galena, and sphalerite commonly coexist with pyrite in sulfidic waste rocks. The aim of this work was to investigate their impact, potentially by galvanic interaction, on pyrite oxidation and acid generation rates under simulated acid and metalliferous drainage conditions. Kinetic leach column experiments using single-minerals and pyrite with one or two of the other sulfide minerals were carried out at realistic sulfide contents (total sulfide <5.2 wt % for mixed sulfide experiments), mimicking sulfidic waste rock conditions. Chalcopyrite was found to be most effective in limiting pyrite oxidation and acid generation with 77-95% reduction in pyrite oxidation over 72 weeks, delaying decrease in leachate pH. Sphalerite had the least impact with reduction of pyrite dissolution by 26% over 72 weeks, likely because of the large band gap and poor conductivity of sphalerite. Galena had a smaller impact than chalcopyrite on pyrite oxidation, despite their similar band gaps, possibly because of the greater extent of oxidation and the significantly reduced surface areas of galena (area reductions of >47% for galena vs <1.5% for chalcopyrite) over 72 weeks. The results are directly relevant to mine waste storage and confirm that the galvanic interaction plays a role in controlling acid generation in multisulfide waste even at low sulfide contents (several wt %) with small probabilities (≤0.23%) of direct contact between sulfide minerals in mixed sulfide experiments.
Subject(s)
Minerals , Sulfides , Acids , Oxidative Stress , SolubilityABSTRACT
Electro-dewatering (EDW) is an emerging technology for improved sludge/sediment dewatering enabling subsequent cost effective treatment for toxicity and pathogenic reduction if required and/or disposal, but the effects of sediment/sludge properties on the efficacy of EDW remain unclear. Here we investigate EDW in the absence of chemical conditioning which can result in secondary pollution. The influence of sediment/sludge volatile solids content (VS), electrical conductivity (EC), pH and zeta potential (ζ), on mechanical and electrical behaviors determining dewaterability and energy consumption (PE) was investigated. Optimization of EDW parameters increased the final solids content (DSf) from 40 wt% to more than 55 wt% for river sediment, while the solids content in municipal sludge was only increased from 10 wt% to 15-20 wt%. Multiple linear regression and statistical analysis showed that electro-dewatering performance is primarily affected by VS and PE is mainly affected by EC. A theoretical basis for engineering design and selection of operational parameters for sludge/sediment electro-dewatering is provided by this study.
Subject(s)
Sewage , Waste Disposal, Fluid , Electric Conductivity , Electricity , Rivers , WaterABSTRACT
The aim of this study was to determine the combined effect of galvanic interaction and silicate addition on the dissolution of pyrite, the major contributor to acid and metalliferous drainage (AMD). Single (pyrite, sphalerite, and galena)- and bi-sulfide (pyrite-sphalerite and pyrite-galena) batch dissolution experiments were carried out with addition of 0.8 mM dissolved silicate for comparison to previously published data. The pyrite dissolution rate was reduced by 98% upon silicate addition at pH 7.4 with little effect at pH 3.0 and 5.0. The effect of galvanic interaction on reducing pyrite dissolution decreased with increasing pH and was greater in the presence of sphalerite than galena. In contrast, the effect of silicate addition increased with increasing pH and was greater in the presence of galena than sphalerite. The greatest combined effect was at pH 7.4, with <0.1% of pyrite leached in both bi-sulfide systems. Silicate addition also significantly reduced the dissolution of sphalerite or galena (by 10-44%, except at pH 3 for the pyrite-sphalerite system). These results suggest that silicate addition, for reducing both pyrite dissolution and metalliferous drainage, may be applicable at a broad pH in mixed sulfide systems.
Subject(s)
Silicates , Sulfides , Iron , Oxidative Stress , SolubilityABSTRACT
Although the acid generating properties of pyrite (FeS2) have been studied extensively, the impact of galvanic interaction on pyrite oxidation, and the implications for acid and metalliferous drainage, remain largely unexplored. The relative galvanic effects on pyrite dissolution were found to be consistent with relative sulfide mineral surface area ratios with sphalerite (ZnS) having greater negative impact in batch leach tests (sulfide minerals only, controlled pH) and galena (PbS) having greater negative impact in kinetic leach column tests (KLCs, uncontrolled pH, >85 wt% silicate minerals). In contrast the presence of pyrite resulted consistently in greater increase in galena than sphalerite leaching suggesting that increased anodic leaching is dependent on the difference in anodic and cathodic sulfide mineral rest potentials. Acidity increases occurred after 44, 20, and 12 weeks in the pyrite-galena, pyrite-sphalerite, and the pyrite containing KLCs. Thereafter acid generation rates were similar with the Eh consistently above the rest potential of pyrite (660 mV, SHE). This suggests that treatment of waste rocks or tailings, to establish and maintain low Eh conditions, may help to sustain protective galvanic interactions and that monitoring of Eh of leachates is potentially a useful indicator for predicting changes in acid generation behavior.
