Metal(loid)s remobilization and mineralogical transformations in smelter-polluted savanna soils under simulated wildfire conditions.

The surroundings of mines and smelters may be exposed to wildfires, especially in semi-arid areas. The temperature-dependent releases of metal(loid)s (As, Cd, Cu, Pb, Zn) from biomass-rich savanna soils collected near a Cu smelter in Namibia have been studied under simulated wildfire conditions. Laboratory single-step combustion experiments (250-850 °C) and experiments with a continuous temperature increase (25-750 °C) were coupled with mineralogical investigations of the soils, ashes, and aerosols. Metals (Cd, Cu, Pb, Zn) were released at >550-600 °C, mostly at the highest temperatures, where complex aerosol particles, predominantly composed of slag-like aggregates, formed. In contrast, As exhibited several emission peaks at ~275 °C, ~370-410 °C, and ~580 °C, reflecting its complex speciation in the solid phase and indicating its remobilization, even during wildfires with moderate soil heating. At <500 °C, As was successively released via the transformation of As-bearing hydrous ferric oxides, arsenolite (As2O3) grains attached to the organic matter fragments, metal arsenates, and/or As-bearing apatite, followed by the thermal decomposition of enargite (Cu3AsS4) at >500 °C. The results indicate that the active and abandoned mining and smelting sites, especially those highly enriched in As, should be protected against wildfires, which can be responsible for substantial As re-emissions.

Characterization and pH-dependent environmental stability of arsenic trioxide-containing copper smelter flue dust.

Increasing amounts of impurities (especially As) in Cu ores have aggravated the problem of flue dust generation in recent years. As an example from a smelter processing As-rich Cu ores, we characterized a flue dust particularly rich in As (>50 wt%) to understand its mineralogy and pH-dependent leaching behavior, with special emphasis on binding, release and solubility controls of inorganic contaminants (As, Bi, Cd, Cu, Pb, Sb, Zn). Whereas arsenolite (As2O3) was the major host for As and Sb, other contaminants were bound in sulfides, arsenates, alloys and slag-like particles. The EU regulatory leaching test (EN 12457-2) indicated that leached As, Cd, Sb and Zn significantly exceeded the limit values for landfills accepting hazardous waste. The pH-dependent leaching test (CEN/TS 14997) revealed that As, Sb and Pb exhibited the greatest leaching at pH 11-12, whereas Cd, Cu and Zn were leached most under acidic condition (pH 3) and Bi leaching was pH-independent. Mineralogical investigation of leached residue coupled with geochemical modeling confirmed that newly formed Ca, Pb and Ca-Pb arsenates (mimetite, Pb5(AsO4)3Cl) partly control the release of As and other contaminants under circumneutral and alkaline conditions and will be of key importance for the fate of smelter-derived contamination in soils or when stabilization technology is employed.

Oral bioaccessibility of inorganic contaminants in waste dusts generated by laterite Ni ore smelting.

The laterite Ni ore smelting operations in Niquelândia and Barro Alto (Goiás State, Brazil) have produced large amounts of fine-grained smelting wastes, which have been stockpiled on dumps and in settling ponds. We investigated granulated slag dusts (n = 5) and fly ash samples (n = 4) with a special focus on their leaching behaviour in deionised water and on the in vitro bioaccessibility in a simulated gastric fluid, to assess the potential exposure risk for humans. Bulk chemical analyses indicated that both wastes contained significant amounts of contaminants: up to 2.6 wt% Ni, 7580 mg/kg Cr, and 508 mg/kg Co. In only one fly ash sample, after 24 h of leaching in deionised water, the concentrations of leached Ni exceeded the limit for hazardous waste according to EU legislation, whereas the other dusts were classified as inert wastes. Bioaccessible fractions (BAF) of the major contaminants (Ni, Co, and Cr) were quite low for the slag dusts and accounted for less than 2 % of total concentrations. In contrast, BAF values were significantly higher for fly ash materials, which reached 13 % for Ni and 19 % for Co. Daily intakes via oral exposure, calculated for an adult (70 kg, dust ingestion rate of 50 mg/day), exceeded neither the tolerable daily intake (TDI) nor the background exposure limits for all of the studied contaminants. Only if a higher ingestion rate is assumed (e.g. 100 mg dust per day for workers in the smelter), the TDI limit for Ni recently defined by European Food Safety Authority (196 µg/day) was exceeded (324 µg/day) for one fly ash sample. Our data indicate that there is only a limited risk to human health related to the ingestion of dust materials generated by laterite Ni ore smelting operations if appropriate safety measures are adopted at the waste disposal sites and within the smelter facility.

