High Concentrations Of Sb Research Articles

Infrared study of the layered magnetic insulator Mn(Bi0.07Sb0.93)2Te4 at low temperatures

Topological insulators with intrinsic magnetic ordering, potentially hosting rare quantum effects, recently attracted extensive attention. MnBi$_2$Te$_4$ is the first established example. The Sb-doped variant Mn(Bi$_{1-x}$Sb$_x$)$_2$Te$_4$ shows a great variety of electronic properties depending on the Sb content~$x$, such as shifts in the Fermi level and the Neel temperature $T_{\mathrm N}$, and the change of the free charge carrier type from $n$- to $p$-type at high Sb substitution ratios. Here, we investigate the effect of magnetic ordering on the bulk electronic structure of Mn(Bi$_{1-x}$Sb$_x$)$_2$Te$_4$ with high Sb content $x=0.93$ by temperature-dependent reflectivity measurements over a broad frequency range. We observe anomalies in the optical response across $T_{\mathrm N}$ when the antiferromagnetic order sets, which suggests a coupling between the magnetic ordering and the electronic structure of the material.

Gold and aurostibite from the metaturbidite-hosted Au–Zn–Pb–Ag Hera deposit, southern Cobar Basin, central NSW, Australia: geochemical and textural evidence for gold remobilisation

AbstractThe Devonian Hera metaturbidite-hosted polymetallic Au–Zn–Pb–Ag deposit of central NSW, Australia, contained a total undepleted resource of 3.6 Mt @ 3.3 g/t Au, 25 g/t Ag, 2.6% Pb and 3.8% Zn. The deposit comprises a number of distinctive lodes with each containing a distinctive ore and alteration/gangue mineralogy, though generally the sulfide ore comprises various mixtures of sphalerite, galena, chalcopyrite, pyrrhotite and relatively common visible gold–electrum. The North Pod and Far West lodes are distinctly Sb rich and contain a more diverse ore mineralogy with arsenopyrite, native silver, native antimony, gudmundite, tetrahedrite-(Fe), argentotetrahedrite-(Fe), acanthite, dyscrasite, nisbite and breithauptite. From analysis of 52,760 assays from across the deposit it was found that there was a very poor correlation between gold and each of Fe, Zn, S, Pb, Cu, As and Ag, whereas Ag correlated reasonably well with both Pb and Zn. Results from EPMA shows that gold varies widely in composition from host-rock associated gold (96 wt.% Au) through more intermediate compositions (88–73 wt.% Au) to electrum (46–27 wt.% Au), commonly associated with Sb-phases and containing significant Sb within the gold itself (1.05–2.58 wt.% Sb). From the Far West lense, aurostibite occurs as distinctive rims around gold. Although aurostibite associated with gold contains no silver, the gold itself contains constant moderate amounts (10.87–12.27 wt.% Ag). We suggest that the aurostibite and other Sb phases formed from a late-stage Sb-rich hydrothermal during low-temperature retrograde skarn alteration. There is abundant evidence for both chemical and physical remobilisation at Hera and this remobilisation is largely responsible for the spectrum of gold compositions observed. The source for these fluids may be an underlying magmatic body, evidence for which occurs as granite pegmatite dykes in various locations throughout the deposit. Furthermore, gold with a moderate to high Sb content may be indicative of a low temperature of formation.

Hydrogeochemical characteristics, sources and human health risk assessment of heavy metal dispersion in the mine pit water–surface water–groundwater system in the largest manganese mine in Ghana

This study was conducted to appraise the hydrogeochemical characteristics and sources of heavy metals and the probable human health risks associated with the consumption of water contaminated with heavy metals in the mine pit water–surface water–groundwater system in the Nsuta manganese mining area in western Ghana. Therefore, a total of 29 samples were collected for hydrochemical analysis and the hydrochemical data was interpreted using multivariate statistical analysis. The results indicate that the pH of water in the mine pit water–surface water–groundwater system is slightly acidic to alkaline in nature. The groundwater evolved from Ca-Mg-SO4, Ca-Mg-HCO3-SO4, Ca-Mg-Na-Cl to Ca-Na-Cl-HCO3 water type with other mixed types, reflecting intense water–rock interaction and dissolution of rocks belonging to the Banded Manganese Formation and the Birimian metasediments in the area. The water is supersaturated with respect to goethite and hematite, pointing to precipitation and dissolution of these minerals. The Water Hazard Index values range from 0.20 to 30.5, implying minimal to extreme toxicity of the water. The mine pit water shows very high Fe, Mn, Ni, As and Sb concentrations, which resulted in hydromorphic dispersion of the heavy metals to the surface water and groundwater. The computed Hazard Index values show higher values (>1) in the surface water and mine pit water, and the carcinogenic risk is low in the groundwater, high in the surface water and extremely high in the mine pit water. Therefore, appropriate control and remedial measures should be urgently put in place to safeguard the health of the people.