Subject(s)
Iron , Sulfides , Acids , MineralsABSTRACT
The aim of this study was to test the performance of a novel method for acid rock drainage (ARD) control through the formation of Al(OH)3-doped passivating surface layers on pyrite. At pH 2.0 and 4.0, there was no obvious inhibition of the pyrite oxidation rate on addition of 20 mg L-1 Al3+ (added as AlCl3·6H2O). In comparison, the pyrite oxidation rate at circumneutral pH (7.4 ± 0.4) decreased with increasing added Al3+ with ≈98% reduction in long-term (282 days) dissolution rates in the presence of 20 mg L-1 Al3+. Al3+ was added to the solution and allowed to equilibrate prior to pyrite addition (2 g L-1). Consequently almost all Al3+ (>99.9%) was initially present as aluminum hydroxide precipitates at pH 7.4. X-ray photoelectron spectroscopy analysis showed a significant concentration of Al3+ (20.3 at. %) on the pyrite surface reacted at pH 7.4 with 20 mg L-1 added Al3+, but no Al3+ on pyrite surfaces reacted at pH 2.0 and 4.0 with added Al3+. Transmission electron microscopy and synchrotron X-ray absorption near edge spectroscopy analyses indicated that compact surface layers containing both goethite and amorphous or nanocrystalline Al(OH)3 formed in the presence of 20 mg L-1 Al3+ at circumneutral pH, in contrast to the porous goethite surface layers formed on pyrite dissolved in the absence of Al3+ under otherwise identical conditions. This work demonstrates the potential for novel Al-based pyrite passivation of relevance to the mining industry where suitable Al-rich waste materials are available for ARD control interventions.
Subject(s)
Aluminum Hydroxide , Iron , Acids , Aluminum , SulfidesABSTRACT
Acid and metalliferous release occurring when sulfide (principally pyrite)-containing rock from mining activities and from natural environments is exposed to the elements is acknowledged as a major environmental problem. Acid rock drainage (ARD) management is both challenging and costly for operating and legacy mine sites. Current technological solutions are expensive and focused on treating ARD on release rather than preventing it at source. We describe here a viable, practical mechanism for reduced ARD through the formation of silicate-stabilized iron oxyhydroxide surface layers. Without silicate, oxidized pyrite particles form an overlayer of crystalline goethite or lepidocrocite with porous structure. With silicate addition, a smooth, continuous, coherent and apparently amorphous iron oxyhydroxide surface layer is observed, with consequent pyrite dissolution rates reduced by more than 90% at neutral pH. Silicate is structurally incorporated within this layer and inhibits the phase transformation from amorphous iron (oxy)hydroxide to goethite, resulting in pyrite surface passivation. This is confirmed by computational simulation, suggesting that silicate-doping of a pseudoamorphous iron oxyhydroxide (ferrihydrite structure) is thermodynamically more stable than the equivalent undoped structure. This mechanism and its controlling factors are described. As a consequence of the greatly reduced acid generation rate, neutralization from on-site available reactive silicate minerals may be used to maintain neutral pH, after initial limestone addition to achieve neutral pH, thus maintaining the integrity of these layers for effective ARD management.
Subject(s)
Iron , Silicates , Sulfides , MiningABSTRACT
Selective removal of Ca and recovery of Mg by precipitation from flue gas desulfurization (FGD) wastewater has been investigated. Thermodynamic analysis of four possible additives, Na2CO3, Na2C2O4, NaF and Na2SO4, indicated that both carbonate and oxalate could potentially provide effective separation of Ca via precipitation from Mg in FGD wastewater. However, it was found experimentally that the carbonate system was not as effective as oxalate in this regard. The oxalate system performed considerably better, with Ca removal efficiency of 96% being obtained, with little Mg inclusion at pH 6.0 when the dosage was ×1.4 the stoichiometric requirement. On this basis, the subsequent recovery process for Mg was carried out using NaOH with two-step precipitation. The product was confirmed to be Mg(OH)2 (using X-ray diffraction and thermo gravimetric analysis) with elemental analysis suggesting a purity of 99.3 wt.%.
