Risk assessment and strontium isotopic tracing of potentially toxic metals in creek sediments around a uranium mine, China.

The contamination of creek sediments near industrially nuclear dominated site presents significant environmental challenges, particularly in identifying and quantifying potentially toxic metal (loid)s (PTMs). This study aims to measure the extent of contamination and apportion related sources for nine PTMs in alpine creek sediments near a typical uranium tailing dam from China, including strontium (Sr), rubidium (Rb), manganese (Mn), lithium (Li), nickel (Ni), copper (Cu), vanadium (V), cadmium (Cd), zinc (Zn), using multivariate statistical approach and Sr isotopic compositions. The results show varying degrees of contamination in the sediments for some PTMs, i.e., Sr (16.1-39.6 mg/kg), Rb (171-675 mg/kg), Mn (224-2520 mg/kg), Li (11.6-78.8 mg/kg), Cd (0.31-1.38 mg/kg), and Zn (37.1-176 mg/kg). Multivariate statistical analyses indicate that Sr, Rb, Li, and Mn originated from the uranium tailing dam, while Cd and Zn were associated with abandoned agricultural activities, and Ni, Cu, and V were primarily linked to natural bedrock weathering. The Sr isotope fingerprint technique further suggests that 48.22-73.84% of Sr and associated PTMs in the sediments potentially derived from the uranium tailing dam. The combined use of multivariate statistical analysis and Sr isotopic fingerprint technique in alpine creek sediments enables more reliable insights into PTMs-induced pollution scenarios. The findings also offer unique perspectives for understanding and managing aqueous environments impacted by nuclear activities.

Microbial features with uranium pollution in artificial reservoir sediments at different depths under drought stress.

The uranium (U) containing leachate from uranium tailings dam into the natural settings, may greatly affect the downstream environment. To reveal such relationship between uranium contamination and microbial communities in the most affected downstream environment under drought stress, a 180 cm downstream artificial reservoir depth sediment profile was collected, and the microbial communities and related genes were analyzed by 16S rDNA and metagenomics. Besides, the sequential extraction scheme was employed to shed light on the distinct role of U geochemical speciations in shaping microbial community structures. The results showed that U content ranged from 28.1 to 70.1 mg/kg, with an average content of 44.9 mg/kg, significantly exceeding the value of background sediments. Further, U in all the studied sediments was related to remarkably high portions of mobile fractions, and U was likely deposited layer by layer depending on the discharge/leachate inputs from uranium-involving anthoropogenic facilities/activities upstream. The nexus between U speciation, physico-chemical indicators and microbial composition showed that Fe, S, and N metabolism played a vital role in microbial adaptation to U-enriched environment; meanwhile, the fraction of Ureducible and the Fe and S contents had the most significant effects on microbial community composition in the sediments under drought stress.

Hidden risks from potentially toxic metal(loid)s in paddy soils-rice and source apportionment using lead isotopes: A case study from China.

Pyrite is a typical sulfide mineral which contains various potentially toxic metal(loid)s (PTMs). The pyrite smelting and subsequent industrial utilization activities usually release numerous amounts of PTMs into nearby ecosystem, which may be enriched in the nearby farmland soils and crops, leading to hidden but irreversible harm to human health via the food chain. Herein, the distribution pattern, source apportionment, and potential health risks of Pb, Zn, Cu, Cd and multiple seldom monitored PTMs (Ag, Bi, Sb, Sr, Th, U, W, and V) in the paddy soils and different organs of the rice plants from ten various sites in a typical industrial zone were investigated, where pyrite ores were used for the production of sulfuric acid and subsequent cement over several decades. The results showed that the contents of Cd, Pb and Zn in studied paddy soils generally exceeded the maximum permissible level (MPL) in China, and the contents of Sb and V were approaching the MPL. Moreover, the rice is easier to bioaccumulate Cd, Cu, and Zn than the other studied elements. The hazard quotient (HQ) calculations indicate that the rice containing such multiple elements may cause a high potential non-carcinogenic and carcinogenic health risk for residents, particularly for the senior group. The Pb isotope tracing method combined with PCA (principal component analysis) further uncovered that the pyrite industrial utilization contributed 18.58-55.41 % to the highly enriched PTMs in paddy soils. All these findings indicate that the paddy soil system has been contaminated by the pyrite industrial activities and certain distances or areas should be rigidly forbidden from rice cultivation in the proximity of the pyrite smelting and related industrial sites.

Microbial diversity in paddy rhizospheric soils around a large industrial thallium-containing sulfide utilization zone.