The pH-dependent leaching behavior of slags from various stages of a copper smelting process: Environmental implications.

The leaching behaviors of primary copper (Cu) slags originating from Ausmelt, reverbatory, and converter furnaces operating under a single technological process were compared to a residual slag tailing obtained by slag re-processing via flotation and metal recovery. The EN 12457-2 leaching test, used for assessment of the hazardous properties, was followed by the CEN/TS 14997 pH-static leaching test (pH range 3-12). Both leaching experiments were coupled with a mineralogical investigation of the primary and secondary phases as well as geochemical modeling. Metals (Cd, Cu, Pb, Zn) exhibit the highest leaching at low pH. Under acidic conditions (pH 3-6), Ausmelt slag and slag tailing exhibited higher metal leaching compared to other slag types. Very low leaching of metals (far below EU limits for non-hazardous waste) was observed at natural pH (7.9-9.0) for all the studied slag samples. In contrast, relatively high leaching of As was observed over the entire pH range, especially for Ausmelt slag (exceeding the EU limit for hazardous waste by 1.7×). However, geochemical modeling and scanning electron microscopy indicated that formation of stable Ca-Cu-Pb arsenates and the binding of As to newly formed Fe (oxyhydr)oxides play an important role in efficient As immobilization at the slag-water interface. In contrast, no controls were predicted for Sb, whose leaching was almost pH-independent. Nevertheless Sb leached concentrations at natural pH were below EU limit for hazardous waste. Re-processing of primary Cu slags for metal recovery, and subsequent co-disposal of the resulting slag tailing with dolomite-rich mine tailing and local laterite is suitable for stabilizing the remaining contaminants (except Sb) and limiting their leaching into the environment.

Isotopic Tracing of Thallium Contamination in Soils Affected by Emissions from Coal-Fired Power Plants.

Here, for the first time, we report the thallium (Tl) isotope record in moderately contaminated soils with contrasting land management (forest and meadow soils), which have been affected by emissions from coal-fired power plants. Our findings clearly demonstrate that Tl of anthropogenic (high-temperature) origin with light isotope composition was deposited onto the studied soils, where heavier Tl (ε(205)Tl ∼ -1) naturally occurs. The results show a positive linear relationship (R(2) = 0.71) between 1/Tl and the isotope record, as determined for all the soils and bedrocks, also indicative of binary Tl mixing between two dominant reservoirs. We also identified significant Tl isotope variations within the products from coal combustion and thermo-desorption experiments with local Tl-rich coal pyrite. Bottom ash exhibited the heaviest Tl isotope composition (ε(205)Tl ∼ 0), followed by fly ash (ε(205)Tl between -2.5 and -2.8) and volatile Tl fractions (ε(205)Tl between -6.2 and -10.3), suggesting partial Tl isotope fractionations. Despite the evident role of soil processes in the isotope redistributions, we demonstrate that Tl contamination can be traced in soils and propose that the isotope data represent a possible tool to aid our understanding of postdepositional Tl dynamics in surface environments for the future.

The pH-dependent release of platinum group elements (PGEs) from gasoline and diesel fuel catalysts: Implication for weathering in soils.