Subject(s)
Calcium/isolation & purification , Magnesium/isolation & purification , Wastewater/chemistry , Water Pollutants, Chemical/isolation & purification , Calcium/chemistry , Chemical Precipitation , Magnesium/chemistry , Thermodynamics , Water Pollutants, Chemical/chemistry , X-Ray DiffractionABSTRACT
Jarosites and schwertmannite can be formed in the unsaturated oxidation zone of sulfide-containing mine waste rock and tailings together with ferrihydrite and goethite. They are also widely found in process wastes from electrometallurgical smelting and metal bioleaching and within drained coastal lowland soils (acid-sulfate soils). These secondary minerals can temporarily store acidity and metals or remove and immobilize contaminants through adsorption, coprecipitation, or structural incorporation, but release both acidity and toxic metals at pH above about 4. Therefore, they have significant relevance to environmental mineralogy through their role in controlling pollutant concentrations and dynamics in contaminated aqueous environments. Most importantly, they have widely different acid release rates at different pHs and strongly affect drainage water acidity dynamics. A procedure for estimation of the amounts of these different forms of nonsulfide stored acidity in mining wastes is required in order to predict acid release rates at any pH. A four-step extraction procedure to quantify jarosite and schwertmannite separately with various soluble sulfate salts has been developed and validated. Corrections to acid potentials and estimation of acid release rates can be reliably based on this method.
Subject(s)
Acids/analysis , Environmental Monitoring/methods , Mining , Waste Products/analysis , Ferric Compounds/chemistry , Hydrolysis , Iron/chemistry , Iron Compounds/isolation & purification , Minerals/analysis , Oxalates/chemistry , Protons , Sulfates/analysis , Sulfates/chemistry , Sulfides/analysis , Sulfides/chemistry , WaterABSTRACT
Eutrophication, the over-enrichment with nutrients, for example, nitrogen and phosphorus, of ponds, reservoirs and lakes, is an urgent water quality issue. The most notorious symptom of eutrophication is a massive proliferation of cyanobacteria, which cause aquatic organism death, impair ecosystem and harm human health. The method considered to be most effective to counteract eutrophication is to reduce external nutrient inputs. However, merely controlling external nutrient load is insufficient to mitigate eutrophication. Consequently, a rapid diminishing of cyanobacterial blooms is relied on in-lake intervention, which may encompass a great variety of different approaches. Coagulation/flocculation is the most used and important water purification unit. Since cyanobacterial cells generally carry negative charges, coagulants are added to water to neutralize the negative charges on the surface of cyanobacteria, causing them to destabilize and precipitate. Most of cyanobacteria and their metabolites can be removed simultaneously. However, when cyanobacterial density is high, sticky secretions distribute outside cells because of the small size of cyanobacteria. The sticky secretions are easily to form complex colloids with coagulants, making it difficult for cyanobacteria to destabilize and resulting in unsatisfactory treatment effects of coagulation on cyanobacteria. Therefore, various coagulants and coagulation methods were developed. In this paper, the focus is on the coagulation of cyanobacteria as a promising tool to manage eutrophication. Basic principles, applications, pros and cons of chemical, physical and biological coagulation are reviewed. In addition, the application of coagulation in water treatment is discussed. It is the aim of this review article to provide a significant reference for large-scale governance of cyanobacterial blooms. PRACTITIONER POINTS: Flocculation was a promising tool for controlling cyanobacteria blooms. Basic principles of four kinds of flocculation methods were elucidated. Flocculant was important in the flocculation process.
Subject(s)
Cyanobacteria , Ecosystem , Humans , Cyanobacteria/metabolism , Water Quality , Lakes/chemistry , Ponds , Eutrophication , Phosphorus/metabolismABSTRACT
The potential for the presence of microplastics (MPs) in municipal solid waste incineration bottom ash (MSWI-BA) has not been fully explored. In this study, surfactant-assisted air flotation separation in aqueous media was used to examine the removal of MPs and other pollutants from different particle size fractions of MSWI-BA. The use of 1 mmol L-1 sodium dodecylbenzene sulfonate (SDBS), at a liquid-solid ratio of 60:1, increased by 66 % the quantity of MPs floated from the MSWI-BA 0-0.3 mm fraction, as compared to pure water. The four most common shapes of the floated MPs were pellets, fragments, films and fibers, and the major polymers were polypropylene, polyethylene, polymethyl methacrylate, and polystyrene (approximately 450 µg g-1 BA). The flotation of <10 µm MPs increased by up to 7 % using this method compared to flotation in saturated NaCl solution. Reuse of the flotation solution with the SDBS concentration maintained resulted in reduced MPs removal abundance by 22 % in the fourth use as compared to the first use. MPs removal correlated positively to SDBS concentration and negatively to turbidity. Precipitation from the fourth flotation solution was evaluated using polyacrylamide (PAM) and polyaluminium chloride (PAC) for the purpose of promoting the regeneration and recycling of the flotation solution. This treatment reduced MPs abundance, turbidity, and potential heavy metals in the recycled flotation solution. It is estimated that 3.4 kg of MPs could be removed from each ton of MSWI-BA. The findings of this study contribute to a better understanding of the redistribution of MPs during MSWI-BA pre-use treatment and provides a reference for the practical application of surfactant-assisted air flotation separation.