Thallium (Tl) is a rare and extremely toxic metal whose toxicity is significantly higher than cadmium (Cd), lead (Pb) and antimony (Sb). The extensive utilization of Tl-bearing minerals, such as mining activities, has led to severe Tl pollution in a variety of natural settings, while little is known to date about its effect on the microbial diversity in paddy soils. Also, the geochemical behavior of Tl in the periodical alterations between dry and wet conditions of paddy soils remains largely unknown. Herein, the sequential extraction method and 16S rRNA gene sequence analysis were adopted to analyze Tl's migration and transformation behavior and the microbial diversity in the paddy soils with different pollution levels. The results indicated that Tl was mainly concentrated in reducible fraction, which is different from other types of soils, and may be closely attributed to the abundance of Fe-Mn (hydr)oxides in the paddy rhizospheric soils. Further analysis revealed that pH, total S, Pb, Sb, Tl and Cd were the dominant environmental factors, and the enrichment level of these potentially toxic metal(loid)s (PTMs) exerted obvious impacts on the diversity and abundance of microorganism in the rhizospheric soils, and regulating microbial community. The geochemical fractionation of Tl was closely correlated to soil microorganisms such as Fe reducing bacteria (Geothrix) and sulfate reducing bacteria (Anaerolinea), playing a critical role in Tl geochemical cycle through redox reaction. Hence, further study on microorganisms of paddy rhizospheric soils is of great significance to the countermeasures for remediating Tl-polluted paddy fields and protect the health of residents.

Transformation and fate of thallium and accompanying metal(loid)s in paddy soils and rice: A case study from a large-scale industrial area in China.

Thallium (Tl) is an extremely toxic metal, while its occurrence and fate in paddy soil environment remain understudied. Herein, the enrichment and migration mechanisms and potential health risks of Tl and metal(loid)s were evaluated in paddy soils surrounding an industrial park utilizing Tl-bearing minerals. The results showed that Tl contamination was evident (0.63-3.16 mg/kg) in the paddy soils and Tl was generally enriched in root of rice (Oryza sativa L.) with a mean content of 1.27 mg/kg. A remarkably high level of Tl(III) (30-50%) was observed in the paddy soils. Further analyses by STEM-EDS and XPS indicated that Tl(I) in the paddy soils was jointly controlled by adsorption, oxidation, and precipitation of Fe/Mn(hydr)oxide (e.g. hematite and birnessite), which might act as important stabilization mechanisms for inhibiting potential Tl uptake by rice grains. The health quotient (HQ) values indicated a potentially high Tl risk for inhabitants via consumption of the rice grains. Therefore, it is critical to establish effective measures for controlling the discharge of Tl-containing waste and wastewater from different industrial activities to ensure food safety in the rice paddy soils.

Microbial response and adaption to thallium contamination in soil profiles.

Thallium (Tl) is a trace metal with high toxicity. Comprehensive investigation of spatial distribution of Tl and microorganism is still limited in soils from mining area. In this study, 16S rRNA sequencing and network analysis were used for deciphering the co-occurrence patterns of bacterial communities in two different types of soil profiles around a typical Tl-bearing pyrite mine. The results showed that geochemical parameters (such as pH, S, Tl, Fe and TOM) were the driving forces for shaping the vertical distribution of microbial community. According to network analysis, a wide diversity of microbial modules were present in both soil profiles and affected by depth, significantly associated with variations in Tl geochemical fractionation. Phylogenetic information further unveiled that the microbial modules were mainly dominated by Fe reducing bacteria (FeRB), Fe oxidizing bacteria (FeOB), S oxidizing bacteria and Mn reducing bacteria. The results of metagenome indicated that Fe, Mn and S cycle in soil are closely involved in the biogeochemical cycle of Tl. The findings of co-occurrence patterns in the bacterial network and correlation between microorganisms and different geochemical fractions of Tl may benefit the strategy of bioremediation of Tl-contaminated soils with indigenous microbes.

Thallium geochemical fractionation and migration in Tl-As rich soils: The key controls.

Thallium (Tl) pollution caused by mining and processing of Tl-enriched ores has become an increasing concern. This study explored the geochemical fractionation and vertical transfer of Tl in a soil profile (200 cm) from a representative Tl-As mineralized area, Southwest China. The results showed that the soils were heavily enriched by Tl and As, with concentration ranging from 3.91-17.3 and 1830-8840 mg/kg (6.79 and 2973 mg/kg in average), respectively. Approximately 50% of Tl occurred in geochemically mobile fractions in the topsoil, wherein the reducible fraction was the most enriched fraction. Further characterization using LA-ICP-MS and TEM revealed that enriched Tl and As in soils were mainly inherited from the weathering of mine tailing piles upstream. XPS characterization indicated that Fe oxides herein may play a critical role in the oxidation of Tl(I) to Tl(III) which provoked further adsorption of Tl onto Fe oxides, thereby facilitating Tl enrichment in the reducible fraction. The findings highlight that the pivotal role of Fe oxides from mineralized area in the co-mobility and migration of Tl and As in the depth profile.