Powdered samples of new and old gasoline catalysts (Pt, Pd, Rh) and new and old diesel (Pt) catalysts were subjected to a pH-static leaching procedure (pH 2-9) coupled with thermodynamic modeling using PHREEQC-3 to verify the release and mobility of PGEs (platinum group elements). PGEs were released under acidic conditions, mostly exhibiting L-shaped leaching patterns: diesel old: 5.47, 0.005, 0.02; diesel new: 68.5, 0.23, 0.11; gasoline old: 0.1, 11.8, 4.79; gasoline new 2.6, 25.2, 35.9 in mg kg(-1) for Pt, Pd and Rh, respectively. Only the new diesel catalyst had a strikingly different leaching pattern with elevated concentrations at pH 4, probably influenced by the dissolution of the catalyst carrier and washcoat. The pH-static experiment coupled with thermodynamic modeling was found to be an effective instrument for understanding the leaching behavior of PGEs under various environmental conditions, and indicated that charged Pt and Rh species may be adsorbed on the negatively charged surface of kaolinite or Mn oxides in the soil system, whereas uncharged Pd and Rh species may remain mobile in soil solutions.

Evaluating the potential of three Fe- and Mn-(nano)oxides for the stabilization of Cd, Cu and Pb in contaminated soils.

The potential of three Fe- and Mn-(nano)oxides for stabilizing Cd, Cu and Pb in contaminated soils was investigated using batch and column experiments, adsorption tests and tests of soil microbial activity. A novel synthetic amorphous Mn oxide (AMO), which was recently proposed as a stabilizing amendment, proved to be the most efficient in decreasing the mobility of the studied metals compared to nano-maghemite and nano-magnetite. Its application resulted in significant decreases of exchangeable metal fractions (92%, 92% and 93% decreases of Cd, Cu and Pb concentrations, respectively). The adsorption capacity of the AMO was an order of magnitude higher than those recorded for the other amendments. It was also the most efficient treatment for reducing Cu concentrations in the soil solution. No negative effects on soil microorganisms were recorded. On the other hand, the AMO was able to dissolve soil organic matter to some extent.

Dust from Zambian smelters: mineralogy and contaminant bioaccessibility.

Metal smelting is often responsible for local contamination of environmental compartments. Dust materials escaping from the smelting facilities not only settle in the soil, but can also have direct effects on populations living close to these operations (by ingestion or inhalation). In this particular study, we investigate dusts from Cu-Co metal smelters in the Zambian Copperbelt, using a combination of mineralogical techniques (XRD, SEM/EDS, and TEM/EDS), in order to understand the solid speciation of the contaminants, as well as their bioaccessibility using in vitro tests in simulated gastric and lung fluids to assess the exposure risk for humans. The leaching of metals was mainly dependent on the contaminant mineralogy. Based on our results, a potential risk can be recognized, particularly from ingestion of the dust, with bioaccessible fractions ranging from 21 to 89% of the total contaminant concentrations. In contrast, relatively low bioaccessible fractions were observed for simulated lung fluid extracts, with values ranging from 0.01% (Pb) up to 16.5% (Co) of total contaminant concentrations. Daily intakes via oral exposure, calculated for an adult (70 kg, ingestion rate 50 mg dust per day), slightly exceeded the tolerable daily intake limits for Co (1.66× for fly ash and 1.19× for slag dust) and occasionally also for Pb (1.49×, fly ash) and As (1.64×, electrostatic precipitator dust). Cobalt has been suggested as the most important pollutant, and the direct pathways of the population's exposures to dust particles in the industrial parts of the Zambian Copperbelt should be further studied in interdisciplinary investigations.

Tracing anthropogenic mercury in soils from Fe-Hg mining/smelting area: Isotopic and speciation insights.

Mercury (Hg) stable isotope ratios supplemented by Hg solid speciation data were determined in soils in a former Fe-Hg mining/smelting area (Jedová hora, Czech Republic, Central Europe). The dominant Hg phase in the studied soils was found to be cinnabar (HgS). A secondary form of soil Hg(II) was represented by Hg weakly and strongly bound to mineral (micro)particles, as revealed by thermo-desorption analysis. These Hg species probably play a key role in local soil Hg processes and biogeochemical cycling. The Hg isotopic data generally showed small differences between HgS (-1.1 to -0.8‰; δ202Hg) and the soil samples (-1.4 to -0.9‰; δ202Hg), as well as limited isotopic variability within the two studied soil profiles. On the other hand, the detected negative δ202Hg shift (∼0.4‰) in organic horizons compared to mineral soils in the highly contaminated profile suggests the presence of secondary post-depositional Hg processes, such as sorption or redox changes. For the less contaminated profile, the observed Hg isotopic variation (∼0.3‰; δ202Hg) in the subsurface mineral soil compared to both overlying and underlying horizons is likely due to cyclic redox reactions associated with Hg isotopic fractionation. We assume that the adsorption of Hg(II) to secondary Fe(III)/Mn(III,IV)-oxides could be of major importance in such cases.

