Distribution, risk evaluation, and source allocation of cesium and strontium in surface soil in a mining city.

Radioactive nuclides cesium (Cs) and strontium (Sr) possess long half-lives, with 135Cs at approximately 2.3 million years and 87Sr at about 49 billion years. Their persistent accumulation can result in long-lasting radioactive contamination of soil ecosystems. This study employed geo-accumulation index (Igeo), pollution load index (PLI), potential ecological risk index (PEPI), health risk assessment model (HRA), and Monte Carlo simulation to evaluate the pollution and health risks of Cs and Sr in the surface soil of different functional areas in a typical mining city in China. Positive matrix factorization (PMF) model was used to elucidate the potential sources of Cs and Sr and the respective contribution rates of natural and anthropogenic sources. The findings indicate that soils in the mining area exhibited significantly higher levels of Cs and Sr pollution compared to smelting factory area, agricultural area, and urban residential area. Strontium did not pose a potential ecological risk in any studied functional area. The non-carcinogenic health risk of Sr to the human body in the study area was relatively low. Because of the lack of parameters for Cs, the potential ecological and human health risks of Cs was not calculated. The primary source of Cs in the soil was identified as the parent material from which the soil developed, while Sr mainly originated from associated contamination caused by mining activities. This research provides data for the control of Cs and Sr pollution in the surface soil of mining city.

Effect of exogenous Ca on the physiology and growth indicators of pakchoi under foliar and root fluorine stress.

Fluorine (F) is not an essential element for vegetation and excessive F can be phytotoxic to plant growth, which can cause fluorosis to human beings by ingesting F-contaminated plant. Although there have been some studies focusing on the toxicity of F to plants and the retarding effect of Ca to F-stress plant, atmospheric F contamination to vegetation and the role of the application of foliar Ca are scantly reported. This study investigated several biochemical parameters to evaluate F toxicity under both F-exposure (root and leaf F-exposure) and the remedial effects of foliar Ca. The results showed that F concentration of pakchoi leaves was correlated with exogenous F level positively in both foliar and root F-exposure series, and F concentration of pakchoi roots was only changed under root F-exposure treatments. Ca supplement (0.5 g/L and 1 g/L) significantly decreased plant F concentration. Both F-exposure treatments caused lipid peroxidation in plants and exogenous Ca alleviated the toxicity of F to pakchoi. Meanwhile, chlorophyll-a concentration was decreased by foliar and root F, whereas chlorophyll-b concentration was only affected by foliar F, and chlorophyll-a concentration could be elevated by exogenous Ca but chlorophyll-b could not. It was concluded that both atmospheric and root F can impair pakchoi growth and disturb photosynthesis, and foliar Ca showed an ameliorative effect to F toxicity of pakchoi through alleviating chlorophyll decomposition, increasing protein content and alleviating oxidative damage.

High-throughput Sequencing Analysis of the Effects of Vanadium on Bacterial Community Structure in Purple Soil.

Vanadium (V) contamination in soil has received extensive attention due to its high toxicity. The change of mobility and bioavailability of soil V and the effects of V on the soil microbial community were studied under conditions of different V(V) spiking concentrations (0, 100, 250, and 500 mg kg-1) and aging time (1, 7, 14, 30, 45, and 60 d). The results showed that soil V mainly presented as V(IV) of all treatments throughout the aging process. At high levels of V(V) loading (250 and 500 mg kg-1), soil V(V) showed a downward trend, while bioavailable V did not change significantly within 60 d's aging. The analysis of soil bacterial community showed that Proteobacteria was the most abundant phylum in all soils, and the dominant genera Sphingomonas and Lysobacter can well adapt to high concentration V. These microorganisms exhibited great potential for bioremediation of V-contaminated soils.

Growth Responses and Accumulation of Vanadium in Alfalfa, Milkvetch Root, and Swamp Morning Glory and Their Potential in Phytoremediation.