Escalating health risk of thallium and arsenic from farmland contamination fueled by cement-making activities: A hidden but significant source.

Soil-to-vegetable migration of toxic metal(loid)s is a pivotal pathway of human exposure to chemical intoxication. Thallium (Tl) and arsenic (As) are highly toxic metal(loid)s but their co-occurrence in soils and vegetables remain poorly understood. Herein, the present study focuses on potential health risk arising from co-occurrence of TlAs in various common vegetables cultivated in different farmlands around an industrial area featured by cement production activities. The results reveal obvious co-contamination of Tl (2.28 ± 1.39 mg/kg) and As (102.0 ± 66.7 mg/kg) in soils. Fine particles bearing sulfide and other minerals associated with Tl and As are detected in fly ash from cement plant, which can be migrated by wind over a long distance with hidden but inevitable pollution. Bioaccumulation Factor (BCF) and Enrichment Factor (EF) show that taro and corn preferentially accumulate Tl especially in underground parts. Hazard Quotient (HQ) indicates that consumption of these vegetables may result in chronic poisoning and/or even carcinogenic risk. The study highlights that the pathway and high risk of co-contamination of TlAs in the nearby farmlands posed by cement-making activities should be highly concerned.

Emergent thallium exposure from uranium mill tailings.

Thallium (Tl) pollution caused by the exploitation of uranium (U) mines has long been neglected due to its low crustal abundance. However, Tl may be enriched in minerals of U ore because Tl has both sulfurophile and lithophile properties. Herein, a semi-dynamic leaching experiment combined with statistical analysis, geochemical speciation and multi-characterization provided novel insight into the distinct features and mechanisms of Tl release from uranium mill tailings (UMT). The results showed that particle size effects prevail over the pH on Tl release, and surface dissolution is the pivotal mechanism controlling Tl release based on Fick's diffusion model. The study revealed that long-term leaching and weathering can lead to the increased acid-extractable and oxidizable fractions of Tl in UMT, and that the exposure and dissolution of Tl-containing sulfides would largely enhance the flux of Tl release. The findings indicate that UMT containing (abundant) pyrite should be paid particular attention due to Tl exposure. Besides, critical concern over the potential Tl pollution in universal U mining and hydrometallurgical areas likewise may need to be seriously reconsidered.

Highly efficient removal of thallium in wastewater by MnFe2O4-biochar composite.

Thallium (Tl), is a highly toxic trace metal in the natural environment. Emerging Tl pollution in waters has gradually become a global concern. However, limited removal technologies are available for Tl-containing wastewater. Herein, MnFe2O4-biochar composite (MFBC) was successfully fabricated via coprecipitation method as a novel and efficient adsorbent for treating Tl(I)-contaminated wastewater. It was found that the MFBC, with a specific surface area of 187.03 m2/g, exhibited high performance across a wide pH range of 4-11, with the superior Tl(I) removal capacity (170.55 mg/g) based on Langmuir model (pH 6.0, a dosage of 1 g/L). The removal mechanisms included physical and chemical adsorption, ion exchange, surface complexation, and oxidation. This investigation revealed that MFBC is a promising and environmentally friendly adsorbent with a low cost, large specific surface area, magnetic properties, and high efficiency for the removal of Tl(I) from wastewater.

Quantitative isotopic fingerprinting of thallium associated with potentially toxic elements (PTEs) in fluvial sediment cores with multiple anthropogenic sources.

Thallium (Tl) is a dispersed trace metal showing remarkable toxicity. Various anthropogenic activities may generate Tl contamination in river sediments, posing tremendous risks to aquatic life and human health. This paper aimed to provide insight into the vertical distribution, risk assessment and source tracing of Tl and other potentially toxic elements (PTEs) (lead, cadmium, zinc and copper) in three representative sediment cores from a riverine catchment impacted by multiple anthropogenic activities (such as steel-making and Pb-Zn smelting). The results showed high accumulations of Tl combined with associated PTEs in the depth profiles. Calculations according to three risk assessment methods by enrichment factor (EF), geoaccumulation index (Igeo) and the potential ecological risk index (PERI) all indicated a significant contamination by Tl in all the sediments. Furthermore, lead isotopes were analyzed to fingerprint the contamination sources and to calculate their quantitative contributions to the sediments using the IsoSource software. The results indicated that a steel-making plant was the most important contamination source (∼56%), followed by a Pb-Zn smelter (∼20%). The natural parental bedrock was found to contribute ∼24%. The findings highlight the importance of including multiple anthropogenic sources for quantitative fingerprinting of Tl and related metals by the lead isotopic approach in complicated environmental systems.

Persistent thallium contamination in river sediments, source apportionment and environmental implications.

