Understanding stable Tl isotopes in industrial processes and the environment: A review.

In this review, a compilation of the current knowledge on stable thallium (Tl) isotopes (205Tl and 203Tl) in specific industrial processes, soils and plants is presented. An overview of the processes that may control Tl concentration and Tl isotope fractionation is compiled, while also overviewing the ability of Tl isotopic ratios to be used as a 'fingerprint' in source apportionment. Thallium isotopic compositions not only depend on their origin, but also on soil processes that may occur over time. One of the most important phases affecting the fractionation of stable Tl isotopes in soils (or sediments) was systematically identified to be specific Mn(III,IV)-oxides (mainly birnessite), due to their potential ability of oxidative Tl sorption, i.e., indicative of redox Tl reactions to be critical controlling factor. It has been established that the Brassica family is a hyperaccumulator of Tl, with clear demonstrations of Tl isotopic fractionation occurring up the translocation pathway. A clear pattern, so far, was observed with Tl isotopic compositions in plants grown on soils that were contaminated and those grown on uncontaminated soils, indicating the importance of the growing medium on Tl uptake, translocation, and isotopic fractionation.

Higher Tl bioaccessibility in white mustard (hyper-accumulator) grown under the soil than hydroponic conditions: A key factor for the phytoextraction use.

The paper deals with the thallium (Tl) access into the white mustard (Sinapis alba L.). We were comparing two approaches: A - hydroponic, B - semi-hydroponic (artificial soil). The kinetics of Tl plant uptake at different available Tl doses (0.1, 0.05 and 0.01 mg L-1) was tested. It was revealed that the hydroponic arrangement did not accelerate the plant uptake of Tl. The concentration of plant Tl was surprisingly roughly double under the semi-hydroponic (artificial soil) conditions as compared to the hydroponic system; the highest Tl concentrations were detected in stems, proving an important role of plant grown strategy on Tl bioaccessibility. We found that almost independently of the initial dose of Tl the juvenile stadium of the mustard can preserve1-2% of the total Tl pool. Up to 95% of this Tl dose is stored in the shoots. The different strategy of the plant growing may strongly affect the path of Tl incorporation. The total Tl input into the leaf tissue in hydroponics may be from 69% (p = 0.01) explained by parallel assimilation of Ca. In contrast, the Tl entry into the leaf grown on the artificial soil could be limited by Mn path (R2 = 0.91, p = 0.01).

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.

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.

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.

High geogenic soil thallium shows limited impact on bacterial community.

Thallium (Tl) is a highly toxic trace metal, included in the US EPA list of priority pollutants. Even though its toxicity is potentially higher or comparable to Cd or Hg, its environmental impact is largely unknown. Despite its toxicity, only a few recent studies are mapping the impact of recently introduced Tl on soil microbial communities, namely in agricultural systems but no studies focus on its long term effect. To complement the understanding of the impact of Tl on soil, this study aims to describe the influence of extremely high naturally occurring Tl concentration (50 mg/kg of potentially bioavailable Tl) on soil microbial communities. Our investigation concentrated on samples collected at Buus (Erzmatt, Swiss Jura, Switzerland), encompassing forest and meadow soil profiles of the local soil formed on hydrothermally mineralized dolomite rock, which is naturally rich in Tl. The soil profiles showed a significant proportion of potentially bioavailable Tl. Yet, even this high concentration of Tl has a limited impact on the richness of the soil bacterial community. Only the meadow soil samples show a reduced richness compared to control samples. Furthermore, our analysis of geogenic Tl contamination in the region unveiled a surprising finding: compared to other soils of Switzerland and in stark contrast to soils affected by recent mining activities, the structure of the bacterial community in Buus remained relatively unaffected. This observation highlights the unique ability of soil microbial communities to withstand extreme Tl contamination. Our study advances the understanding of Tl's environmental impact and underscores the resilience of soil microbes in the face of severe long-term contamination.

Thallium in Technosols from Allchar (North Macedonia): Isotopic and speciation insights.

Allchar (North Macedonia) mining area is known for anomalous background Tl concentrations. In this study, we combine accurate detection of Tl stable isotope ratios with data on mineralogy/speciation and chemical extraction of Tl in Tl-contaminated Technosol profiles. We demonstrate that Tl in the studied soils varies significantly in both concentration (500 mg/kg-18 g/kg) and isotopic composition (-1.6 and +3.2 of ε205Tl, a ∼0.5‰ spread), which is due to changes in the phase chemistry and/or mineralogy of Tl. Moreover, the observed 205Tl/203Tl ratios do not reflect the extent to which individual soils undergo Tl isotopic fractionation during mineral weathering and soil formation. Clearly, they reflect the initial isotopic signal(s) of the primary ore or ore minerals, and thus, the general history or type of their genesis. As the Tl carriers, various types of Tl-Me-arsenates, mixtures of jarosite and dorallcharite and minor Mn-oxides predominated. We revealed intense adsorption of Tl by the identified Mn-oxides (≤6.7 at.%). It is hypothesized that these phases are of key importance in the fractionation of Tl isotopes, meaning at this type of secondary oxide-soil solution interface. However, model studies involving primary/secondary components (sulfides, sulfates, oxides and arsenates) are required to understand the mechanisms that may lead to post-depositional Tl isotopic redistribution in soils, as well as Tl isotope systematics in mining wastes in general.