Pot experiments with alfalfa, milkvetch root and swamp morning glory were conducted to elucidate the effect of soil vanadium (V) on plant growth and to evaluate their phytoremediation potential under V(V) exposure. Based on biomass analysis, swamp morning glory showed higher tolerance than alfalfa and milkvetch root in response to different soil V(V) levels. The accumulation of V in plants increased with the increasing soil V and the V concentration in roots was 1.95-4.31 times that in shoots. After planting, soil total V, V(V), bioavailable V and water-soluble V all reduced, and the decreases in bioavailable V and V(V) showed significant. The decreased percentage of V(V) in total V in soils demonstrated that the planting process may stimulate the mechanism of V(V) reduction to V(IV). Therefore, the three tested plants, particularly swamp morning glory can be promising phytostabilizers applied to V phytoremediation practices.

Photo-induced reduction of vanadium in vanadium-containing iron/manganese oxide agglomerates by oxalic acid.

The stockpiling of vanadium-containing tailings allows vanadium to migrate into the surrounding area, resulting in toxic metal contamination. By using the vanadium-bearing iron/manganese (Fe/Mn) oxide agglomerates as the simulated tailings, the feasibility of photo-induced reduction of vanadium by oxalic acid was investigated. Batch effects of the available light and the reducing agents on agglomerates were investigated. Results showed that oxalic acid (5 mmol L-1) can convert V(V) to V(IV) and convert Fe(III) released from the Fe/Mn oxide agglomerates to Fe(II) under both light and dark conditions. After 45 d of reaction in the dark, oxalic acid converted 33.54% Fe(III) and 100% V(V) in the leachate into Fe(II) and V(IV). The Fenton reaction occurred by light irradiation significantly increased the redox potential in the solution, and also caused V(IV) to be oxidized. Overall, oxalic acid can rapidly reduce V(V) to V(IV), but sunlight may have an inhibitory effect on the reduction reaction. Present study can deepen the understanding of the mechanism for valence transformation of elements in minerals by sunlight, and can help in implementing tailings treatment and environmental remediation by using oxalic acid and avoiding light.

Dynamics of vanadium and response of inherent bacterial communities in vanadium-titanium magnetite tailings to beneficiation agents, temperature, and illumination.

Vanadium-titanium (V-Ti) magnetite tailings contain toxic metals that could potentially pollute the surrounding environment. However, the impact of beneficiation agents, an integral part of mining activities, on the dynamics of V and the microbial community composition in tailings remains unclear. To fill this knowledge gap, we compared the physicochemical properties and microbial community structure of V-Ti magnetite tailings under different environmental conditions, including illumination, temperature, and residual beneficiation agents (salicylhydroxamic acid, sodium isobutyl xanthate, and benzyl arsonic acid) during a 28-day reaction. The results revealed that beneficiation agents exacerbated the acidification of the tailings and the release of V, among which benzyl arsonic acid had the greatest impact. The concentration of soluble V in the leachate of tailings with benzyl arsonic acid was 6.4 times higher than that with deionized water. Moreover, illumination, high temperatures, and beneficiation agents contributed to the reduction of V in V-containing tailings. High-throughput sequencing revealed that Thiobacillus and Limnohabitans adapted to the tailings environment. Proteobacteria was the most diverse phylum, and the relative abundance was 85.0%-99.1%. Desulfovibrio, Thiobacillus, and Limnohabitans survived in the V-Ti magnetite tailings with residual beneficiation agents. These microorganisms could contribute to the development of bioremediation technologies. The main factors affecting the diversity and composition of bacteria in the tailings were Fe, Mn, V, SO42-, total nitrogen, and pH of the tailings. Illumination inhibited microbial community abundance, while the high temperature (39.5 °C) stimulated microbial community abundance. Overall, this study strengthens the understanding of the geochemical cycling of V in tailings influenced by residual beneficiation agents and the application of inherent microbial techniques in the remediation of tailing-affected environments.

Shewanella oneidensis MR-1 and oxalic acid mediated vanadium reduction and redistribution in vanadium-containing tailings.