Hydrochemical characteristics and health risk assessment of groundwater in karst areas of southwest China: A case study of Bama, Guangxi

The southwest karst area is considered to have the most vulnerable groundwater environment in China. Groundwater quality is an important factor restricting sustainable economic development. In this study, traditional water chemistry method, water quality index (WQI), and hazard index (HI) were applied to comparatively analyze the hydrochemical characteristics of groundwater and the water quality in the exposed karst region (EKR) and buried karst region (BKR) in Bama, a typical karst area in southwest China. Generally, the main water type was Ca/Mg–HCO3. Due to the predominance of dissolution of carbonate rocks in EKR and silicate rocks in BKR, higher total dissolved solids (TDS), Ca and HCO3− concentrations, and lower H2SiO3 content were detected in groundwater in EKR compared with BKR. As affected by weathering of rocks such as lead-zinc ore, the maximum concentrations of Zn and Sr were 11.23 mg/L and 13.30 mg/L, showing that mineral water resources are widely distributed in Bama. The ion ratios and isotope abundances (δD and δ18O) in groundwater samples indicated stronger evaporation and rock-water interaction in EKR than BKR. Human activities exerted a more significant influence on the water quality in EKR compared to BKR. The mean WQI value also suggested that the groundwater quality was better in BKR (9.56) than EKR (12.17). Although 95.7% of the water samples in the study area were classified as excellent based on their WQI values, 4.3% of the water samples still had significant health risks (HI > 1) due to the high Sb, Zn, As, and Sr concentrations. It is recommended to reduce anthropogenic pollution in EKR and develop a plan for clean production of mineral water industry according to local conditions, which will help the sustainable development of the local economy.

Environmental management and potential valorization of wastes generated in passive treatments of fertilizer industry effluents

A phosphogypsum stack located in SW Spain releases highly acidic and contaminated leachates to the surrounding estuarine environment. Column experiments, based on a mixture of an alkaline reagent (i.e., MgO or Ca(OH)2) dispersed in an inert matrix (dispersed alkaline substrate (DAS) technology), have shown high effectiveness for the treatment of phosphogypsum leachates. MgO-DAS and Ca(OH)2-DAS treatment systems achieved near total removal of PO4, F, Fe, Zn, Al, Cr, Cd, U, and As, with initial reactive mass:volume of leachate treated ratios of 3.98 g/L and 6.35 g/L, respectively. The precipitation of phosphate (i.e., brushite, cattiite, fluorapatite, struvite and Mn3Zn(PO4)2·2H2O) and sulfate (i.e., despujolsite and gypsum) minerals could control the solubility of contaminants during the treatments. Therefore, the hazardousness of these wastes must be accurately assessed in order to be properly managed, avoiding potential environmental impacts. For this purpose, two standardized leaching tests (EN-12457-2 from the European Union and TCLP from the United States) were performed. According to European Union (EN-12457-2) regulation, some wastes recovered from DAS treatments should be classified as hazardous wastes because of the high concentrations of SO4 or Sb that are leached. However, according to United States (US EPA-TCLP) legislation, all DAS wastes are designated as non-hazardous wastes. Moreover, the solids generated in the DAS systems could constitute a promising secondary source of calcite and/or P. This research could contribute to worldwide suitable waste management for the fertilizer industry.