Subject(s)
Metals, Heavy , Refuse Disposal , Incineration , Solid Waste/analysis , Refuse Disposal/methods , Coal Ash , Microplastics , Plastics , Surface-Active Agents , Metals, Heavy/analysis , LipoproteinsABSTRACT
The immobilization of heavy metal pollutants in river and lake sediments is critical for environmental health and safety. In this study, combined electrokinetic and chemical immobilization were used to remediate Cd and Pb polluted river sediments. The effect of the concentrations of the immobilization reagents and the applied voltage were investigated. Immobilization ratios for Cd and Pb of 98.6% and 84.3%, respectively, was achieved at 7.5 V cm-1 using seven successive rounds of recycling of the immobilization solution of mixed 1.0 g L-1 CO32- and 3.0 g L-1 H2PO4- at the volume ratio of 1:9 with 100 mL immobilization solution to 100 g sediment. The enhancement effect of the electric field is mainly attributed to the increased contact between the immobilization reagents and the heavy metals due to electroosmosis. This study provides a new method for the treatment of heavy metal-polluted sediments.
Subject(s)
Metals, Heavy , Water Pollutants, Chemical , Cadmium , Lead , Geologic Sediments , Environmental Monitoring , Rivers , Water Pollutants, Chemical/analysis , Metals, Heavy/analysis , Risk Assessment , ChinaABSTRACT
Waste activated sludge and food waste are two typical important domestic low-value organic solid wastes (LOSW). LOSW contains significant organic matter and water content resulting in the transboundary transfer of liquid-solid-gas and other multi-mediums, such that the complexity of microplastics (MPs) migration should be of greater concern. This article provides a review of the literature focusing on the separation and extraction methods of MPs from LOSW. The occurrence and source of MPs are discussed, and the output and impact of MPs on LOSW heat and biological treatments are summarized. The fate and co-effects of MPs and other pollutants in landfills and soils are reviewed. This review highlights the migration and transformation of MPs in domestic source LOSW, and future perspectives focused on the development of a unified extraction and analysis protocol. The objective of this review is to promote the technological development of decontamination of MPs in LOSW by sufficient understanding of the fate of MPs, their interaction with coexisting pollutants and the development of targeted preventive research strategies.
Subject(s)
Environmental Pollutants , Refuse Disposal , Water Pollutants, Chemical , Microplastics , Plastics , Solid Waste/analysis , Food , Environmental Pollutants/analysis , Water Pollutants, Chemical/analysis , Wastewater/analysisABSTRACT
Soil heavy metal pollution poses a serious threat to the eco-environment. Municipal sludge-based passivators and clay minerals have been widely applied to immobilize heavy metal contamination in soils. However, little is known about the immobilization effect and mechanisms of raw municipal sludge and clay in reducing the mobility and bioavailability of heavy metals in soils. Here, municipal sludge, raw clay and mixtures of thereof were used to remediate Pb-contaminated soil from a Pb-acid battery factory. The remediation performance was evaluated through acid leaching, sequential extraction, and plant assay. Results showed that the leachable Pb content in the soil decreased from 5.0â mg kg-1 to 4.8, 4.8 and 4.4â mg kg-1 after 30 d of remediation with MS and RC added at equal weights to give total dosage of 20, 40â wt% and 60â wt %, respectively. The leachable Pb further decreased to 1.7, 2.0 and 1.7â mg kg-1 after 180 d of remediation. Speciation analysis of the soil Pb indicated that the exchangeable and Fe-Mn oxide-bound Pb were transformed into residual Pb in the early stage of remediation, and the carbonate-bound Pb and organic matter-bound Pb were transformed into residual Pb in the later stage of remediation. As a result, Pb accumulation in mung beans decreased by 78.5%, 81.1% and 83.4% after 180 days of remediation. These results indicate that the leaching toxicity and phytotoxicity of Pb in remediated soils were significantly reduced, presenting a better and low-cost method for soil remediation.
