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Geochemical anomalies are gaining importance due to the Europe's renewed prospecting activities for technologically critical metals, such as nickel (Ni) and cobalt (Co). In this context, soils developed on Ni laterites near old open pit mining and exploration works near Křemže in southern Czech Republic were investigated using multi-method approach to assess the distribution, solid speciation, and (bio)availability of the trace metals, with a particular focus on Ni, chromium (Cr), and Co. The total concentrations of metals in the studied soils (Ni: 170–4950 mg/kg, Cr: 56–1190 mg/kg, Co: 14–424 mg/kg) exceeded the median world regulatory guideline values (Ni: 112 mg/kg; Cr: 250 mg/kg; Co: 50 mg/kg) as well as the Czech concentration limits for agricultural soils for most of the samples. The concentration of metals in the soil profiles generally increased as a function of depth with surface horizons in agricultural plots homogenized by ploughing. The effect of a former open pit mine (already closed for ca 80 years) on the vertical distribution of metallic elements has not been demonstrated. The extractable metals were relatively low (extraction efficiency order: water < DTPA < EDTA). The mean EDTA-extractable values corresponded to 4.2 % Ni tot , 8.6 % Co tot, and only 0.14 % Cr tot. This contrasting metal availability is strictly related to the metal speciation in the solid phase. The primary minerals (olivine, clinopyroxene) are highly weathered to secondary phyllosilicates (lizardite, talc) and Fe oxyhydroxides and Mn oxides, all representing important carriers for Ni. Cobalt was exclusively hosted by Mn oxides, and the less mobile Cr was mainly bound in insoluble phases, likely spinel-family oxides. Despite the relatively low metal availability, elevated concentrations of Ni in the crop biomass (86 mg/kg) collected in the agricultural area suggest a metal uptake from the soil, which should be further investigated in detail. [Display omitted] • High Ni, Cr, and Co in laterite soils in southern Czech Republic • Metal concentrations in soil profiles generally increase with depth. • Ni is mainly bound to secondary phyllosilicates and oxides, and Co in Mn oxides. • Mean EDTA-extractable metals are 4.2 % Ni tot , 8.6 % Co tot and only 0.14 % Cr tot. • Implications for environmental contamination and transfer of Ni and Co to plants [ABSTRACT FROM AUTHOR]

Human activities in cities affect properties of urban soils. In particular, urban soils often contain high contents of harmful metals even in deeper horizons added to them from diverse sources over centuries of the city development. This is reflected in complex distribution of metals in bulk soils with depth and the complex metal fractionation, but the exact sources of the metals are difficult to identify. This is also the situation in soils from Wroclaw, one of the largest cities in Poland. Potentially harmful elements Pb, Cd and Hg were examined in six profiles located along the major communication route and compared to two non-urban soils profiles located close to the same route. In all of the urban profiles, Pb and Cd exceeded the element contents observed in non-urban profiles and showed an erratic distribution compared to the more predictable one in non-urban soils. The differences between urban and non-urban profiles were explained as the result of contamination coming from more pollution sources in the case of urban soils, the conclusion supported by Pb isotope analyses. In fact, Pb isotopes showed that the contamination sources in urban soils included leaded petrol, coal combustion, smelting and possibly old pre-industrial ore processing, whereas leaded petrol and pre-industrial lead were the only possible anthropogenic sources in non-urban soils. The comparison of Wrocöaw soils with those from cities of comparable size Kraków and Poznań show similar ranges of metal contents with implication that urban pollution oversteps diverse geogenic chemical background. On the other hand, the comparison with other European cities show large variability in metal contents and suggest that urban soils contamination is time integrated and reflects long-term industrial evolution of each country. [ABSTRACT FROM AUTHOR]

