Is Cladophora fracta an efficient tool of accumulating critical raw materials from wastewater and there a potential health risk of use of algae as organic fertilizer?

In this study investigation of accumulations of critical raw materials (cobalt (Co), antimony (Sb), vanadium (V), lanthanum (La) and tungsten (W)) from wastewater by using C. fracta were aimed. Besides, assessment of the potential health risks in terms of the use of organic fertilizer obtained from the macroalga to be harvested from the treatment were also aimed. Highest Co, Sb, V, La and W accumulations by algae in reactor were 125±6.2%, 201.25±10%, 318.18±15%, 357.97±18%, and 500±25%, respectively. When compared with control, Co, Sb, V, La and W in algae increased 2.25, 3.01, 4.18, 4.58, and 6 times, respectively. The algae was very high bioaccumulative for Co and La. Highest MPI was calculated as 3.94. Non-carcinogenic risk of CRMs according to different exposure types (ingestion, inhalation, and dermal) were calculated for man, woman and child. There is not any non-carcinogenic risk from the investigated exposure ways of algae as organic fertilizer.

How iron-bearing minerals affect the biological reduction of Sb(V): A newly discovered function of nitrate reductase.

As a toxic element of global concern, the elevated concentration of antimony (Sb) in the environment has attracted increasing attention. Microorganisms have been reported as important driving forces for Sb transformation. Iron (Fe) is the most important metal associated element of Sb, however, how Fe-bearing minerals affect the biological transformation of Sb is still unclear. In this study, the effects of Fe-bearing minerals on biological Sb(V) reduction were investigated by employing a marine Shewanella sp. CNZ-1 (CNZ-1). Our results showed that the presence of hematite, magnetite and ferrihydrite (1 g/L) resulted in a decrease in Sb(III) concentration of ~19-31 % compared to the Fe(III)-minerals free system. The calculated Sb(V) reduction rates are 0.0256 (R2 0.71), 0.0389 (R2 0.87), 0.0299 (R2 0.96) and 0.0428 (R2 0.95) h-1 in the hematite-, magnetite-, ferrihydrite-supplemented and Fe(III)-minerals free systems, respectively. The cube-shaped Sb2O3 was characterized as a reductive product by using XRD, XPS, FTIR, TG and SEM approaches. Differential proteomic analysis showed that flagellar protein, cytochrome c, electron transfer flavoprotein, nitrate reductase and polysulfide reductase (up-regulation >1.5-fold, p value <0.05) were supposed to be included in the electron transport pathway of Sb(V) reduction by strain CNZ-1, and the key role of nitrate reductases was further highlighted during this reaction process based on the RT-qPCR and confirmatory experiments. Overall, these findings are beneficial to understand the environmental fate of Sb in the presence of Fe-bearing minerals and provide guidance in developing the bacteria/enzyme-mediated control strategy for Sb pollution.

Coupled sorptive and oxidative antimony(III) removal by iron-modified biochar: Mechanisms of electron-donating capacity and reactive Fe species.

Sorption and oxidation are two potential pathways for the decontamination of trivalent antimony (Sb(III))-bearing water, using iron (Fe)-modified biochar (FeBC). Here we investigated the sorption and oxidation behavior of FeBC for Sb(III) in aqueous solutions. Results revealed that Sb(III) removal by FeBC was significantly improved showing the maximum Sb(III) sorption (64.0 mg g-1). Density functional theory (DFT) calculations indicated that magnetite (Fe3O4) in FeBC offered a sorption energy of -0.22 eV, which is 5 times that of non-modified biochar. With the addition of peroxymonosulfate (PMS), the sorption of Sb(III) on FeBC was 7 times higher than that on BC, indicating the sorption capacity of FeBC for Sb(III) could be substantially increased by adding oxidizing agents. Electrochemical analysis showed that Fe modification imparted FeBC higher electron-donating capacity than that of BC (0.045 v. s. 0.023 mmol e- (g biochar)-1), which might be the reason for the strong Sb(III) oxidation (63.6%) on the surface of FeBC. This study provides new information that is key for the development of effective biochar-based composite materials for the removal of Sb(III) from drinking water and wastewater. The findings from this study have important implications for protecting human health and agriculture.