Different responses of bacteria and fungi to environmental variables and corresponding community assembly in Sb-contaminated soil

Bacterial communities in antimony (Sb) polluted soils have been well addressed, whereas the important players fungal communities are far less studied to date. Here, we report different responses of bacterial and fungal communities to Sb contamination and the ecological processes controlling their community assembly. Soil samples in the Xikuangshan mining area were collected and subjected to high through-put sequencing of 16S rRNA and ITS1 to investigate bacterial and fungal communities, respectively, along an Sb gradient. Sb speciation in the soil samples and other physicochemical parameters were analyzed as well. Bacterial communities were dominated by Deltaproteobacteria in the soil with highest Sb concentration, whereas Chloroflexi were dominant in the soil with lowest Sb concentration. Fungal communities in high-Sb soils were predominated by unclassified Fungi, whilst Leotiomycetes were dominant in low-Sb soil samples. Multivariate analysis indicated that Sb, pH and soil texture were the main drivers to strongly impact microbial communities. We further identified Sb-resistant microbial groups via correlation analysis. In total, 18 bacterial amplicon sequence variants (ASVs) were found to potentially involve in biogeochemical cycles such as Sb oxidation, sulfur oxidation or nitrate reduction, whereas 12 fungal ASVs were singled out for potential heavy metal resistance and plant growth promotion. Community assembly analysis revealed that variable selection contributed 100% to bacterial community assembly under acidic or high Sb concentration conditions, whereas homogeneous selection dominated fungal community assembly with a contribution over 78.9%. The community assembly of Sb-resistant microorganisms was mainly controlled by stochastic process. The results offer new insights into microbial ecology in Sb-contaminated soils, especially on the different responses of microbial communities under identical environmental stress and the different ecological processes underlining bacterial and fungal community assembly.

The Formation of Magmatic-Hydrothermal Features in Sn-Mineralized and Barren Tasmanian Intrusions, Southeast Australia: Insights from Quartz Textures, Trace Elements, and Microthermometry

Abstract Tasmania is the most important tin province in Australia, having been endowed with >0.65 Mt Sn. Some granitic intrusions in western Tasmania have distinctive tourmaline- and quartz-rich magmatic-hydrothermal features, whether they are mineralized (e.g., Heemskirk Granite) or barren (Pieman Heads Granite). The Devonian Heemskirk and Pieman Heads plutons crop out on the western coast of Tasmania and are characterized by similar mineralogical and geochemical compositions and ages. The magmatic-hydrothermal textural features include tourmaline patches, tourmaline orbicules, and tourmaline-muscovite veins, as well as miarolitic cavities and quartz-fluorite-sulfide veins in the Heemskirk Granite. Cathodoluminescence (CL) imaging, laser ablation-inductively coupled plasma-mass spectrometry, and microthermometric analyses of quartz have revealed the physicochemical evolution of the magmatic-hydrothermal fluids from which these tourmaline- and quartz-bearing assemblages precipitated. High Ti quartz (20–28 ppm) in tourmaline patches, orbicules, and cavities typically have homogeneous CL-bright intensity, whereas CL-dark fractures have cut and/or offset the CL-bright and -gray domains that characterize low Ti quartz (3.4–8.5 ppm) from the tourmaline veins. The earliest fluid inclusion assemblages in the quartz-tourmaline orbicules and cavities have a salinity range from 3 to 14 wt % NaCl equiv with intermediate density and were probably trapped at lithostatic pressures of 1.57 ± 0.2 kbar and temperatures of 550° to 570°C, suggesting a depth of 5.9 ± 0.8 km. Prolonged depressurization and cooling may have led to the evolution of a brine (~39 wt % NaCl equiv salinity) from the primary magmatic liquid, which formed halite-bearing hypersaline inclusions in the tourmaline orbicules. Continuous pressure decrease explains the intense brittle failure and fluid migration outward from the apical portions of the pluton, where magmatic fluids partially mixed with and were cooled by external meteoric water. These mechanisms triggered the formation of tourmaline-muscovite-quartz veins and local cassiterite-bearing greisens from a moderate-salinity fluid (~12 wt % NaCl equiv) at temperatures of ~300°C and hydrostatic pressures of 120 bars. Retrograde dissolution textures evident from CL-bright quartz cores surrounded by oscillatory growth zones with gray CL response characterize the low Ti (<1 ppm) and high Al (500–1,000 ppm) quartz from the fluorite-sulfide veins that precipitated from a low-salinity (5.7 wt % NaCl equiv) acidic fluid at temperatures of 200° ± 25°C and hydrostatic pressures of <50 bars. High Sb concentrations (up to 80 ppm) in quartz may be an indicator of low-temperature base metal mineralization related to granitic intrusions. Abundant fluid percolation, protracted fractional crystallization, and high tin concentrations in exsolved hydrothermal fluids may explain why the Heemskirk Granite is well endowed in Sn and base metal deposits, whereas the Pieman Heads Granite is barren.