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.

Sorption of tebuconazole onto selected soil minerals and humic acids.

The aim of the present study was to investigate tebuconazole sorption on common soil minerals (birnessite, ferrihydrite, goethite, calcite and illite) and humic acids (representing soil organic matter). Tebuconazole was used (i) in the commercial form Horizon 250 EW and (ii) as an analytical grade pure chemical. In the experiment with the commercially available tebuconazole, a significant pH-dependent sorption onto the oxides was observed (decreasing sorption with increasing pH). The highest sorption was found for ferrihydrite due to its high specific surface area, followed by humic acids, birnessite, goethite and illite. No detectable sorption was found for calcite. The sorption of analytical grade tebuconazole on all selected minerals was significantly lower compared to the commercial product. The sorption was the highest for humic acids, followed by ferrihydrite and illite and almost negligible for goethite and birnessite without any pH dependence. Again, no sorption was observed for calcite. The differences in sorption of the commercially available and analytical grade tebuconazole can be attributed to the additives (e.g., solvents) present in the commercial product. This work proved the importance of soil mineralogy and composition of the commercially available pesticides on the behavior of tebuconazole in soils.

Geochemical position of Pb, Zn and Cd in soils near the Olkusz mine/smelter, South Poland: effects of land use, type of contamination and distance from pollution source.

The soils adjacent to an area of historical mining, ore processing and smelting activities reflects the historical background and a mixing of recent contamination sources. The main anthropogenic sources of metals can be connected with historical and recent mine wastes, direct atmospheric deposition from mining and smelting processes and dust particles originating from open tailings ponds. Contaminated agriculture and forest soil samples with mining and smelting related pollutants were collected at different distances from the source of emission in the Pb-Zn-Ag mining area near Olkusz, Upper Silesia to (a) compare the chemical speciation of metals in agriculture and forest soils situated at the same distance from the point source of pollution (paired sampling design), (b) to evaluate the relationship between the distance from the polluter and the retention of the metals in the soil, (c) to describe mineralogy transformation of anthropogenic soil particles in the soils, and (d) to assess the effect of deposited fly ash vs. dumped mining/smelting waste on the mobility and bioavailability of metals in the soil. Forest soils are much more affected with smelting processes than agriculture soils. However, agriculture soils suffer from the downward metal migration more than the forest soils. The maximum concentrations of Pb, Zn, and Cd were detected in a forest soil profile near the smelter and reached about 25 g kg(- 1), 20 g kg(- 1) and 200 mg kg(- 1) for Pb, Zn and Cd, respectively. The metal pollutants from smelting processes are less stable under slightly alkaline soil pH then acidic due to the metal carbonates precipitation. Metal mobility ranges in the studied forest soils are as follows: Pb > Zn ≈ Cd for relatively circum-neutral soil pH (near the smelter), Cd > Zn > Pb for acidic soils (further from the smelter). Under relatively comparable pH conditions, the main soil properties influencing metal migration are total organic carbon and cation exchange capacity. The mobilization of Pb, Zn and Cd in soils depends on the persistence of the metal-containing particles in the atmosphere; the longer the time, the more abundant the stable forms. The dumped mining/smelting waste is less risk of easily mobilizable metal forms, however, downward metal migration especially due to the periodical leaching of the waste was observed.

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.

Evolution of bioavailable copper and major soil cations in contaminated soils treated with ethylenediaminedisuccinate: a two-year experiment.

This study evaluates the long-term behavior of metals in soils treated with ethylenediaminedisuccinate for remediation purposes. The addition of the chelant led to a significant increase of water-extractable copper, iron, aluminum contents and their uptake by poplar. Increased concentrations of the metals were present in the soil solution even after the 2 years of the experiment (up to a 30-, 170- and 270-fold increase for copper, iron and aluminum, respectively). Therefore, soils treated with chelants must be monitored not only for the targeted metal concentrations but also for major soil cations originating from chelant-induced dissolution of soil oxides.

Arsenic fractionation and mobility in sulfidic wetland soils during experimental drying.