Determination of heavy metals and risk assessment in nail cosmetics sold in Seoul, Korea.

OBJECTIVE: The objective of this study was to evaluate some toxic levels of nail cosmetics marketed in Seoul, Korea and health risk assessment on humans. METHODS: We collected 45 random nail cosmetics and analysed for lead, cadmium, arsenic and antimony by inductively coupled plasma-optical emission spectrometry (ICP-OES). RESULTS: Four metals concentrations were Pb 0.037 ± 0.083 (

Adsorption and immobilization performance of pine-cone pristine and engineered biochars for antimony in aqueous solution and military shooting range soil: An integrated novel approach.

Antimony (Sb-V), a carcinogenic metalloid, is becoming prevalent in water and soil due to anthropogenic activities. Biochar could be an effective remedy for Sb(V)-contaminated water and soil. In this study, we used pristine and engineered pinecone-derived biochar as an innovative approach for treating Sb(V)-contaminated water and shooting range soil. Biochar was produced from pine-cone waste (pristine biochar) and enriched with Fe and Al salts via saturation (engineered biochar). Adsorption tests in water revealed that iron-modified biochar showed higher adsorption capacity (8.68 mg g-1) than that of the pristine biochar (2.49 mg g-1) and aluminum-modified biochar (3.40 mg g-1). Isotherm and kinetic modeling of the adsorption data suggested that the adsorption process varied from monolayer to multilayer, with chemisorption as the dominant interaction mechanism between Sb(V) and the biochars. The post-adsorption study of iron-modified biochar by Fourier Transform Infrared (FTIR) and X-ray diffraction (XRD) further supported the chemical bonding and outer-sphere complexation of Sb(V) with Fe, N-H, O-H, C-O and CC components. The pristine and iron-modified biochars also successfully immobilized Sb(V) in a shooting range soil, more so in the latter. Subsequent sequential extractions and post-analysis by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), and elemental dot mapping revealed that Sb in the treated soil transformed to a more stable form. It was concluded that iron-modified biochar could act as an efficient material for the adsorption and immobilization of Sb(V) in water and soil, respectively.

Immobilization of antimony in soil and groundwater using ferro-magnesium bimetallic organic frameworks.

Sb(III) is often detected in contaminated soil and groundwater. Hence, high-efficiency technology is needed. In this study, bimetallic organic frameworks were used for the first time to immobilize Sb(III) from contaminated soil and groundwater. The materials were synthesized by the hydrothermal method. Both ends of the prepared material were hexagonal tip rods, and the length became shorter as the ratio of Fe/Mg decreased. The bimetallic organic framework with a Fe/Mg feeding ratio of 0.5 was the optimum material for Sb(III) removal, which could effectively immobilize Sb(III). The adsorption isotherm was fitted well with the Freundlich model, and the optimal adsorption capacity can reach 106.97 mg/g. The adsorption capacity of 84% can be completed in 10 min, which conformed to the pseudo-second-order kinetics. The Fe3+ could enhance the stability of the material, and the Mg2+ was conducive to freeing up adsorption sites for binding Sb(III) and forming stable chemical adsorption. Ion exchange is the predominant mechanism to remove Sb(III). After 14 days of remediation of Sb(III) contaminated soil, the Toxicity Characteristic Leaching Procedure (TCLP)-leached concentrations of Sb(III) were reduced by 86%, 91% and 94% when the material dosages were 1%, 2% and 3%, respectively. Immobilization of Sb(III) in soil resulted in a conversion of antimony speciation from more easily bioavailable species to less bioavailable species, further contributing to reduce the environmental risk of antimony. The results indicate that ferro-magnesium bimetallic organic frameworks may serve as a kind of promising materials for the immobilization of Sb(III) in contaminated soil and groundwater.

Concurrent sorption of antimony and lead by iron phosphate and its possible application for multi-oxyanion contaminated soil.