ABSTRACT
The critical role of the Auger parameter in providing insight into both initial state and final state factors affecting measured XPS binding energies is illustrated by analysis of Ni 2p(3/2) and L(3)M(45)M(45) peaks as well as the Auger parameters of nickel alloys, halides, oxide, hydroxide and oxy-hydroxide. Analyses of the metal and alloys are consistent with other works, showing that final state relaxation shifts, ΔR, are determined predominantly by changes in the d electron population and are insensitive to inter-atomic charge transfer. The nickel halide Auger parameters are dominated by initial state effects, Δε, with increasing positive charge on the core nickel ion induced by increasing electronegativity of the ligands. This effect is much greater than the final state shifts; however, the degree of covalency is reflected in the Wagner plot where the more polarizable iodide and bromide have greater ΔR. The initial state shift for NiO is much smaller than those of Ni(OH)(2) or NiOOH and the effective oxidation state is much less than that inferred from the average electronegativity of the ligand(s). Auger parameter analysis indicates that the bonding in NiO appears to have stronger contributions from initial state charge transfer from the oxygen ligands than that in the hydroxide and oxyhydroxide consistent with the considerable differences in the Ni-O bond lengths in these compounds with some relaxation of this state occurring during final state phenomena. The Auger parameter of NiOOH is, however, shifted positively, like the iodide, indicating greater polarizability of the ligands and covalency in this bonding. There is support for more direct use of relative bond lengths in interpreting differences between related compounds rather than more general electronegativity or similar parameters.
ABSTRACT
Sludge conditioning is important for improved dewatering, with the sludge characteristics impacting the effect of conditioning. A composite conditioner, Fe2+-activated sodium persulfate (Fe2+/SPS) combined with phosphogypsum (PG), was used to examine its impact on sludges with different organic contents (34.6-43.8%) or different solid contents (2.8-5.9%). Response surface optimization analysis shows that when the best conditioning is achieved, the reduction of the specific resistance to filtration (SRF) is not sensitive to organic matter content, but the dewatering performance of the sludge is greatly affected by the solid content. The oxidation role of Fe2+/SPS and the skeleton builder role of PG together affect the conditioning, oxidation playing a major role in conditioning, especially for greater organic matter content. The organic content (maximum ηSOL value was 0.32) also affects the effectiveness of the skeleton builder more than the solid content (Maximum ηSOL value was 0.25). Changes in PG significantly impacts the optimal molar ratio and dosage of Fe2+/SPS. Sludge with greater solid content requires greater Fe2+/SPS dosage to provide stronger oxidation to destroy flocs, and the maximum Fe2+:SPS molar ratio was 1.14 with solid content of 5.9 wt%. The composite conditioning decreases the content of extracellular polymeric substances and proteins/polysaccharides. This study provides new insight into the relationship between the oxidation role of Fe2+/SPS and the skeleton builder role of PG for sludge conditioning strategies according to the optimal conditions.
Subject(s)
Sewage , Water , Extracellular Polymeric Substance Matrix , Filtration , Oxidation-Reduction , Skeleton , Waste Disposal, FluidABSTRACT
Sewage treatment plants act as both sinks and sources of microplastics with elevated concentrations of microplastics accumulating in the sludge. Consequently, the effects of sludge conditioning and dewatering processes on the fate of microplastics need to be clarified. Microplastic characteristics in sludge, before and after advanced oxidation Fe(II)-activated persulfate conditioning were studied using a microplastics dynamic flotation separator (MDFS). In the unconditioned sludge (no dewatering), white and transparent microplastics dominated and seven types of plastic polymer were detected with polyethylene (30.3%) and polypropylene (23.9%) being the main ones. Pellet microplastics were found to be the dominant morphology, accounting for 67.0% of the total number of microplastics. The abundance of microplastics extracted using the MDFS device from the unconditioned (no dewatering) sludge was 320 ± 3 particles g-1 dried sludge, which was greater by 37% than extracted using microplastics static flotation separation. Due to the release of the adsorbed microplastics from the destroyed sludge flocs after conditioning, the abundance of extractable microplastics increased by 19 ± 2% as compared to the unconditioned sludge (both with no dewatering). After filter presses (plate-frame filter, vacuum filter) and centrifuge dewatering, 81-90% of the microplastics were present in the filter cake, of which microplastics <500 µm accounted for more than 80% of the total number. The abundance of microplastics per unit volume of filtrate after filter press dewatering was significantly smaller than after centrifuge dewatering (3.2-4.4 × 103 cf 13.0 × 103 particles L-1, respectively). The difference increments in relative abundance of <10 µm microplastics in the centrifuge filtrate was about twice that of the filter presses. The surface morphology of the microplastics did not change in the conditioning process. This study highlights the need to assess the application of advanced oxidation conditioning which has significant influence on the microplastics distribution via the subsequent sludge dewatering.