The microbially- and chemically-mediated redox process is critical in controlling the fate of vanadium (V) in tailing environment. Although the microbial reduction of V has been widely studied, the coupled biotic reduction mediated by beneficiation reagents and the underlying mechanism remain unclear. Herein, the reduction and redistribution of V in V-containing tailings and Fe/Mn oxide aggregates mediated by Shewanella oneidensis MR-1 and oxalic acid were explored. The dissolution of Fe-(hydr)oxides by oxalic acid promoted the microbe-mediated V release from solid-phase. After 48-day of reaction, the dissolved V concentrations in the bio-oxalic acid treatment reached maximum values of 1.72 ± 0.36 mg L-1 and 0.42 ± 0.15 mg L-1 in the tailing system and the aggregate system, respectively, significantly higher than those in control (0.63 ± 0.14 mg L-1 and 0.08 ± 0.02 mg L-1). As the electron donor, oxalic acid enhanced the electron transfer process of S. oneidensis MR-1 for V(V) reduction. The mineralogical characterization of final products indicates that S. oneidensis MR-1 and oxalic acid promoted solid-state conversion from V2O5 to NaV6O15. Collectively, this study demonstrates that microbe-mediated V release and redistribution in solid-phase were promoted by oxalic acid, suggesting that the role of organic agents for the V biogeochemical cycle in natural systems deserves greater attention.

Vanadium mobilization and redistribution during mineral transformation of vanadium-titanium magnetite tailings with different weathering degrees.

Due to the long-term open stockpile, the release of vanadium (V) from V-containing tailings will cause continuous V pollution in the mining area. Previous studies on the concentration and speciation of V primarily focused on surface tailings at a regional scale. However, the mobilization and redistribution of V within the tailing profile during the mineral transformation of tailings remain unclear. Herein, a series of concentrations of V(V) (0-200 mg L-1) solutions were added to the vanadium­titanium magnetite tailings at different depths separately to simulate the redistribution of dissolved V released from tailings in the solid phase of tailings. During the 56-day incubation, the concentrations of aqueous V in the surface tailings were significantly lower than those in the deep tailings under the same level of V(V) treatment, indicating that the shallow tailings had a stronger immobilization capacity for V than the deep tailings. Morphological analysis and color overlays of the elements demonstrated that most of V was immobilized into the tailings and adsorbed or precipitated by the Fe (hydr)oxides in the tailings in 200 mg L-1 V(V) treatment. This portion of V mainly occurred in acid-soluble and reducible fractions in the tailings after a 7-day incubation, accounting for >71.7 % of the total V. However, these two factions of V with high bioavailability were gradually mineralized over time and transferred to residual V, which is difficult to move and has low bioavailability. Mineral phase analysis revealed that additional V(V) favored the formation of melanovanadite (Ca2V8O20·10H2O) and chromium vanadium oxide (Cr2V4O13) in the tailings. This study reveals that the dissolved V influenced the fractionation and redistribution of solid-phase V during tailing weathering, improving the understanding of the geochemical processes of V in tailing profiles and providing important guidance for the management of V-containing tailings.

Transcriptomic and metabolomic perspectives for the growth of alfalfa (Medicago sativa L.) seedlings with the effect of vanadium exposure.

Hitherto, the effect of vanadium on higher plant growth remains an open topic. Therefore, nontargeted metabolomic and RNA-Seq profiling were implemented to unravel the possible alteration in alfalfa seedlings subjected to 0.1 mg L-1 (B group) and 0.5 mg L-1 (C group) pentavalent vanadium [(V(V)] versus control (A group) in this study. Results revealed that vanadium exposure significantly altered some pivotal transcripts and metabolites. The number of differentially expressed genes (DEGs) markedly up- and down-regulated was 21 and 23 in B_vs_A, 27 and 33 in C_vs_A, and 24 and 43 in C_vs_B, respectively. The number for significantly up- and down-regulated differential metabolites was 17 and 15 in B_vs_A, 43 and 20 in C_vs_A, and 24 and 16 in C_vs_B, respectively. Metabolomics and transcriptomics co-analysis characterized three significantly enriched metabolic pathways in C_vs_A comparing group, viz., α-linolenic acid metabolism, flavonoid biosynthesis, and phenylpropanoid biosynthesis, from which some differentially expressed genes and differential metabolites participated. The metabolite of traumatic acid in α-linolenic acid metabolism and apigenin in flavonoid biosynthesis were markedly upregulated, while phenylalanine in phenylpropanoid biosynthesis was remarkably downregulated. The genes of allene oxide cyclase (AOC) and acetyl-CoA acyltransferase (fadA) in α-linolenic acid metabolism, and chalcone synthase (CHS), flavonoid 3'-monooxygenase (CYP75B1), and flavonol synthase (FLS) in flavonoid biosynthesis, and caffeoyl-CoA O-methyltransferase (CCoAOMT) in phenylpropanoid biosynthesis were significantly downregulated. While shikimate O-hydroxycinnamoyltransferase (HCT) in flavanoid and phenylpropanoid biosynthesis were conspicuously upregulated. Briefly, vanadium exposure induces a readjustment yielding in metabolite and the correlative synthetic precursors (transcripts/unigenes) in some branched metabolic pathways. This study provides a practical and in-depth perspective from transcriptomics and metabolomics in investigating the effects conferred by vanadium on plant growth and development.