Concurrent stabilization of oxyanions such as antimony (Sb), arsenic (As), and heavy metals including lead (Pb) and manganese (Mn) in contaminated soils is difficult because of their diverse chemical properties. Antimony and As are stabilized by sorption with iron oxides while heavy metals are stabilized by phosphate. Hence, iron phosphate can be used to simultaneously stabilize Sb and Pb. Therefore, this study aimed to evaluate the possibility of simultaneous stabilization of Sb and Pb using iron phosphate. A single and a mixed solution of Sb and Pb were reacted with synthesized iron phosphate. Contaminated soil by Sb, As, Mo, Cr, and Mn was treated with iron phosphate, and bioavailable metal concentrations were evaluated by extracting the soil with 0.05 M ammonium sulfate. In a single solution, Sb(III) and Sb(V) sorption rate ranged up to 97% and 65%, respectively. In a mixed metal solution, Sb sorption increased compared to the single solution and Pb removal reached more than 95% in all cases. The sorption of Sb increased as the pH decreased, but the Sb(III) sorption was less affected by the pH than Sb(V). In various pH ranges, Sb(III) and Sb(V) sorption rates increased by 26 ~ 32% and 38 ~ 68%, respectively, compared to the single solution. Especially, Sb(V) sorption significantly increased in the presence of Pb at lower pH because of the lower solubility of iron phosphate. In soil, iron phosphate slightly decreased bioavailable As, Cr, Mo, Sb, and Mn concentrations. Therefore, metalloids and metals can be simultaneously stabilized by iron phosphate both in solution and soil.

Aluminum adsorption and antimonite oxidation dominantly regulate antimony solubility in soils.

Soil antimony (Sb) contamination occurs globally due to natural processes and human activities. Total Sb concentration in soils fails to assess its ecological risk, while determined by the concentration of available Sb, which is readily for biological uptake. Available Sb in different soils varied significantly according to soil properties. However, so far it is unknown how soil properties regulate Sb availability, and no model has been established to predict it through soil properties. In this study, 19 soils spiked with antimonite [Sb(III)] were used to identify the major factors controlling Sb availability and establish its predicting models. The results showed that available Sb in different soils varied largely depending on the contents of free aluminum (fAl), free iron (fFe) and electric conductivity (EC), which explained 33%, 27% and 24.9% of the total variation, respectively. During the first 42 days of soil aging, fAl and EC effectively predicted the concentrations of available Sb with R2 = 0.64, while during the later stages (70-150 d) of soil aging, fAl content was the unique parameter employed into the predicting model (R2 = 0.53). These results firstly demonstrate that the content of free aluminum (fAl) is the most important factor regulating Sb availability in soils, although the content of fAl is much lower than that of fFe. This finding can help to develop new remediation materials for Sb-contaminated soils. The prediction models can provide promising tools of assessing the ecological risk. In addition, Sb availability was also affected by the oxidation of Sb(III). After 150 days aging, 1-61% of Sb(III) was oxidized to pentavalent Sb [Sb(V)], which was significantly positively correlated with available Sb, suggesting that Sb(III) oxidization mobilizes Sb in soils. All these findings would help to understand Sb migration and transformation in soils, and to develop new strategies for remediating Sb-contaminated soils.

Impact of Biochars on the Iron Plaque Formation and the Antimony Accumulation in Rice Seedings.

Biochar was a kind of restoration material for soil pollution. Investigation about biochar amendment on the Sb transformation in rice plants is scarce. The pot experiment was conducted to evaluate the impact of biochar on the iron plaque formation in Sb-contaminated soil, and the translocation and accumulation of Sb in rice seedings. After the straw and husk biochar amendments (5% by weight), the levels increased on average by 20.0% and 16.0% for exchangeable Sb in soil, and by 233.3% and 74.8% for soluble Sb in pore water, respectively; but the residual fractions of Sb decreased by 18.5% and 15.1%. The iron plaque formation on rice root surface was enhanced, but its sequestration capacity for Sb decreased due to increasing competition for binding sites led by the elevated phosphorus and silicon levels in pore water after biochar application. The shoot Sb content sharply increased by 215.8% upon straw biochar application.

Removal performance and mechanisms of Pb(II) and Sb(V) from water by iron-doped phosphogypsum: single and coexisting systems.