Antimony distribution and mobility in different types of waste derived from the exploitation of stibnite ore deposits

Wastes derived from the exploitation of stibnite ore deposits were studied to determine their mineralogical, chemical, and environmental characteristics and establish the Sb distribution and the current and long-term risks of Sb mobilization. Representative samples of mine waste rocks, mine tailings, and smelting waste were studied by X-ray powder diffraction, polarized light microscopy, electron microprobe analysis, and digestion, leaching, and extraction procedures. The main Sb-bearing minerals and phases identified in the smelting waste were natrojarosite, iron (oxyhydr)oxides, mixtures of iron and antimony (oxyhydr)oxides, and tripuhyite; those in the mine tailings and mine waste rocks were iron (oxyhydr)oxides and/or mixtures of iron and antimony (oxyhydr)oxides. Iron (oxyhydr)oxides and natrojarosite had high Sb contents, with maximum values of 16.51 and 9.63 wt% Sb2O5, respectively. All three types of waste were characterized as toxic; the mine waste rocks and mine tailings would require pretreatment to decrease their leachable Sb content before they would be acceptable at hazardous waste landfills. Relatively little of the Sb was in desorbable forms, which accounted for <0.01 and <0.8% of the total Sb content in the smelting waste and mine waste rocks/mine tailings, respectively. Under reducing conditions, further Sb mobilization from mine waste rocks and mine tailings could occur (up to 4.6 and 3.3% of the total content, respectively), considerably increasing the risk that Sb will be introduced into the surroundings. Although the smelting waste had the highest total Sb content, it showed the lowest risk of Sb release under different environmental conditions. The significant Fe levels in the smelting waste facilitated the formation of various Fe compounds that greatly decreased the Sb mobilization from these wastes.

Efficiency and mechanisms of Sb(III/V) removal by Fe-modified biochars using X-ray absorption spectroscopy

Fe-modified biochars (FeBC) are effective antimony (Sb) removal materials; however, the removal mechanisms require further investigation. In this study, aqueous Sb(III) and Sb(V) removal by FeBC (300, 600, and 900 °C) was evaluated, with the adsorption mechanisms investigated using X-ray absorption spectroscopy (XAS). Screening results (based on removal efficiencies) using different types of FeBC indicated the 900 °C FeCl3-modified biochar (FeCl3BC900) achieved the best Sb(III/V) removal performance. The kinetics of the Sb(III/V) removal process were best fitted by a pseudo-second-order model. Additionally, the isothermal results were described by Langmuir and Redlich-Peterson models. Aqueous analysis and X-ray absorption near-edge structure data fitting indicated Sb(III) was oxidized to Sb(V) in the Sb(III)-spiked system, and the oxidation extent increased with increasing pyrolysis temperature. The oxidation process rapidly occurred in both the solution and biochar. No Sb(V) was reduced to Sb(III) in the Sb(V)-spiked system. The XAS results of the isothermal experiment indicated the oxidation capacity of FeCl3BC900 was limited for high initial Sb(III) concentrations. The Sb-Fe1 and Sb-Fe2 bonding distances were 3.05–3.10 and 3.47–3.54 Å, respectively, indicating inner-sphere complexes were formed during the Sb(III/V) removal processes. The Sb(III/V) removal mechanisms included electrostatic adsorption, inner-sphere complexes, and coprecipitation. Oxidation was also involved in Sb(III) removal.

Response of antimony and arsenic in karst aquifers and groundwater geochemistry to the influence of mine activities at the world’s largest antimony mine, central China