Abstract Ore mining and processing in semi-arid areas is responsible for the generation of metal(loid)-containing dust, which is easily transported by wind to the surrounding environment. To assess the human exposure to dust-derived metal(loid)s (As, Cd, Cu, Pb, Sb, Zn), as well as the potential risks related to incidental dust ingestion, we studied mine tailing dust (n = 8), slag dust (n = 5) and smelter dust (n = 4) from old mining and smelting sites in northern Namibia (Kombat, Berg Aukas, Tsumeb). In vitro bioaccessibility testing using extraction in simulated gastric fluid (SGF) was combined with determination of grain-size distributions, chemical and mineralogical characterizations and leaching tests conducted on original dust samples and separated PM 10 fractions. The bulk and bioaccessible concentrations of the metal(loid)s were ranked as follows: mine tailing dusts < slag dusts ≪ smelter dusts. Extremely high As and Pb bioaccessibilities in the smelter dusts were caused by the presence of highly soluble phases such as arsenolite (As 2 O 3) and various metal-arsenates unstable under the acidic conditions of SGF. The exposure estimates calculated for an adult person of 70 kg at a dust ingestion rate of 50 mg/day indicated that As, Pb (and also Cd to a lesser extent) grossly exceeded tolerable daily intake limits for these contaminants in the case of slag and smelter dusts. The high risk for smelter dusts has been acknowledged, and the safety measures currently adopted by the smelter operator in Tsumeb are necessary to reduce the staff's exposure to contaminated dust. The exposure risk for the local population is only important at the unfenced disposal sites at Berg Aukas, where the PM 10 exhibited high levels of bioaccessible Pb. Graphical abstract Unlabelled Image Highlights • Large amounts of dust in old mining sites in semi-arid areas of northern Namibia • Multi-method dust characterization for elucidation of metal(loid) binding/release • Metal(loid) bioaccessibility increase for mine tailings < slags ≪ smelter dusts • Highest risks of As, Pb (and Cd) intake for smelter-derived dusts [ABSTRACT FROM AUTHOR]

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 ≪ 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. [Display omitted] • Dust generated during mining and processing of non-sulfide Zn ores in an arid area. • High levels of bioaccessible metals in fine dust fractions (<48 μm and <10 μm). • Low intake risk for metals in dust local ores, tailings, and soils. • High Pb and Cd intake from imported ores used for blending before hydrometallurgy. [ABSTRACT FROM AUTHOR]

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. [Display omitted] • Silver isotopes are applicable for anthropogenic Ag source/load tracing. • Silver isotopes have a potential to trace variations in anthropogenic phases. • Silver of metallurgical origin is geochemically stable in soils. [ABSTRACT FROM AUTHOR]

We studied arid desert soils from Namibia (Rosh Pinah) that were contaminated with up to 7 mg kg −1 of thallium (Tl) via dust emitted from a local flotation tailing dam. Chemical extractions of waste and soil materials indicated that most of the Tl is strongly bound, in accordance with X-ray diffraction and X-ray absorption spectroscopy data that point to the predominant association of Tl with metal sulfides and phyllosilicates. The isotope fractionation factor ε 205 Tl of the soil samples (from −0.4 to +3.8) shows a positive linear relationship (R 2  = 0.62) with 1/Tl, indicative for the mixing of two major Tl pools, presumably anthropogenic Tl and geogenic Tl. The ε 205 Tl value for the topmost soil samples (∼+3) closely matches the ε 205 Tl value for post-flotation waste particles with a diameter of <0.05 mm, whereas the bulk flotation waste exhibits a significantly larger ε 205 Tl value (∼+6). These variations are in accordance with predominant atmospheric transfer of Tl from the tailings to the adjacent soils via fine (dust) particles. The identified minimal Tl alteration in soils indicates that only a small part of the Tl could be potentially released and passively enter the vegetation, local population and/or food chain in the long term. From this viewpoint, Tl does not represent such an important environmental concern as other (abundant) contaminants at the locality. Furthermore, there could be a relevance for other alkaline desert soils, including those where Tl pollution plays a major role. [ABSTRACT FROM AUTHOR]

Dust emissions from copper smelters processing arsenic-bearing ores represent a risk to soil environments due to the high levels of As and other inorganic contaminants. Using an in situ experiment in four different forest and grassland soils (pH 3.2–8.0) we studied the transformation of As-rich (>50 wt% As) copper smelter dust over 24 months. Double polyamide bags with 1 g of flue dust were buried at different depths in soil pits and in 6-month intervals; then those bags, surrounding soil columns, and soil pore waters were collected and analysed. Dust dissolution was relatively fast during the first 6 months (5-34%), and mass losses attained 52% after 24 months. The key driving forces affecting dust dissolution were not only pH, but also the water percolation/retention in individual soils. Primary arsenolite (As 2 O 3 ) dissolution was responsible for high As release from the dust (to 72%) and substantial increase of As in the soil (to a 56 × increase; to 1500 mg kg −1 ). Despite high arsenolite solubility, this phase persisted in the dust after 2 years of exposure. Mineralogical investigation indicated that mimetite [Pb 5 (AsO 4 ) 3 (Cl,OH)], unidentified complex Ca-Pb-Fe-Zn arsenates, and Fe oxyhydroxides partly controlled the mobility of As and other metal(loid)s. Compared to As, other less abundant contaminants (Bi, Cu, Pb, Sb, Zn) were released into the soil to a lesser extent (8-40% of total). The relatively high mobility of As in the soil can be seen from decreases of bulk As concentrations after spring snowmelt, high water-extractable fractions with up to ∼50% of As(III) in extracts, and high As concentrations in soil pore waters. Results indicate that efficient controls of emissions from copper smelters and flue dust disposal sites are needed to prevent extensive contamination of nearby soils by persistent As. [ABSTRACT FROM AUTHOR]