The serious environmental risks caused by Pb(II) and Sb(V) co-contamination increase the need for their efficient and simultaneous removal. In this study, the remediation feasibility by Fe-doped phosphogypsum (FPG) was elucidated for single systems with Pb or Sb pollutant and coexisting systems with both from water. As for single systems, Fe doping effectively enhanced the Pb(II) removal performance by phosphogypsum (PG) at low Pb(II) concentrations of below 100 mg/L via the combination of precipitation and complexation. The optimal removal rate of Sb(V) by FPG increased by 2.08-3.31 times as compared to that of by PG (10-120 mg/L), mainly due to the strong affinity of iron hydroxyl (≡Fe-O-H) towards Sb(V). Compared with the single systems, the coexistence greatly enhanced the Pb(II) and Sb(V) removal performance by FPG, and the interaction behavior between Pb(II) and Sb(V) on the FPG was concentration dependent. Briefly, the sorption of FPG controlled the elimination of low coexisting concentrations of Pb(II) and Sb(V), whereas the co-precipitation process between Pb(II) and Sb(V) predominated with high ions concentration. The significant synergistic effects were found during the removal of Pb(II) and Sb(V) on FPG in the coexisting system, which mainly attributed to precipitation, bridging complexation and electrostatic attraction. Considering the advantages such as facile preparation, low cost and high removal capacity, FPG is a promising material to uptake Pb(II) and/or Sb(V) from contaminated water.

Aerosol mass and size-resolved metal content in urban Bangkok, Thailand.

Inhalable particulate matter (PM) is a health concern, and people living in large cities such as Bangkok are exposed to high concentrations. This exposure has been linked to respiratory and cardiac diseases and cancers of the lung and brain. Throughout 2018, PM was measured in northern Bangkok near a toll road (13.87°N, 100.58°E) covering all three seasons (cool, hot and rainy). PM10 was measured in 24- and 72-h samples. On selected dates aerodynamic size and mass distribution were measured as 3-day samples from a fixed 5th floor inlet. Particle number concentration was measured from the 5th floor inlet and in roadside survey measurements. There was a large fraction of particle number concentration in the sub-micron range, which showed the greatest variability compared with larger fractions. Metals associated with combustion sources were most found on the smaller size fraction of particles, which may have implications for associated adverse health outcomes because of the likely location of aerosol deposition in the distal airways of the lung. PM10 samples varied between 30 and 100 µg m-3, with highest concentrations in the cool season. The largest metal fractions present in the PM10 measurements were calcium, iron and magnesium during the hot season with average airborne concentrations of 13.2, 3.6 and 2.0 µg m-3, respectively. Copper, zinc, arsenic, selenium, molybdenum, cadmium, antimony and lead had large non-crustal sources. Principal component analysis (PCA) identified likely sources of the metals as crustal minerals, tailpipe exhaust and non-combustion traffic. A health risk analysis showed a higher risk of both carcinogenic and non-carcinogenic health effects in the drier seasons than the wet season due to ingestion of nickel, arsenic, cadmium and lead.

Hydrochemical evaluation of groundwater quality and human health risk assessment of trace elements in the largest mining district of South Khorasan, Eastern Iran.

The groundwater resources of mining areas have been in a challenging condition in terms of metal pollution and human health. Therefore, this study investigated the concentration of cobalt (Co), molybdenum (Mo), selenium (Se), tin (Sn), and antimony (Sb) in groundwater samples (wells, qanats, and springs) in a heavily contaminated mining district, South Khorasan, Eastern Iran. Human health risk of the studied metals to target groups was assessed, and water quality of the studied groundwater was investigated in the study area. A total of 367 sampling sites (279 wells, 74 qanats, and 14 springs) in South Khorasan Province were selected to collect the groundwater samples from June to July 2020. Sampling was performed thrice for each sampling point, and hydrochemical parameters were evaluated using a portable multiparameter. Inductively coupled plasma mass spectrometry (ICP-MS) was used to detect the metal concentrations. Results showed an order of Se > Mo > Sn > Co > Sb, and hazard index (HI) demonstrated a warning condition for south of South Khorasan (drinking application), southwest of South Khorasan (Irrigation application), and east and center of South Khorasan (drinking-irrigation application). Hydrochemical parameters showed a classification of "Na + K type" and "Mixed Ca-Mg-Cl type" with an overall group of "Na-Cl-HCO3" for sampled waters. Ficklin-Caboi diagram depicted a classification of "near-neutral low metal," and Schoeller diagram classified studied groundwater as "good" for drinking and irrigation consumptions and "Na-Cl" type based on ion balance diagram. Based on the correlation analysis, positive relationships were recorded among EC, TDS, Cl-, Na+, sulfate, Ca2+, salt, total hardness, Mg2+, ammonia, and K+ measured in the water samples. In essence, arid regions of the world greatly rely upon groundwater resources for drinking and irrigation consumptions, and mining districts with a heavy load of active mines can be a serious threat to the groundwater quality and human health.