Subject(s)
Microplastics , Sewage , Ferrous Compounds , Plastics , Waste Disposal, Fluid , WaterABSTRACT
Selenium (Se) has been mobilised by leaching from coal and associated waste rock exposed by mining activities in Western Canada, with deleterious impact on aquatic wildlife. Waste rock characterisation indicates that up to 7% of the Se, as Se(IV), may be associated with organic matter, with ≈9%, as Se(0), associated with euhedral pyrite. Small 1-2 µm mineral particles with average Se concentration of 1.0 ± 0.4 wt% account for the remaining Se with the largest components likely to be associated with Fe oxide/hydroxide/carbonate as Se(0) and framboidal pyrite as Se(IV) and Se(0). No evidence was found for the presence of Se(-I), Se(-II) or Se(VI). In the first 8 weeks of leaching Se release was not correlated to the addition of aqueous silicate, added to aid pyrite passivation, but was reduced by approximately one third when the waste was treated with manure. This suggests the primary initial source of leached Se was not pyrite. Added organic C results in increased microbial numbers, particularly aerobic microbes, and promotes the formation of extensive coating of extracellular polymeric substances resulting in depletion of O2 at particle surfaces, reducing oxidation of Se(IV) and therefore reducing the leach rate of Se. Subsequent to 8 weeks of leaching the rates of release of Se from the treated wastes were similar regardless of treatment strategy but were reduced as compared to the untreated waste rock, suggestive of partial framboidal pyrite geochemical and microbial passivation. Se leaching was not correlated to S leaching, but the source(s) of the leached S was not known as approximately half of the S within the waste rock was non-sulfidic. These results indicate that utilisation of local organic carbon-containing wastes for coverage of coal waste rock may be a cost-effective strategy to reduce Se leaching to acceptable rates of release regardless of whether the Se is associated with framboidal pyrite or organics.
Subject(s)
Selenium , Carbonates , Coal , Mining , Oxidation-Reduction , Selenium/analysisABSTRACT
The effect of impurities in the zinc sulfide mineral sphalerite on surface wettability has been investigated theoretically to shed light on previously reported conflicting results on sphalerite flotation. The effect of iron and copper impurities on the sphalerite (110) surface energy and on the water adsorption energy was calculated with the semi-empirical method modified symmetrically orthogonalized intermediate neglect of differential overlap (MSINDO) using the cyclic cluster model. The effect of impurities or dopants on surface energies is small but significant. The surface energy increases with increasing surface iron concentration while the opposite effect is reported for increasing copper concentration. The effect on adsorption energies is much more pronounced with water clearly preferring to adsorb on an iron site followed by a zinc site, and copper site least favorable. The theoretical results indicate that a sphalerite (110) surface containing iron is more hydrophilic than the undoped zinc sulfide surface. In agreement with the literature, the surface containing copper (either naturally or by activation) is more hydrophobic than the undoped surface.
ABSTRACT
We report the in-flight CVD coating with smooth 1-2 nm thick SiO(2) of pure and doped rutile particles via the oxidation of SiCl(4) vapour introduced in the high temperature zone of a purpose built thermal reactor. The effectiveness of the coatings was determined by a combination of electron microscopy, surface analysis and photocatalytic measurements. No excess Cl was detected on the coated pigment particles indicating the complete oxidation of the SiCl(4) precursor. In conjunction with the experimental outcomes of this optimised deposition process, we use first-principles density functional and semi-empirical quantum chemical calculations to examine the underlying electronic processes which determined the morphology and photocatalytic properties of the coated titania. We highlight the presence of low lying valence electronic states which reduce photocatalytic activity, and as a consequence decrease the population of photo-excited titania electrons which transfer to the surrounding matrix. Born-Oppenheimer molecular dynamics (MD) simulations indicate that the coating process is completed within the order of 10 ps.