Understanding of aquaporins (AQPs) facilitating the transport of water and many other small solutes including metalloids like silicon (Si) and arsenic (As) is important to develop stress tolerant cultivars. In the present study, 40 AQPs were identified in the genome of pigeonpea (Cajanus cajan), a pulse crop widely grown in semi-arid region and areas known to affected with heavy metals like As. Conserved domains, variation at NPA motifs, aromatic/arginine (ar/R) selectivity filters, and pore morphology defined here will be crucial in predicting solute specificity of pigeonpea AQPs. The study identified CcNIP2-1 as an AQP predicted to transporter Si (beneficial element) as well as As (hazardous element). Further Si quantification in different tissues showed about 1.66% Si in leaves which confirmed the predictions. Furthermore, scanning electron microscopy showed a higher level of Si accumulation in trichomes on the leaf surface. A significant alleviation in level of As, Sb and Ge stress was also observed when these heavy metals were supplemented with Si. Estimation of relative water content, H₂O₂, lipid peroxidation, proline, total chlorophyll content and other physiological parameters suggested Si derived stress tolerance. Extensive transcriptome profiling under different developmental stages from germination to senescence was performed to understand the tissue-specific regulation of different AQPs. For instance, high expression of TIP3s was observed only in reproductive tissues. Co-expression network developed using transcriptome data from 30 different conditions and tissues, showed interdependency of AQPs. Expression profiling of pigeonpea performed using real time PCR showed differential expression of AQPs after Si supplementation. The information generated about the phylogeny, distribution, molecular evolution, solute specificity, and gene expression dynamics in article will be helpful to better understand the AQP transport system in pigeonpea and other legumes.

Exposure of the general population to airborne metals remains poorly estimated despite the potential health risks. Passive moss biomonitoring can proxy air quality at fine resolution over large areas, mainly in rural areas. We adapted the technique to urban areas to develop fine concentration maps for several metals for Constances cohort's participants. We sampled Grimmia pulvinata in 77 and 51 cemeteries within ∼50 km of Paris and Lyon city centers, respectively. We developed land-use regression models for 14 metals including cadmium, lead, and antimony; potential predictors included the amount of urban, agricultural, forest, and water around cemeteries, population density, altitude, and distance to major roads. We used both kriging with external drift and land use regression followed by residual kriging when necessary to derive concentration maps (500 × 500 m) for each metal and region. Both approaches led to similar results. The most frequent predictors were the amount of urban, agricultural, or forest areas. Depending on the metal, the models explained part of the spatial variability, from 6% for vanadium in Lyon to 84% for antimony in Paris, but mostly between 20% and 60%, with better results for metals emitted by human activities. Moss biomonitoring in cemeteries proves efficient for obtaining airborne metal exposures in urban areas for the most common metals.

We aimed to explore the effects of mixtures of lead and various metals on blood pressure (BP) and the odds of pre-hypertension (systolic blood pressure (SBP) 120–139 mmHg, and/or diastolic blood pressure (DBP) 80–89 mmHg) and hypertension (SBP/DBP ≥140/90 mmHg) among Chinese adults in a cross-sectional study. This study included 11,037 adults aged 18 years or older from the 2017–2018 China National Human Biomonitoring. Average BP and 13 metals (lead, antimony, arsenic, cadmium, mercury, thallium, chromium, cobalt, molybdenum, manganese, nickel, selenium, and tin) in blood and urine were measured and lifestyle and demographic data were collected. Weighted multiple linear regressions were used to estimate associations of metals with BP in both single and multiple metal models. Weighted quantile sum (WQS) regression was performed to assess the relationship between metal mixture levels and BP. In the single metal model, after adjusting for potential confounding factors, the blood lead levels in the highest quartile were associated with the greater odds of both pre-hypertension (odds ratio (OR): 1.56, 95% CI: 1.22–1.99) and hypertension (OR:1.75, 95% CI: 1.28–2.40) when compared with the lowest quartile. We also found that blood arsenic levels were associated with increased odds of pre-hypertension (OR:1.31, 95% CI:1.00–1.74), while urinary molybdenum levels were associated with lower odds of hypertension (OR:0.68, 95% CI:0.50–0.93). No significant associations were found for the other 10 metals. WQS regression analysis showed that metal mixture levels in blood were significantly associated with higher SBP (β = 1.56, P < 0.05) and DBP (β = 1.56, P < 0.05), with the largest contributor being lead (49.9% and 66.8%, respectively). The finding suggests that exposure to mixtures of metals as measured in blood were positively associated with BP, and that lead exposure may play a critical role in hypertension development.