The elevated levels of antimony (Sb) and arsenic (As) in groundwater caused by mine activities is of particular global concern. Understanding pollution mechanism of Sb and As related to mine activities and their influence on karst groundwater geochemistry is of great significance. However, it is still unclear. To address such questions, Sb and As and major ions, δ34S and δ18O of dissolved sulfate as well as δD and δ18O of water were analyzed for groundwater sampled from three main karst aquifers at the Xikuangshan (XKS) antimony mine from 2013 to 2017. Spatial and temporal variations of Sb and As of the three main karst aquifers were characterized as that, (1) Sb concentrations, rather than As, varied with aquifers, with high Sb (1–50 mg/L) of the D3s2 and C1y3 aquifers and low Sb (0.01–1.0 mg/L) of the D3x4 aquifer; (2) As concentrations had significant seasonal effect that was higher in winter and lower in summer, whereas Sb concentrations did not differ seasonally. Here we applied a recently developed cluster analysis method as well as geochemical indicators to identify pollution types of Sb and As in groundwater related to complex mine activities, and further to reveal main effects on karst groundwater geochemistry. The cluster analysis yielded a classification of four clusters, which was confirmed by principal component analysis. The groundwater of cluster 3 is of weakly alkaline HCO3-Ca type with low Sb (<0.015 mg/L) and low As (<0.005 mg/L), which is typical karst groundwater controlled by limestone dissolution. Whereas the other three clusters with high concentrations of Sb and As were identified to represent three pollution patterns dominated by oxidative dissolution of stibnite, leaching of mine wastes, and mixed pollution, respectively. Moreover, the effects of long-term mine activities on karst groundwater geochemistry are revealed, including: (1) Hydrogeochemical compositions of groundwater changed from HCO3-Ca type to SO4-Ca type. (2) Sulfuric acid significantly participated in carbonate weathering. (3) Weathering of silicate (main as silicified limestone) by H2CO3 and H2SO4 was accelerated. (4) Cation-exchange was enhanced to dominate groundwater geochemistry. Another striking finding is that sulfur and oxygen isotopes of sulfate can effectively distinguish sulfate sources related to mine activities and to trace Sb sources in karst groundwater.

The effects of post-cumulus alteration on the distribution of chalcophile elements in magmatic sulfide deposits and implications for the formation of low-S-high-PGE zones: The Luanga deposit, Carajás Mineral Province, Brazil

ABSTRACT Most of the World's platinum-group element ore deposits occur as thin stratiform layers within layered intrusions. These layers generally contain disseminated base-metal sulfides or chromite. However, cryptic platinum-group element deposits also occur without chromite or base-metal sulfides in what are known as low-S-high platinum-group element deposits. The origin of these deposits is not clearly understood. The Luanga Complex hosts the largest platinum-group elements resource in South America (i.e., 142 Mt at 1.24 ppm Pt + Pd + Au and 0.11% Ni) and hosts both a platinum-group element deposit containing disseminated base-metal sulfides (style 1) and a low-S-high platinum-group element deposit (style 2). It therefore offers the opportunity to compare the two deposit types in the same overall geological setting and consider how the low-S-high platinum-group element deposit could have formed. The first deposit style is termed the Sulfide zone and consists of a 10–50 meter-thick interval with disseminated base metal sulfides, whereas the second style is named low-S-high-Pt-Pd zone and consists of 2–10 meter-thick discontinuous lenses of 1–5 meter-thick sulfide- and oxide-free harzburgite and orthopyroxenite with discrete platinum-group minerals. Secondary assemblages commonly replace primary igneous minerals to a variable extent throughout the deposit, and thus allow for investigating the effects of post-cumulus alteration on the distribution of a wide range of chalcophile elements in a magmatic sulfide deposit at both whole-rock and mineral scale. This study presents the whole-rock distribution of S, platinum-group elements, and Te, As, Bi, Sb, and Se in both mineralization styles and the concentration of trace elements in base-metal sulfides from the Sulfide zone. The Sulfide zone has Pt/Pd ratios around 0.5 and high concentrations of Te, As, Bi, Sb, and Se, whereas the low-S-high-platinum-group element zone has Pt/Pd ratios greater than 1 and much lower Se, Te, and Bi concentrations, but comparable As and Sb contents. This is reflected in the platinum-group element assemblage, comprising bismuthotellurides in the Sulfide zone and mostly arsenides and antimonides in the low-S, high platinum-group elements zone. Moreover, the base-metal sulfides from the Sulfide zone have anomalously high As contents (50–500 ppm), which suggest that the sulfide liquid segregated from a very As-rich silicate magma, possibly illustrated by an average komatiitic basalt that assimilated a mixture of upper continental crust and black shales. We interpret the low-S-high platinum-group elements zone as a product of S loss from magmatic sulfides during post-cumulus alteration of the Luanga Complex. Selenium, Te, Bi, and Pd were also lost together with S, whereas As and Sb were expelled from base-metal sulfide structures and combined with platinum-group elements to form platinum-group minerals, suggesting they may play a role fixating platinum-group elements during alteration. The remobilization of chalcophile elements from magmatic sulfide deposits located in the Carajás Mineral Province may represent a potential source for hydrothermal deposits found in the region.