Stabilization of arsenic and antimony Co-contaminated soil with an iron-based stabilizer: Assessment of strength, leaching and hydraulic properties and immobilization mechanisms.

Soils with relatively high concentrations of arsenic (As) and antimony (Sb) in mining areas would impose significant risks to human health and ecosystem. A new stabilizer PFSC composed of polymerized ferric sulfate (PFS) and calcium hydroxide (Ca(OH)2) is proposed to stabilize the soil with co-existed As and Sb sampled at an abandoned arsenic factory site. The effects of stabilizer dosage on the properties of the stabilized soil including leached concentrations of As and Sb, unconfined compressive strength (UCS), and hydraulic conductivity (kw) were investigated. The mechanisms of As and Sb immobilization in the soils were interpreted by Tessier's sequential extraction procedure (SEP), scanning electron microscope (SEM), and X-ray diffraction (XRD) results. The results showed increasing PFSC dosage was effective for reducing leached concentrations of As and Sb. When the PFSC dosage increased from 2% to 10%, the UCS and kw increased from 84 to 206 kPa and decreased from 6.48 × 10-8 to 6.33 × 10-9 m s-1, respectively. Tessier's SEP results showed that the leachable As and Sb fractions decreased from 12% to 5.6% and 7.5% to 3.8%, while the Fe-Mn oxides bound fractions increased from 22.3% to 29.4% and 13.2% to 19.5%. The SEM images and XRD patterns of untreated and PFSC stabilized contaminated soils indicated that hematite and calcite (CaCO3) were the main products of PFSC stabilization processes. Adsorption on ferrihydrite, entrapment in hematite lattices, and co-precipitate with calcite might were the main mechanisms of As and Sb immobilization.

Fast automated method for the direct determination of total antimony in grape juice samples by hydride generation and atomic fluorescence spectrometric detection without external pretreatment.

Matrix complexity of fruit juices and their low antimony level requires sensitive, cost-effective instruments, time-consuming and error-prone sample pretreatment methods. Therefore, a flow-batch procedure (HG-FBA-AFS) was developed for the fast and sensitive determination of total inorganic Sb in grape juice samples by hydride generation atomic fluorescence spectrometry. The sample pretreatment, pre-reduction and stibine formation steps run through the mixing chamber. The HCl and NaBH4 concentrations, and carrier gas flowrate were optimized through a Box-Behnken design. The detection limit (LOD) was 20 ng L-1, intra and inter-day precision ranged in 3.0 - 3.5 %, and low errors within (- 2.4 to 6.6 %) for samples containing 1.23 - 4.58 µg L-1 total Sb. Both HG-FBA-AFS and reference method agreed at 95% confidence level. An 87 h-1 sample throughput, and a 1.15 mL total waste per determination attest that HG-FBA-AFS is a fast, and ecofriendly tool for determining Sb in grape juices.

Evaluation of Pollution Level, Spatial Distribution, and Ecological Effects of Antimony in Soils of Mining Areas: A Review.