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. [Display omitted] • Prolonged (168 days) tank leaching test performed on monolithic Cu slags. • Initial diffusion-controlled release of Cu and Co, followed by dissolution. • Copper (but not Co) partly controlled by sorption to secondary lepidocrocite and goethite. • Cumulative releases (in mg/m2) useful for the long-term prediction of metal (loid) leaching. [ABSTRACT FROM AUTHOR]

Metallurgical slags enriched in Ga (144–156 mg/kg) and Ge (285–441 mg/kg) were investigated as potential sources of these technologically critical elements. Conventional mineralogical techniques (SEM/EDS, EPMA) were coupled with automated mineralogy using a Tescan Integrated Mineral Analyzer (TIMA) to quantitatively determine the partitioning of Ga and Ge in the slags. Both elements are primarily bound in the slag glass (90.5–95.4% of Ga and 95.9–96.7% of Ge). Extraction experiments conducted in 0.5 M H 2 SO 4 , 1 M HNO 3 , and 1 M HCl were used to simulate the hydrometallurgical recovery in view of the potential recovery of Ga and Ge. The leaching of Ga and Ge (and other valuable metals: Zn, Pb) was investigated as a function of time (2–12 h), temperature (25 and 70 °C), and particle size (original granulated slag and ultrafine-milled slag). Compared to other treatments, the highest Ga and Ge extractability was found in 0.5 M H 2 SO 4. No significant effect of the particle size, temperature, and time was observed on the Ga and Ge leaching. The optimum conditions for the extraction were: sulfuric acid treatment, original granulated slag (to limit the additional cost of crushing/milling), 25 °C, and at least 6 h of extraction. Despite the high extractabilities of Ga and Ge, more tests are needed to validate the economic feasibility of their full-scale recovery, especially due to the highly fluctuating prices of these elements on the global market. [Display omitted] • Ga- and Ge-rich metallurgical slags as potential sources of these critical elements. • Automated mineralogy: Ga and Ge mostly bound in the slag glass (90.5–96.7%). • The highest Ga and Ge extractability in H 2 SO 4 treatment as compared to other acids. • No significant effect of particle size and temperature on the Ga/Ge leaching. • More tests needed to validate the economic viability of the Ga and Ge recovery. [ABSTRACT FROM AUTHOR]

The laterite nickel (Ni) ore smelting operation in Niquelândia (Goiás state, Brazil) produced large amounts of smelting wastes, stockpiled on dumps (slags) and in settling ponds (fly ash). In this study we present data on the chemistry, mineralogy and pH-dependent leaching behaviours of these two waste materials. Bulk chemical analyses indicated that both wastes contained significant amounts of potentially toxic elements (PTEs), with substantially higher concentrations in the case of the fly ash (up to 2.51 wt% Ni, 1870 mg/kg Cr and 488 mg/kg Co). The mineralogical investigations carried out using X-ray diffraction analysis (XRD), scanning electron microscopy (SEM) and electron microprobe (EPMA) indicated that the slag was mainly composed of silicate glass, olivine and pyroxene. In contrast, the fly ash was composed of Ni-bearing serpentine-like phases (originating from the furnace feed), Ni-bearing glass, olivine, pyroxene and spinel. The pH-dependent leaching behaviour was performed according the EU standard experimental protocol (CEN/TS 14997) in the pH range of 3–12. The leaching was highly pH-dependent for both materials, and the highest releases of PTEs occurred at pH 3. The slag generally exhibited an U-shaped leaching behaviour of the PTEs as a function of pH, and was found to release up to 48.0 mg/kg Ni, 25.6 mg/kg Cr, and 1.42 mg/kg Co. The fly ash was significantly more reactive, and exhibited its highest leaching level of PTEs between pH 3 and 7. The maximum observed release corresponded to 5750 mg/kg Ni, 4.35 mg/kg Cr, and 112 mg/kg Co. The leached Ni concentrations after 24 h of leaching in deionized water exceeded the limit for hazardous waste by more than 100x according to the EU legislation (40 mg/kg Ni). X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structures (EXAFS) spectra indicated that Ni in the fly ash is predominantly bound in a serpentine-like phase, and during the fly ash experimental alteration it was mainly released from the second shell (corresponding to the atomic distances between Ni and Si, Mg, Fe in high-temperature silicates, glass, and partially dissolved serpentine). This study shows that disposal sites for the fly ash can represent a significant source of local pollution, and direct recycling of the fly ash in the smelting technology (as currently adopted at the Barro Alto new smelter and since few years also at the Niquelândia smelter) is the best environment-friendly option for handling of fly ash in the future. [ABSTRACT FROM AUTHOR]