Concentration and distribution of metals, total fluorine, per- and poly-fluoroalkyl substances (PFAS) in vertical soil profiles in industrialized areas.

The widespread usage of per- and poly-fluoroalkyl substances (PFAS) has caused great concern due to their potential toxicology to human and environmental health. However, there have been limited investigations on the vertical distribution of PFAS in fluorine (F) contaminated soils. In this study, the spatial and vertical distribution of metals, total F, and PFAS in the soil profiles were investigated at different areas in an industrial city. The higher F concentrations in the farmland soils with intensive agricultural activities suggested the impacts of soil tillage. The ΣPFAS concentrations ranged from 0.187 to 1.852 ng g-1 in all soil samples, with PFOA as the dominant pollutant, which accounted for 17.2%-51.6% of the ΣPFAS in all samples. Highest level of PFAS was found in the shallow layer of the soil profiles. The long-chain PFAS such as PFUdA and PFTeDA tended to remain in the topsoil, while the short-chains (PFBA, PFPeA, and PFHxA) have migrated to depth of 100 cm in the vertical soil profile. The application of F-enriched phosphorus fertilizers and atmospheric deposition may be important sources of F and PFAS in soils in this area. Correlation analysis indicated that most of PFAS have similar common sources, and the significantly positive correlation between Zn and PFAS suggested they may share similar sources. This study highlights the need for further work to monitor the PFAS level in soil environments in industrialized areas, in addition to focusing on soil metal and F pollution.

Multiple heavy metal distribution and microbial community characteristics of vanadium-titanium magnetite tailing profiles under different management modes.

Vanadium-titanium (V-Ti) magnetite tailings have caused great concern due to their safety hazards and environmental risks. However, the microbial community structure and the key geochemical factors of V-Ti magnetite tailing profiles under different management modes remain unclear. Therefore, we investigated the heavy metal distribution and the microbial community structure of the soils and tailings at varied depths of V-Ti magnetite tailing profiles with and without soil coverage. The results indicated that the topsoil covering measures retarded the acidification of tailings during stockpiling. However, As, Mn, and V in tailings have the ability to migrate to the overlying soil. Based on 16S rRNA gene amplicon sequencing, Proteobacteria was the dominant genus in the topsoil-covered tailings, whereas the most abundant genus in the exposed tailings was Betaproteobacteria. Furthermore, Rhodobacter, Hydrogenophaga, Novosphingobium, and Geobacter enriched in tailings may potentially contribute to V(V) biotransformation and the development of mine bioreremediation technologies. RDA and Spearman correlation analysis showed that pH, EC, Cd, Mn, Pb, and V were the main influencing factors regulating microbial community composition. Overall, this study provides insights for evaluating the soil covering management mode and the engineering applications of microbial technologies to manage V-Ti magnetite tailings.

Contrasted speciation distribution of toxic metal(loid)s and microbial community structure in vanadium-titanium magnetite tailings under dry and wet disposal methods.