The first global-scale assessment of Sb contamination in soil that was related to mining/smelting activities was conducted based on 91 articles that were published between 1989 and 2021. The geographical variation, the pollution level, the speciation, the influencing factors, and the environmental effects of Sb that were associated with mining/smelting-affected soils were analyzed. The high Sb values mainly occurred in developed (Poland, Italy, Spain, Portugal, New Zealand, Australia) and developing (China, Algeria, Slovakia) countries. Sb concentrations of polluted soil from mining areas that were reported in most countries significantly exceeded the maximum permissible limit that is recommended by WHO, except in Turkey and Macedonia. The soil Sb concentrations decreased in the order of Oceania (29,151 mg/kg) > North Africa (13,022 mg/kg) > Asia (1527 mg/kg) > Europe (858 mg/kg) > South America (37.4 mg/kg). The existing extraction methods for Sb speciation have been classified according to the extractant, however, further research is needed in the standardization of these extraction methods. Modern analytical and characterization technologies, e.g., X-ray absorption spectroscopy, are effective at characterizing chemical speciation. Conditional inference tree (CIT) analysis has shown that the clay content was the major factor that influenced the soil Sb concentration. Non-carcinogenic risks to the public from soil Sb pollution were within the acceptable levels in most regions. An Sb smelter site at the Endeavour Inlet in New Zealand, an abandoned open-pit Sb mine in Djebel Hamimat, Algeria, an old Sb-mining area in Tuscany, Italy, and Hillgrove mine in Australia were selected as the priority control areas. Cynodon dactylon, Boehmeria, Pteris vittata, and Amaranthus paniculatus were found to be potential Sb accumulators. All of the values of bioaccumulation factors for the crops were less than one. However, ingestion of Sb through crop consumption posed potential non-carcinogenic health risks, which should not be neglected. The soil variables (pH, Eh, total sulfur, carbon nitrogen ratio, total organic carbon, and sulfate), the total Sb and the bioavailable Sb, and heavy metal(loid)s (As, Pb, and Fe) were the major parameters affecting the microbial community compositions.

Accumulation, regional distribution, and environmental effects of Sb in the largest Hg-Sb mine area in Qinling Orogen, China.

In this study, knowledge gaps on Sb concentration in rocks, ores, tailings, soil, river water, sediments, and crops of mine areas were identified and discussed in terms of contamination levels, spatial distribution, and environmental effects. Accordingly, Xunyang Hg-Sb mine, the largest Hg-Sb deposit in China as research region in this study, field sampling and laboratory analysis were conducted. The results showed elevated concentrations of Sb in the soil, sediment, and river water. The X-ray diffraction analysis indicated that the main minerals of the rocks were quartz, dolomite, calcite, and margarite. Based on the TESCAN integrated mineral analyzer analysis, the main ore minerals in the Gongguan mine were dolomite (93.97%), cinnabar (2.50%), stibnite (2.48%), calcite (0.38%), and quartz (0.38%). The µ-XRF analysis indicated that Sb distribution was similar to those of S and O, instead of those of Hg and As. The clear spatial variation of Sb concentration in environmental media, mines, tailings, and settling ponds affected Sb accumulation. Actinobacteriota, Proteobacteria, Acidobacteriota, and Chloroflexi were the dominant phyla in the soil. Patescibacteria, Proteobacteria, and Bdellovibrionota were negatively correlated with Sb in the soil (p < 0.05). Exposure to Sb through maize grain and cabbage consumption poses serious non-carcinogenic health risk for residents. This work provides a scientific basis for the environmental quality assessment of Sb mine areas and development of applicable guidelines.

Source identification and groundwater health risk assessment of PTEs in the stormwater runoff in an abandoned mining area.

Xikuangshan antimony mine in Lengshuijiang, China, has been developed for many years, and stormwater runoff contains high levels of potentially toxic elements (PTEs). The aims were to find the sources of PTEs by statistical analysis and local spatial distribution of industrial activity and simulate transport process of PTEs in the soil to evaluate pollution extent and health risk. The PTEs in this study were antimony, cadmium, zinc, nickel, lead, and copper. The result showed antimony and a minor portion of zinc were derived from the antimony processing activities, copper derived from agricultural activities, and most of the zinc came from the zinc industry. Nickel, lead, and cadmium came from a mixed source of atmospheric transportation, vehicle transport, and other local industrial activities. Besides, antimony was the most hazardous element in this mining area. In the fourth year, the groundwater in the whole area was uncontaminated by antimony, and there was no non-carcinogenic health risk. Except for the southern area of Lianxi River and the area enclosed by South mine, Zhumushan village, and Tailing Dam, there was a non-carcinogenic risk at year 5.4. These sources of PTEs found in the stormwater runoff are useful for locals to control of PTEs pollution. And the health risk assessment method helps evaluate the risk of PTEs caused by stormwater runoff.

Impacts of Redox Conditions on Arsenic and Antimony Transformation in Paddy Soil: Kinetics and Functional Bacteria.