Advancing thermoelectrics by vacancy engineering and band manipulation in Sb-doped SnTe–CdTe alloys

A decrease in valence band energy offset can considerably improve the thermoelectric performance of SnTe, and alloying CdTe in SnTe has been confirmed to be efficient for inducing band convergence. However, the low solubility of CdTe in SnTe severely limits the further decrease in the energy offset and the reduction of lattice thermal conductivity. Inspired by the high solubility of Sb in SnTe-based thermoelectric materials, the trivalent Sb is introduced into SnTe–CdTe alloys, aiming at manipulating the thermoelectric transport properties. Combined with the valence band model, it is demonstrated that high concentration of Sb in SnTe–CdTe enables a further optimization in valence band structures, resulting in an improvement in density-of-state effective mass, thus significantly reinforces the power factor in the whole temperature range. Meanwhile, we propose the solid solution mode of Sb in SnTe, which always generates vacancies to balance the valence state, and the introduction of vacancies explains the reduced lattice parameters and almost constant carrier concentration. Particularly, the Debye–Callaway model quantitatively compares the contribution of Sb substitutional defects and vacancy defects. As a result, an enhanced zT of ∼1.1 has been achieved for Sn0.83Cd0.05Sb0.12Te at 823 K. This work clearly shows the critical role of Sb for enhancing the thermoelectric performance of SnTe–CdTe materials.

Dopant Redistribution in High-Temperature-Grown Sb-Doped Ge Epitaxial Films

Heavily doped n-type Ge crystals are essential for Ge-based electronics and optical applications. In this report, we describe the mechanism of dopant redistribution via out-diffusion and re-evaporation processes in Sb-doped Ge epitaxial films grown by molecular beam epitaxy (MBE). The temperature-modulated depositions yielded a uniformly distributed and high Sb concentration (1019 to 1021 cm–3) on highly ordered crystalline Ge films. Here, the deposition temperatures (Td) control the transition of amorphous to epitaxial growth, as well as the Sb concentration profiles. A significant difference in the dopant levels is attributed to Sb out-diffusion that correlated with the diffusion parameters, followed by the re-evaporation from the Ge crystal in high-temperature conditions. Meanwhile, the substituted Sb atoms act as donors that form the n-type Ge film. This understanding of dopant behavior in the epitaxially grown Ge film opens a path to achieve well-defined n+-Ge thin films for Ge-based devices with improved electrical properties.

Microstructural Examinations of Copper Antimony Alloys

Abstract Among other materials, fahlores were used in the Bronze Age copper ore smelting process. These contain, apart from sulfur, arsenic and antimony. Therefore, these elements can be found in Bronze Age copper casting ingots or artifacts. In order to study the behavior of Sb more closely, two copper alloys containing 10 and 30 wt. % Sb were melted and subjected to a metallographic examination. On the one hand, microstructures with copper dendrites and homogeneous interdendritic areas primarily composed of intermetallic phase could be found. On the other hand, at higher Sb concentrations, first Cu3Sb precipitated which, in turn, transformed to Cu10Sb3 upon cooling. The crystals in these microstructures were characterized by numerous parallel cracks. No further phases were observed by XRD.

Characteristics of potentially toxic elements and multi-isotope signatures (Cu, Zn, Pb) in non-exhaust traffic emission sources

Non-exhaust emissions (e.g., particles from brake pads, asphalt, curb, road paint, tire) are important sources of potentially toxic elements (PTEs) pollution in urban environments and are potential causes of PTEs pollution in road dust. We present the PTEs concentrations (Cr, Ni, Cu, Zn, As, Cd, Sn, Sb, Pb) of non-exhaust emission sources and pollution degree of PTEs. Isotopic signatures of Cu, Zn, and Pb were also analyzed to distinguish these sources. Among PTEs, the Cu concentration in all brake pads was significantly high and brake pads from Korea showed remarkably high Sb concentrations. Asphalt had a higher Pb concentration than other non-exhaust emission sources. Mean of δ65CuAE647, δ66ZnIRMM3702, and 206Pb/207Pb values of non-exhaust emission sources in this study ranged from −0.49‰ to +0.19‰, −0.24‰ to +0.16‰, and 1.1535 to 1.4471, respectively. Non-exhaust emission sources could be discriminated by plotting the concentration and isotopic composition of Cu. Cu isotopic compositions (δ65CuAE647) were clearly distinguished between brake pads including domestic and imported products and tires. Zn isotope values (δ66ZnIRMM3702) of brake pads, tires, and asphalt overlapped, but discriminated from road paint and curb. Our results indicate that the combination of Cu and Zn isotopic signatures can distinguish various non-exhaust traffic emissions, especially brake pads and tires.