The adverse impacts of detrimental thallium (Tl) contamination are of increasing concerns to sustainable development. Herein, the contents, distributions and sources of Tl and potential toxic elements (PTEs) (Pb, As, Cr, Cu, Ni, Co, Sb, Cd and U) were investigated in sediments collected in Gaofeng River, which has been contaminated by long-term mining activities, located in Yunfu City, Southern China. Results indicated that excessive Tl levels were found in sediments (1.80-16.70 mg/kg). Sequential extraction procedure indicated that despite a large amount of Tl entrapped in residual fraction, a significant level of Tl (0.28-2.34 mg/kg) still exhibited in geochemically labile fractions, which was easy for Tl mobilization and availability. Pb isotope tracing method further confirmed that the pyrite exploitations may be the prime contaminated contributor (47-76%) to these sediments. These findings highlight that it is essential to establish more effective measures for Tl contamination control and call for engineered remediation countermeasures towards polluted river sediments.

Microbial insights into the biogeochemical features of thallium occurrence: A case study from polluted river sediments.

Thallium (Tl) is a trace element with extreme toxicity. Widespread Tl pollution in riverine systems, mainly due to escalating mining and smelting activities of Tl-bearing sulfide minerals, has attracted increasing attention. Insights into the function of the microbial communities with advanced characterization tools are critical for understanding the biogeochemical cycle of Tl. Herein, microbial communities and their adaptive evolution strategies in river sediments from a representative Tl-bearing pyrite mine area in southern China were profiled via 16S rRNA gene sequence analysis and shotgun metagenomic analysis. In total, 64 phyla and 778 genera of microorganisms were observed in the studied sediments. The results showed that pH, Tl, Pb, Zn and total organic carbon (TOC) had a significant influence on microbial community structure. Some important reductive microorganisms (such as Erysipelothrix, Geobacter, desulfatiferula, desulfatihabadium and fusibacter) were involved in the biogeochemical cycle of Tl. The ruv, rec, ars and other resistance genes enhanced the tolerance of microorganisms to Tl. The study suggested that relevant C, N and S cycle genes were the main metabolic paths of microorganisms surviving in the high Tl-polluted environment. The findings were critical for establishment, operation and regulation in the microbial treatment of Tl containing or related wastewater.

Geochemical transfer of cadmium in river sediments near a lead-zinc smelter.

Cadmium (Cd) is a highly toxic element and non-essential to human. Herein, the source and fate of Cd were examined in a typical sediment profile from the North River, South China, which was affected by the massive Pb-Zn smelting activities for decades. An exceptionally high enrichment of Cd, 107-441 mg/kg, was observed across the whole profile. Approximately 50-75% of Cd was retained in the weak acid soluble fraction. Risk assessment based on geoaccumulation index (Igeo), potential ecological risk index (Eri), bioavailable metal index (BMI) and toxic risk index (TRI) further indicated an extremely strong degree of potential ecological pollution and high toxic risks. The mineralogical composition of particles from the sediment profile exhibited the presence of pyrite, magnetite, wurtzite and greenockite. This further confirmed that Cd was migrated from smelting slags to the North River basin and enriched in sediment profile. Sediment Cd speciation analysis also implied a possible transformation of Cd from metal oxides in smelting slags to adsorbed phases and carbonates, which enhances the bioavailability of Cd. The findings indicate proper countermeasures or remediation approaches should be promptly taken towards high ecological risks of Cd arising from the depth profile extending nearly 1 m, due to lead-zinc smelting related activities.

Legacy of multiple heavy metal(loid)s contamination and ecological risks in farmland soils from a historical artisanal zinc smelting area.

Farmland soil contamination of heavy metal(loid)s (HM) derived from smelting activities is a global concern, owing to its potential threat for human health through food chain. This study aims to evaluate total contents and bioavailability of HMs (Pb, Zn, Tl, Cd, Cu, As, Ag, Co, Cr and Ni) in farmland soils distributed over ten different villages from a former artisanal zinc smelting area in the northwest Guizhou province, China. The results showed that most of the studied soils still exhibited exceptionally high enrichment of Pb, Zn, Cd and As. High levels of bioavailable HMs were also observed in some samples, which may enter the human food chain through agricultural activities. Further analyses by Scanning Transmission Electron Microscopy - Energy Dispersive Spectroscopy (STEM-EDS), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) showed the presence of Zn smelting by-products such as Fe oxides, ZnO and PbSO4 even in nanoscale particles retained by the soils. Elemental mapping by EDS confirmed a close association of the studied HMs with the smelting waste particles. All these results signify that high levels of HM-contamination from historical artisanal zinc smelting activities still persist and threaten the health of local residents, despite the fact that the major industrial-derived-contamination period ended >15 years ago. Our findings highlight pivotal concerns in similar artisanal-smelting-affected farmland soils of suspected contamination, due to less-expected toxic elements such as Tl, which may cause high ecological health risks.