This review summarizes over 160 studies focused on soil contamination near non-ferrous metal smelters. The methods of these investigations were examined with an emphasis on the combinations of traditional (geo)chemical approaches with various mineralogical and metal isotope techniques that are particularly helpful for depicting the fate of smelter-derived contamination in the soil. Differences in the distributions and binding of metal(loid)s in smelter-affected soils from temperate and (sub)tropical climatic zones indicate the greater vulnerability of the latter. Prevailing wind direction is a key factor affecting the dispersion of smelter emissions and their subsequent deposition into the soils, with greater importance found especially in arid areas. Whereas the greatest contamination is generally observed in the surface soil layers, downward migration of metal(loid)s in the soil profiles has been documented at numerous sites. Contamination of smelter soils significantly affects both plants and soil organisms, but suitable remediation techniques (such as chemical stabilization of soils by amendments) can be used for reducing the bioavailability of contaminants. [ABSTRACT FROM AUTHOR]

Tropical soils from the vicinity of the Mufulira copper smelter (Zambian Copperbelt) were found to contain high levels of metals, particularly in the upper parts of soil horizons. Metal concentrations varied within the ranges: 37–8980 mg Cu/kg, 3–46 mg Co/kg, < 2.5–42 mg Pb/kg, and 16–83 mg Zn/kg. The EDTA extractions indicated that a considerable percentage of the metals were bound in the “labile” fractions of the soil (up to 55% of total Cu concentration, 36% Co, 41% Pb, 30% Zn). The mineralogical investigation of the heavy mineral fraction of the most contaminated soil showed that the Cu is mainly present as Cu-(Fe) sulphides (chalcocite, chalcopyrite), metallic Cu, complex Cu-(Fe) oxides, and Cu-bearing sulphates. To determine the toxicity of these soils, we adopted a standardized OECD reproduction test using Enchytraeus crypticus . The number of reproduced enchytraeids correlated negatively with total Cu and Co concentrations ( r = − 0.97 and − 0.94 at p < 0.001, respectively), and EDTA-extractable Cu ( r = − 0.89, p < 0.001); whereas no effects of the soil properties (pH, CEC, C org ) were observed. No reproduction was possible in soils with Cu levels > 5000 mg/kg. Median effect concentration (EC50) was calculated for total Cu concentration, and corresponded to 351 mg/kg. [ABSTRACT FROM AUTHOR]

Kinetic batch leaching of the flotation wastes from Berg Aukas and Kombat mining districts (northern Namibia) in 500 μM solutions of citric, oxalic and acetic acids was performed to simulate the release of trace metals and As in the rhizosphere-like environment. The obtained data demonstrate that citric acid may significantly contribute to mineral waste alteration accompanied by contaminant mobilization; the maximum dissolution rates corresponded to 7% (Cu), 3% (As), 2% (Cd), 0.8% (Pb) and 0.3% (Zn) of their total amounts. In contrast, the role of oxalic and acetic acids in the complex process of contaminant leaching was usually negligible and/or comparable with water. The precipitation of newly formed Fe (hydr)oxides followed by the adsorption of Pb, Cd and eventually Zn from the model solutions seems to be the key mechanism which led to the metals' stabilization, as predicted by speciation modeling. Considering the neutral and slightly alkaline (and lowly organic) character of soils around the investigated flotation waste dams, Cu and As, present as neutral or anionic species, are suggested to be contaminants with the highest potential for rhizospheric mobilization and subsequent vertical mobility in local soils and/or transfer to plants. [ABSTRACT FROM AUTHOR]