Antimony contamination and its risk management in complex environmental settings: A review

Antimony (Sb) is introduced into soils, sediments, and aquatic environments from various sources such as weathering of sulfide ores, leaching of mining wastes, and anthropogenic activities. High Sb concentrations are toxic to ecosystems and potentially to public health via the accumulation in food chain. Although Sb is poisonous and carcinogenic to humans, the exact mechanisms causing toxicity still remain unclear. Most studies concerning the remediation of soils and aquatic environments contaminated with Sb have evaluated various amendments that reduce Sb bioavailability and toxicity. However, there is no comprehensive review on the biogeochemistry and transformation of Sb related to its remediation. Therefore, the present review summarizes: (1) the sources of Sb and its geochemical distribution and speciation in soils and aquatic environments, (2) the biogeochemical processes that govern Sb mobilization, bioavailability, toxicity in soils and aquatic environments, and possible threats to human and ecosystem health, and (3) the approaches used to remediate Sb-contaminated soils and water and mitigate potential environmental and health risks. Knowledge gaps and future research needs also are discussed. The review presents up-to-date knowledge about the fate of Sb in soils and aquatic environments and contributes to an important insight into the environmental hazards of Sb. The findings from the review should help to develop innovative and appropriate technologies for controlling Sb bioavailability and toxicity and sustainably managing Sb-polluted soils and water, subsequently minimizing its environmental and human health risks.

Trace Element Geochemistry of Chalcopyrites and Pyrites from Golpu and Nambonga North Porphyry Cu-Au Deposits, Wafi-Golpu Mineral District, Papua New Guinea

Studying elemental geochemistry of hypogene sulphides can discriminate the hydrothermal fluids responsible for ore formation. To determine whether Golpu porphyry Cu-Au deposits are related to the Nambonga North porphyry system which is located 2.5 km apart in the Wafi-Golpu Mineral District, Papua New Guinea, we compare the trace element compositions of drill core chalcopyrites and pyrites analysed using Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICPMS). The results for the Golpu chalcopyrites revealed high concentrations of Au, As, Se, Mo, Sb, Te and Bi and lower concentrations of Ag and Zn compared to those from Nambonga. Pd and Pt were below the detection limit in chalcopyrites for both deposits. The results for the Golpu pyrites indicated high concentrations of Pt, Au, Se, Mo, Sb, and Te and lower concentrations of Cu, Zn, As, Ag, Pb, Pd and Bi compared to those from Nambonga North. Au concentrations in the pyrites from both the porphyry deposits were higher compared to chalcopyrites, which mean that pyrite is the Au-bearing sulphide responsible for the higher Au content. In contrast, Cu values in pyrites from Nambonga North are higher than those from Golpu. Overall, it is envisaged that the ore fluids were exsolved at different times during the evolution of both porphyry deposits, although these porphyry centres may be related in space and time.

Associations of exposure to cadmium, antimony, lead and their mixture with gestational thyroid homeostasis

Maintaining thyroid homeostasis during pregnancy is vital for fetal development. The few studies that have investigated associations between metal exposure and gestational thyroid function have yielded mixed findings. To evaluate the association of exposure to a mixture of toxic metals with thyroid parameters in 824 pregnant women from the Rhea birth cohort in Crete, Greece. Concentrations of three toxic metals [cadmium (Cd), antimony (Sb), lead (Pb)] and iodine were measured in urine using inductively coupled plasma mass spectrometry and thyroid hormones [Thyroid Stimulating Hormone (TSH), free thyroxine (fT4), and free triiodothyronine (fT3)] were measured in serum in early pregnancy. Associations of individual metals with thyroid parameters were assessed using adjusted regression models, while associations of the metal mixture with thyroid parameters were assessed using Bayesian Kernel Machine Regression (BKMR).Women with high (3rd tertile) concentrations of urinary Cd, Sb and Pb, respectively, had 13.3 % (95%CI: 2.0 %, 23.2 %), 12.5 % (95%CI: 1.8 %, 22.0 %) and 16.0 % (95%CI: 5.7 %, 25.2 %) lower TSH compared to women with low concentrations (2nd and 1st tertile). In addition, women with high urinary Cd had 2.2 % (95%CI: 0.0 %, 4.4 %) higher fT4 and 4.0 % (95%CI: −0.1 %, 8.1 %) higher fT3 levels, and women with high urinary Pb had 4 % (95%CI: 0.2 %, 8.0 %) higher fT3 levels compared to women with low exposure. The negative association of Cd with TSH persisted only when iodine sufficiency was unfavorable. BKMR attested that simultaneous exposure to toxic metals was associated with decreased TSH and increased fT3 and revealed a potential synergistic interaction of Cd and Pb in association with TSH. The present results suggest that exposure to toxic metals even at low levels can alter gestational thyroid homeostasis.