Sensitivity of microbial bioindicators in assessing metal immobilization success in smelter-impacted soils.

While plant toxicity reduction remains the primary metric for judging the success of metal immobilization in soil, the suitability of microorganisms as universal indicators of its effectiveness in various contaminated soils remains a point of contention. This study assessed the sensitivity of microbial bioindicators in monitoring metal immobilization success in smelter-impacted soils. It compared plants and microorganisms as indicators of the efficiency of natural Fe-Mn nodules from the Gulf of Finland in immobilizing metals in soils contaminated by a Ni/Cu smelter, on the Kola Peninsula, Murmansk region, Russia. Perennial ryegrass (Lolium perenne) was grown on nodule-amended and control soils. Plant responses in the smelter-impacted soils proved to be sensitive and robust indicators of successful metal immobilization. However, microbial responses exhibited a more complex story. Despite the observed reductions in soluble metal concentrations, shoot metal contents in ryegrass, and significant improvements in plant growth, certain microbial bioindicators were unresponsive to metal immobilization success brought about by the addition of Fe-Mn nodules. Among microbial bioindicators studied, community-level physiological profiling, microbial biomass carbon, and basal respiration were sensitive indicators of metal immobilization success, whereas the number of saprotrophic, oligotrophic, and Fe-oxidizing bacteria and fungi, the biomass of bacteria and fungi, and enzymatic activity were less robust indicators. Interestingly, the correlations between different microbial responses measured were weak or even negative. Some microbial responses also exhibited negative correlations with plant biomass. These findings underscore the need for further research on comparative evaluations of plants and microorganisms as reliable indicators of metal immobilization efficacy in polluted environments.

Contaminant release from massive copper metallurgical slags: Insights from long-term monolithic leaching tests.

Compared to compliance leaching tests performed on granular materials, leaching experiments on monolithic slags are more suitable for predicting the contaminant release when large boulders or poured slag layers are submerged in water, a specific environmental scenario typical for many smelting sites. We conducted EN 15863 dynamic monolithic leaching tests on massive copper slags over a prolonged period of 168 d. The patterns of the major contaminant (Cu, Co) fluxes indicated an initial diffusion process followed by the dissolution of primary sulfides with the maximum cumulative releases attaining 75.6 mg/m2 Cu and 4.20 mg/m2 Co. A multi-method mineralogical investigation showed that lepidocrocite (γ-FeOOH) and goethite (α-FeOOH) started to form on the slag surface already after 9 d of leaching and partly immobilized Cu (but not Co). Vanadium and other trace elements (Zn, Pb, Cd) were leached to a much lower extent, initially controlled by diffusion followed by depletion and/or sorption to Fe oxyhydroxides. The results of the long-term leaching of the monolithic slag provide new information about the key processes affecting the release of metal (loid) contaminants under specific submerged conditions and have implications for the environmental management of slag disposal sites and/or potential reuse of slags in civil engineering.

Smelter-derived soil contamination in Luanshya, Zambia.