Tailing disposal technologies such as dry and wet disposal methods have a profound effect on the ecosystem of mining areas. However, the chemical speciation of metal(loid)s and microbial community structure in tailings under different disposal methods are still poorly understood. Here we compared the bioavailable fraction of metal(loid)s and the microbial community in vanadium-titanium (V-Ti) magnetite tailing profiles derived from dry and wet stockpiled methods. In wet tailings, the bioavailability of Cr, Cu, Mn, Ni, V, and Zn was higher than that in dry tailings as identified by BCR sequential extraction. Especially for Cu and Ni, the oxidizable fraction was the predominant fraction except the residual fraction, accounting for 37.2-59.0% and 23.2-36.6% of the total concentration in wet tailings, respectively. Based on 16 S rRNA high-throughput sequencing, totally 12 indicator bacterial taxa were detected in dry tailings against 68 in wet tailings. As the biomarkers in wet tailings, genera Sulfuricurvum, Geobacter, and Pseudomonas were expected to be applied to the transformation of metal(loid)s in the tailings. Our results emphasize the importance of dehydration treatment of tailings before stockpiling to minimize the environmental risks caused by toxic metal(loid)s, and provide insights into the engineering application of microbial technologies in V-Ti magnetite tailing area.

Remediation of fluoride contaminated soil with nano-hydroxyapatite amendment: Response of soil fluoride bioavailability and microbial communities.

Nano-hydroxyapatite (NHAP), possessing high defluoridation capacity, has been widely used to remove fluoride (F) from polluted water, but little is known about how it affects the bioavailability and toxicity of soil F towards plants. Here, the impact of NHAP (2% w/w) amendment on immobilization, speciation and accumulation of F was studied in a soil-plant system. The results revealed that the NHAP amendment worked effectively to reduce levels of water-soluble F (37.3%-87.8%) and increase available P (76.6%-147%). X-ray photoelectron spectroscopy analysis indicated that the formation of insoluble CaF2 and the ion exchange of F- with OH- into NHAP might be involved in the mechanism of F immobilization and soil pH elevation. Exposure to NHAP significantly decreased the abundance of Cyanobacteria in tested soils, and Gemmatimonadetes abundance in bulk soil was significantly higher than that in rhizosphere soil at 1,000 mg kg-1 F spiked level. Additionally, NHAP amendment decreased F accumulation in wheat shoots (9.10%-18.7%) and roots (3.88%-22.4%), which could mainly be attributed to the reduction of soil bioavailable F and the supplement of Ca from NHAP. These results suggest that NHAP could be a promising amendment to be applied to acidic soil contaminated with F.

Agricultural activities impact on soil and sediment fluorine and perfluorinated compounds in an endemic fluorosis area.

Perfluorinated compounds (PFCs) are organo-fluorine compounds which have been identified at significant levels in soils due to their widespread usage in industrial and commercial applications. However, few studies are available regarding the occurrence of PFCs in the environment of endemic fluorosis areas. To address the issue, soils collected from an endemic fluorosis area of southwestern China were analyzed for the distribution of fluorine and 21 kinds of PFCs. The average water-soluble fluorine concentration in cultivated soil (4.87 mg kg-1) was significantly higher than that in uncultivated soil (3.15 mg kg-1), which mainly ascribed to the utilization of fluorine-enriched fertilizers during agricultural practices. Concentrations of ΣPFCs in all soils ranged from 0.508 to 6.83 ng g-1, with an average of 2.81 ng g-1, dominated by perfluorononanoic acid (PFNA) and perfluorooctanoic acid (PFOA). Highest ΣPFCs was found in the soil samples collected from cropland with intensive agricultural activities. Long-chain PFCs, including four perfluoroalkylcarboxylic acids (PFCAs, C ≥ 8) and one perfluoroalkylsulfonic acids (PFSAs) (perfluorooctane sulfonate (PFOS), C8), exhibited high levels in soils, probably due to their higher hydrophobicity and lower water-solubility than short-chain PFCs. While in sediments, short-chain PFCAs were the dominant compounds. Based on correlation analysis, the relationship between total fluorine and PFCs was insignificant, and soil organic matter was a relevant factor affecting PFCs distribution in soils. This study is expected to present a more comprehensive information about fluorine contamination under the influence of agricultural activities in an endemic fluorosis area.