Trace elements in pyrite and pyrrhotite in the Pitangui Orogenic Au deposit, Pitangui greenstone belt, São Francisco Craton: Implications for the ore-forming fluids and metal sources

Orogenic Au deposits represent one of the largest sources of gold in the world and in Brazil, particularly at the Quadrilátero Ferrífero, southeastern portion of the São Francisco Craton. In the last decades, advances in in-situ analytical techniques allowed a detailed investigation of the chemistry of sulfides. This can reveal information about the origin and composition of the mineralizing fluids, potential sources of metals and sulfur and the fluid-rock interaction during the ore-forming processes. In this paper we combine Electron Microprobe Analysis and LA-ICP-MS analyses to put constraints on the nature and evolution of the Pitangui gold deposit. The Pitangui deposit represents an important Orogenic Au deposit hosted in clastic metasedimentary rocks of the Pitangui greenstone belt, northwestern portion of the Quadrilátero Ferrífero. Detailed drill hole, petrographic observations and in-situ chemical analyses of the hydrothermal alteration zones show that pyrite is the dominant ore mineral in the deposit and two possible origins are suggest including (i) syngenetic pyrite development at the early stages of the greenstone belt evolution and (ii) epigenetic pyrite, which is associated with hydrothermal processes during the Orogenic Au event. Syngenetic pyrite (PyI) has high Co, Bi, Pb, Sb, Te, Se, Ag and Au concentrations. The PyI could represent an important source of metals, a set of trace elements and likely sulfur for the later Orogenic Au mineralization. Epigenetic pyrites (PyII, PyIII and PyIV), conversely, are mainly found in association with hydrothermal minerals and within the mineralized carbonate-quartz-vein. The variations at Co, Ni, Pb, Te, Sn, Se, As, Bi, Sb, Ag, Mo and W in the epigenetic pyrite indicate that the dehydration PGB sequences during orogenesis constitutes the main fluids sources. The PyV, in turn, only appears at metamafic dyke, but its origin remains unclear.

Antimonate Controls Manganese(II)-Induced Transformation of Birnessite at a Circumneutral pH.

Manganese (Mn) oxides, such as birnessite (δ-MnO2), are ubiquitous mineral phases in soils and sediments that can interact strongly with antimony (Sb). The reaction between birnessite and aqueous Mn(II) can induce the formation of secondary Mn oxides. Here, we studied to what extent different loadings of antimonate (herein termed Sb(V)) sorbed to birnessite determine the products formed during Mn(II)-induced transformation (at pH 7.5) and corresponding changes in Sb behavior. In the presence of 10 mM Mn(II)aq, low Sb(V)aq (10 μmol L-1) triggered the transformation of birnessite to a feitknechtite (β-Mn(III)OOH) intermediary phase within 1 day, which further transformed into manganite (γ-Mn(III)OOH) over 30 days. Medium and high concentrations of Sb(V)aq (200 and 600 μmol L-1, respectively) led to the formation of manganite, hausmannite (Mn(II)Mn(III)2O4), and groutite (αMn(III)OOH). The reaction of Mn(II) with birnessite enhanced Sb(V)aq removal compared to Mn(II)-free treatments. Antimony K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy revealed that heterovalent substitution of Sb(V) for Mn(III) occurred within the secondary Mn oxides, which formed via the Mn(II)-induced transformation of Sb(V)-sorbed birnessite. Overall, Sb(V) strongly influenced the products of the Mn(II)-induced transformation of birnessite, which in turn attenuated Sb mobility via incorporation of Sb(V) within the secondary Mn oxide phases.