Extensive mining and smelting contributed to the declining quality of Luanshya soils. The local smelter was the epicenter of contamination as shown by a spatial distribution analysis. Closeby soil profiles smelter exhibit extremely high Cu concentrations (up to 46,000 mg kg-1 Cu) relative to deeper layers where only background levels of trace elements were observed. A remote profile did not exhibit significant contamination. Lead isotopic ratios revealed that Pb contamination in the Luanshya soils was not smelter-derived. It was shown in this way that the historical usage of leaded gasoline was the main source of this metal. Although the Luanshya smelter also produced Co, this metal was not an important contaminant. Copper leaching was a concern in Luanshya. Upwards of 52 % of Cu was extractable in the exchangeable step of a sequential extraction procedure (SEP), but only for samples where Cu concentrations were high, suggesting that Cu was released exclusively from anthropogenic particles. This was supported by the SEP results for similar depths at the remote soil, where only a small fraction of Cu was labile (5.6 %). Lead and Co were strongly bound in the soils throughout. The excess of Cu in the topsoils was mostly bound in smelter-derived particles. These appeared as spherical fast-cooled droplets composed mostly of sulfides, oxides, and glass. X-ray diffraction and electron probe microanalysis of those particles allowed for a phase classification. Compositions were regularly not stoichiometric so most particles were classified as intermediate solid solutions. However, molecular proportions often closely resembled those of bornite, chalcanthite, cuprospinel, covellite, delafossite, diginite, or hydrous ferric oxides. Concentrations of Cu were often 100 % near the center of the particles indicating an inefficient smelting process. Weathering to some degree was common, which in conjunction with the susceptibility of Cu leaching was highly alarming.

Silver isotopes: A tool to trace smelter-derived contamination.

Here, for the first time, we report the concentrations and isotopic data of Ag in a variety of ore and metallurgical samples and forest soils that have been polluted due to Ag-Pb smelter emissions. Similar to the Ag concentrations, we identified a large range of δ109Ag values (from -0.8 to +2.4‰), a ∼3‰ spread, within the primary and secondary materials (i.e., galena, fly ash, slag and matte). This phenomenon, however, is evidently unrelated to Ag isotopic fractionation during the smelting process, but it reflects the starting 109Ag/107Ag signal in ore mineral and/or the specific type of ore genesis. The two studied soil profiles differed in Ag isotopic composition, but on the other hand, they consistently showed significantly lighter Ag (≤+0.8‰) of metallurgical origin in the upper horizons compared to the bottom horizons and bedrocks, with low Ag amounts depleted of 107Ag (≤+2.9‰). This isotopic pattern can be attributed to a ternary mixing relationship involving two major anthropogenic Ag components and a minor contribution from geogenic Ag. Accordingly, we did not observe any post-depositional isotopic fractionation in our soils, since Ag was geochemically stable and it was not subjected to leaching. In summary, the Ag isotopes have a potential to trace variations in anthropogenic phases, to monitor specific geochemical processes, and are clearly applicable as anthropogenic Ag source and Ag load proxies.

Bioaccessible metals in dust materials from non-sulfide Zn deposit and related hydrometallurgical operation.

Mining and processing of ores in arid (desert) areas generates high amounts of dust, which might be enriched in potentially harmful elements. We studied dust fractions of ores, soils, and technological materials from mining and related hydrometallurgical operation at former Skorpion Zinc non-sulfide Zn deposit in southern Namibia (closed and placed under maintenance in 2020). Chemical and mineralogical investigation was combined with oral bioaccessibility testing of fine dust fractions (<48 µm and <10 µm) in simulated gastric fluid (SGF) to assess potential risk of intake of metallic contaminants (Cd, Cu, Pb, Zn) for staff operating in the area. The bulk metals concentrations were largely variable and ranked as follows: soils < tailings â‰ª Skorpion ores < imported ores and dross used for feed ore blending. Maximum contaminant concentrations in the original granular materials were 927 mg Cd/kg, 9150 mg Cu/kg, 50 g Pb/kg and 706 g Zn/kg, respectively, and generally increased as a function of decreasing grain size. The highest bioaccessible concentrations of Cd and Pb yielded imported ores from Taiwan and Turkey and, together with the milled dross, these samples also exhibited the highest Zn bioaccessibilities. The exposure estimates calculated for a worker (weighing 70 kg) in this mining/ore processing operation at a dust ingestion rate of 100 mg/day indicated that most dust samples (soils, tailings, Skorpion ores) exhibited metals intake values far below tolerable daily intake limits. The overall health risk was limited in all mining and ore processing areas except for the ore blending area, where imported ores and recycled dross enriched in bioaccessible Cd, Pb and/or Zn were used for the ore blending. Safety measures required by the mine operator (wearing of masks by the operating staff) helped to prevent the staff's exposure to potentially contaminated dust even in this blending ore area.

Experimental in situ transformation of Pb smelter fly ash in acidic soils.