Arsenic (As) and antimony (Sb) are known carcinogens and are present as contaminants in paddy soils. However, the complicated dynamics of the mobility of these metalloids have not been well understood due to changing redox conditions in paddy soils. Herein, the kinetics of dissolved As and Sb, and functional bacteria/genes were examined in a paddy soil cultured under aerobic and anaerobic conditions. Under aerobic condition, dissolved As(V) and Sb(V) increased constantly due to sulfide oxidation by O2 and bound As and Sb were released. Under anaerobic condition, the reduction of As(V) and Sb(V) occurred, and the mobility of As and Sb were affected by soil redox processes. The bacteria with functional genes aioA and arrA were responsible for the direct As/Sb transformation, while Fe- and N-related bacteria had an indirect effect on the fate of As/Sb via coupling with the redox processes of Fe and N. These findings improve understanding of the mobility of As and Sb in paddy soil systems under different redox conditions.

Effect of antimony in soils of an Sb mine on the photosynthetic pigments and antioxidant system of Dittrichia viscosa leaves.

Antimony is a toxic element whose concentration in soil and water has been rising due to anthropogenic activities. This study focuses on its accumulation in leaves of Dittrichia viscosa growing in soils of an abandoned Sb mine, and the effect on oxidant/antioxidant systems and photosynthetic efficiency. The results showed leaves to have a high Sb accumulation capacity. The amount of total chlorophyll decreased depending on Sb concentration and of carotenoids increased slightly, with a consequent increase in carotenoid/chlorophyll ratio. Photosynthetic efficiency was unaffected. The amount of O 2 .- rose, although there was no increase in cell membrane damage, with lipid peroxidation levels being similar to normal. This response may be due to considerable increases that were observed in total phenolics, PPO activity, and enzymatic antioxidant system. SOD, POX, and DHAR activities increased in response to increased Sb amounts in leaves. The ascorbate/glutathione cycle was also affected, with strong increases observed in all of its components, and consequent increases in total contents of the ascorbate and glutathione pools. However, the ratio between reduced and oxidized forms declined, reflecting an imbalance between the two, especially that between GSH and GSSG. Efficient detoxification of Sb may take place either through increases in phenolics, carotenoids, and components of the glutathione-ascorbate cycle or through the enzymatic antioxidant system. Since Dittrichia viscosa accumulates large amounts of Sb without suffering oxidative damage, it could be used for phytoremediation.

Investigation of pollution history in XKS mining area in China using dendrochronology and LA-ICP-MS.

Past pollution episodes and the intensity of mining activity in a contaminated region can be unraveled, using archived elemental information in tree rings. Elemental dendrochronology can be utilized with laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to make a timeline of metal(loid)s uptake in trees. In this study, six tree core samples from five tree species were collected around the XKS antimony mine region in Hunan, China, which is impacted by metal pollution: NM1 shuitong (Camptotheca acuminate L.), M1 shuitong (Camptotheca acuminate L.), G1 xiangchun (Toona sinensis L.), J2 wutong (Firmiana platanifolia L.), BSN kulian (Melia azedarach L.), and MT1 zhang (Cinnamomum camphora L.). Tree cores were dated by counting annual rings, and concentrations of As, Ca, Pb, Sb, and Zn were determined using LA-ICP-MS. Results demonstrate that the highest concentrations of Sb are present in the areas closer to mining activity: NM1 - north mine (shuitong), MT1 - mine tailing site (zhang), and BSN - between south and north mine (kulian) tree cores have average Sb concentrations of 18.8 mg/kg, 13 mg/kg, and 4.8 mg/kg, respectively. In comparison, at the village sites located farther away from the mining areas, G1 xiangchun, J2 wutong, and M1 shuitong have average Sb concentrations of 0.69 mg/kg, 0.57 mg/kg, and 0.66 mg/kg, respectively. NM1 shuitong, G1 xiangchun, and MT1 zhang all have large Sb and Zn peaks around 1986, while BSN kulian has larger Sb peaks slightly later around 1988-1990. J2 wutong has Sb peaks somewhat earlier, at 1977 and 1980. Unlike the others trees, M1 shuitong has greater Sb concentrations in more recent years (2009, 2015-2016) demonstrating Sb pollution.