In this study, two Czech wetland soils enriched in authigenic sulfide minerals (especially realgar) were collected from the saturated zone (60-100 cm), flooded with local groundwater and allowed to dry for up to 98 days. The objective was to examine the mobility of As, Fe, S and trace metals using selective chemical extractions, S isotopes and X-ray diffraction through the drying process. During the initial stage of incubation (∼20 days), the re-flooding of the soils triggered a microbially-mediated SO42- reduction, which immobilized the Co, Cu and Ni. The reductive dissolution of As-bearing Fe (oxyhydr)oxides and the release of As were documented only in the Fe-rich/organic-low soil. Over the next stage of incubation (∼75 days), the exposure and drying of the soils led to the oxidation of the Fe and As sulfides. The arsenic and trace metals released via oxidation of the sulfide phases (particularly Fe sulfides) were almost entirely sequestered by the Fe(III) (oxyhydr)oxides, but acidification during the oxidation stage of the incubation resulted in the pH-dependent release of the As and trace metals (Co, Cu, Ni) (especially in the Fe-rich/organic-low soil). These findings suggest that sulfidic soils in wetlands can be considered as long-term sources of As during major drought events.

Thallium and lead variations in a contaminated peatland: A combined isotopic study from a mining/smelting area.

Vertical profiles of Tl, Pb and Zn concentrations and Tl and Pb isotopic ratios in a contaminated peatland/fen (Wolbrom, Poland) were studied to address questions regarding (i) potential long-term immobility of Tl in a peat profile, and (ii) a possible link in Tl isotopic signatures between a Tl source and a peat sample. Both prerequisites are required for using peatlands as archives of atmospheric Tl deposition and Tl isotopic ratios as a source proxy. We demonstrate that Tl is an immobile element in peat with a conservative pattern synonymous to that of Pb, and in contrast to Zn. However, the peat Tl record was more affected by geogenic source(s), as inferred from the calculated element enrichments. The finding further implies that Tl was largely absent from the pre-industrial emissions (>~250 years BP). The measured variations in Tl isotopic ratios in respective peat samples suggest a consistency with anthropogenic Tl (ε205Tl between ~ -3 and -4), as well as with background Tl isotopic values in the study area (ε205Tl between ~0 and -1), in line with detected 206Pb/207Pb ratios (1.16-1.19). Therefore, we propose that peatlands can be used for monitoring trends in Tl deposition and that Tl isotopic ratios can serve to distinguish its origin(s). However, given that the studied fen has a particularly complicated geochemistry (attributed to significant environmental changes in its history), it seems that ombrotrophic peatlands could be better suited for this type of Tl research.

Slag dusts from Kabwe (Zambia): Contaminant mineralogy and oral bioaccessibility.

The former Pb-Zn mining town of Kabwe in central Zambia is ranked amongst the worst polluted areas both in Africa and in the world. The fine dust particles from the ISF and Waelz slags deposited in Kabwe represent a health risk for the local population. Here, we combined a detailed multi-method mineralogical investigation with oral bioaccessibility testing in simulated gastric fluid (SGF; 0.4 M glycine, pH 1.5, L/S ratio of 100, 1 h, 37 °C) to evaluate the risk related to the incidental dust ingestion. The slag dust fractions contain up to 2610 mg/kg V, 6.3 wt% Pb and 19 wt% Zn. The metals are mainly bound in a slag glass and secondary phases, which formed during the slag weathering or were windblown from nearby tailing stockpiles (carbonates, Fe and Mn oxides, phosphates, vanadates). The bioaccessible fractions (BAFs) are rather high for all the main contaminants, with the BAF values generally higher for the ISF slags than for the Waelz slags: Pb (24-96%), V (21-100%) and Zn (54-81%). The results clearly indicate the potential risks related to the incidental slag dust ingestion. Even when a conservative value of the dust daily intake (100 mg/day) is considered, the daily contaminant intake significantly exceeds the tolerable daily intake limits, especially for Pb â‰« V > Zn. At higher ingestion rates, other minor contaminants (As, Cd) also become a health risk, especially for children. The slag heaps in Kabwe should be fenced to prevent local people entering and should be covered to limit the dust dispersion.

Thallium isotopic fractionation in soil: the key controls.

We studied the key geochemical and mineralogical factors that could affect the fractionation of stable thallium (Tl) isotopes in soil. A set of grassland soil samples enriched in geogenic Tl in combination with selected Tl-containing mineral materials from the Czech Republic (Kluky) were investigated for this purpose. The results demonstrate significant incorporation of Tl in pedogenic (specific) Mn-oxide, which led to a large accumulation of the heavy 205Tl isotope (∼+14 ε205Tl units), presumably resulting from oxidative Tl sorption. Consequently, we concluded that the Mn-oxide-controlled Tl uptake is the primary cause of the observed 205Tl enrichment in the middle profile zone, at the A/B soil horizon interface, with up to +4 of ε205Tl. Furthermore, our results displayed a clear relationship between the Tl isotopic fractionation degree and the Mn-oxide soil concentration (R2 = 0.6), as derived from the oxalate-extractable data. A combination of soil and mineralogical considerations suggests that 205Tl enrichment in respective soil samples is also partly due to the Tl present in micaceous clay minerals, mainly illite, which is the predominant pedogenic Tl host phase. In line with our previous results, this Tl behavior can be inferred from systematic Mn-oxide degradation and the associated Tl (enriched in 205Tl) cycling in the studied soils and thus, presumably in the redoximorphic soils in general.