Soils in the vicinity of nonferrous metal smelters are often highly polluted by inorganic contaminants released from particulate emissions. We used a technique with double polyamide experimental bags (1-µm mesh) to study the in situ transformation of fly ash (FA) from a secondary Pb smelter in acidic soil profiles. Between 62 and 66% of the FA dissolved after one year's exposure in the soils, leading to complete dissolution of primary caracolite (Na(3)Pb(2)(SO(4))(3)Cl) and KPb(2)Cl(5), with formation of secondary anglesite (PbSO(4)), minor PbSO(3), and trace carbonates. Release of Pb was pH-dependent, whereas not for Cd and Zn. Significant amounts of metals (mainly Cd and Zn) partitioned into labile soil fractions. The field data agreed with laboratory pH-static leaching tests performed on FA, which was washed before the experiment to remove soluble salts. This indicates that appropriate laboratory leaching can accurately predict FA behavior in real-life scenarios (e.g., exposure in soil).

Transmission electron microscopy investigation of colloids and particles from landfill leachates.

Leachates collected at two (active and closed) municipal solid waste (MSW) landfills were examined for colloids and particles by transmission electron microscopy, energy dispersive spectrometry, selected area electron diffraction and for the chemical compositions of the filtrates after the filtration to 0.1 µm and ultrafiltration to 1 kDa (~ 1 nm). Six groups of colloids/particles in the range 5 nm to 5 µm were determined (in decreasing order of abundance): carbonates, phyllosilicates (clay minerals and micas), quartz, Fe-oxides, organics and others (salts, phosphates). Inorganic colloids/particles in leachates from the active landfill predominantly consist of calcite (CaCO(3)) and minor clay minerals and quartz (SiO(2)). The colloids/particles in the leachates from the closed landfill consist of all the observed groups with dominant phyllosilicates. Whereas calcite, Fe-oxides and phosphates can precipitate directly from the leachates, phyllosilicates and quartz are more probably either derived from the waste or formed by erosion of the geological environment of the landfill. Low amounts of organic colloids/particles were observed, indicating the predominance of organic molecules in the 'truly dissolved' fraction (fulvic compounds). Especially newly formed calcite colloids forming particles of 500 nm and stacking in larger aggregates can bind trace inorganic contaminants (metals/metalloids) and immobilize them in landfill environments.

Contaminant Binding and Bioaccessibility in the Dust From the Ni-Cu Mining/Smelting District of Selebi-Phikwe (Botswana).

We studied the dust fractions of the smelting slag, mine tailings, and soil from the former Ni-Cu mining and processing district in Selebi-Phikwe (eastern Botswana). Multi-method chemical and mineralogical investigations were combined with oral bioaccessibility testing of the fine dust fractions (<48  and <10 µm) in a simulated gastric fluid to assess the potential risk of the intake of metal(loid)s contaminants. The total concentrations of the major contaminants varied significantly (Cu: 301-9,600 mg/kg, Ni: 850-7,000 mg/kg, Co: 48-791 mg/kg) but were generally higher in the finer dust fractions. The highest bioaccessible concentrations of Co, Cu, and Ni were found in the slag and mine tailing dusts, where these metals were mostly bound in sulfides (pentlandite, pyrrhotite, chalcopyrite). On the contrary, the soil dusts exhibited substantially lower bioaccessible fractions of these metals due to their binding in less soluble spinel-group oxides. The results indicate that slag dusts are assumed to be risk materials, especially when children are considered as a target group. Still, this exposure scenario seems unrealistic due to (a) the fencing of the former mine area and its inaccessibility to the local community and (b) the low proportion of the fine particles in the granulated slag dump and improbability of their transport by wind. The human health risk related to the incidental ingestion of the soil dust, the most accessible to the local population, seems to be quite limited in the Selebi-Phikwe area, even when a higher dust ingestion rate (280 mg/d) is considered.

Effect of peat organic matter on sulfide weathering and thallium reactivity: Implications for organic environments.

Weathering of Tl-containing sulfides in a model (12-week) peat pot trial was studied to better understand their geochemical stability, dissolution kinetics, alteration products and the associated release and mobility of anthropogenic Tl in organic environments. We also present the effect of industrial acid rainwater on sulfide degradation and Tl migration in naturally acidic peat. Sphalerite (ZnS) was much less stable in peat than other Tl-containing sulfides (galena and pyrite), and thus acted as a major phase responsible for Tl mobilization. Furthermore, Tl incongruently leached out over Zn from ZnS, and accumulated considerably more in the peat solutions (≤5 µg Tl/L) and the peat samples (≤0.4 mg Tl/kg) that were subjected to acid rain watering compared to a deionized H2O regime. This finding was in good agreement with the absence of secondary Tl-containing phases, which could potentially control the Tl flux into the peat. The behavior of Tl was not as conservative as Pb throughout the trial, since a higher peat mobility and migration potential of Tl was observed compared to Pb. In conclusion, industrial acid precipitations can significantly affect the stability of ZnS even in acidic peat/organic environments, making it susceptible to enhanced weathering and Tl release in the long term.

Evaluation of thallium isotopic fractionation during the metallurgical processing of sulfides: An update.

In this study, we report combined Tl isotopic and Tl mineralogical and speciation data from a set of Tl-rich sulfide concentrates and technological wastes from hydrometallurgical Zn extraction. We also present the first evaluation of Tl isotopic ratios over a cycle of sulfide processing, from the ore flotation to pyro- and hydrometallurgical stages. The results demonstrate that the prevailing Tl form in all samples is Tl(I), without any preferential incorporation into sulfides or Tl-containing secondary phases, indicating an absence of Tl redox reactions. Although the Tl concentrations varied significantly in the studied samples (~9-280 mg/kg), the overall Tl isotopic variability was small, in the range of -3.1 to -4.4 ± 0.7 (2σ) ε205Tl units. By combining present ε205Tl results with the trends first found for a local roasting plant, it is possible to infer minimum Tl isotopic effects throughout the studied industrial process. As a result, the use of Tl isotopic ratios as a source proxy may be complicated or even impossible in areas with naturally high/extreme Tl background contents. On the other hand, areas with two or more isotopically contrasting Tl sources allow for relatively easy tracing, i.e., in compartments which do not suffer from post-depositional isotopic redistributions.

Mechanisms and efficiency of the simultaneous removal of metals and cyanides by using ferrate(VI): crucial roles of nanocrystalline iron(III) oxyhydroxides and metal carbonates.

The reaction of potassium ferrate(VI), K(2)FeO(4), with weak-acid dissociable cyanides--namely, K(2)[Zn(CN)(4)], K(2)[Cd(CN)(4)], K(2)[Ni(CN)(4)], and K(3)[Cu(CN)(4)]--results in the formation of iron(III) oxyhydroxide nanoparticles that differ in size, crystal structure, and surface area. During cyanide oxidation and the simultaneous reduction of iron(VI), zinc(II), copper(II), and cadmium(II), metallic ions are almost completely removed from solution due to their coprecipitation with the iron(III) oxyhydroxides including 2-line ferrihydrite, 7-line ferrihydrite, and/or goethite. Based on the results of XRD, Mössbauer and IR spectroscopies, as well as TEM, X-ray photoelectron emission spectroscopy, and Brunauer-Emmett-Teller measurements, we suggest three scavenging mechanisms for the removal of metals including their incorporation into the ferrihydrite crystal structure, the formation of a separate phase, and their adsorption onto the precipitate surface. Zn and Cu are preferentially and almost completely incorporated into the crystal structure of the iron(III) oxyhydroxides; the formation of the Cd-bearing, X-ray amorphous phase, together with Cd carbonate is the principal mechanism of Cd removal. Interestingly, Ni remains predominantly in solution due to the key role of nickel(II) carbonate, which exhibits a solubility product constant several orders of magnitude higher than the carbonates of the other metals. Traces of Ni, identified in the iron(III) precipitate, are exclusively adsorbed onto the large surface area of nanoparticles. We discuss the relationship between the crystal structure of iron(III) oxyhydroxides and the mechanism of metal removal, as well as the linear relationship observed between the rate constant and the surface area of precipitates.