Antimony (Sb) and arsenic (As) are chemical analogs, but their behaviors in plants are different. To investigate the Sb uptake, translocation and speciation in As-hyperaccumulator P. cretica, a hydroponic experiment was conducted. In this study, P. cretica was exposed to 0.2-strength Hoagland nutrient solution, which contained 0.5 or 5 mg/L antimonite (SbIII) or antimonate (SbV). After 14 d exposure, P. cretica took up 1.4–2.8 times more SbIII than SbV. Since P. cretica was unable to translocate Sb, its roots accumulated >97% Sb with the highest at 7965 mg/kg. In both SbIII and SbV treatments, SbIII was the predominant species in P. cretica, with 90–100% and 46–100% SbIII in the roots. As the first barrier against Sb to enter plant cells, more Sb was accumulated in cell wall than cytosol or organelles. The results suggest that P. cretica may detoxify Sb by reducing SbV to SbIII and immobilizing it in root cell walls. Besides, the presence of SbIII significantly reduced the concentrations of dissolved organic C including organic acids in P. cretica root exudates. Further, increasing Sb levels promoted P accumulation in the plant, especially in the fronds, which may help P. cretica growth. The information from this study shed light on metabolic transformation of Sb in As-hyperaccumulators P. cretica, which helps to better understand Sb uptake and detoxification by plants.

Microbial-mediated Sb volatilization is a poorly understood part of the Sb biogeochemical cycle. This is mostly due to a lack of laboratory and field-deployable methods that are capable of quantifying low-level emissions of Sb from diffuse sources. In this study, we validated two methods using a H₂O₂ -HNO₃ liquid chemotrap and an activated coconut shell charcoal solid-phase trap, achieving an absolute limit of detection of 4.6 ng and below 2.0 ng Sb, respectively. The activated charcoal solid-phase trapping method, the most easily operated method, was then applied to contaminated shooting range soils. Four treatments were tested: 1) flooded, 2) manure amended + flooded, 3) 70 % water holding capacity, and 4) manure amendment +70 % water holding capacity, since agricultural practices and flooding events may contribute to Sb volatilization. Volatile Sb was only produced from flooded microcosms and manure amendment greatly influenced the onset and amount of volatile Sb produced. The highest amount of volatile Sb produced, up to 62.1 ng kg⁻¹ d⁻¹, was from the flooded manure amended soil. This suggests that anaerobic microorganisms may potentially be drivers of Sb volatilization. Our results show that polluted shooting range soils are a source of volatile Sb under flooded conditions, which may lead to an increase in the mobility of Sb. Some of these volatile Sb species are toxic and genotoxic, highlighting the role of Sb volatilization on environmental health, especially for individuals living in contaminated areas exposed to wetlands or flooded conditions (e.g., rice paddy agriculture surrounding mining areas). This work paves way for research on Sb volatilization in the environment.

Pollution by antimony (Sb) and arsenic (As) in soil can pose a great threat to human health. Straw-returning is widely applied to paddy fields for improving and remediating soil. A pot experiment was conducted to investigate the effect of straw-returning on Sb and As transformation and translocation in a soil–rice system. In this study, Sb and As co-contaminated soil was thoroughly mixed with different proportions (0, 0.5, 1, and 2%) of straw and used for growing rice plants through the entire growing stage in a pot experiment and 4 weeks in a microcosm experiment. The straw application significantly increased Sb and As mobility. The concentrations of total Sb and As in soil-pore water increased after the application of straw in most growing stages. The Sb volatilization in the pot and microcosm experiments was also stimulated by straw application. With the high dose of straw application (2%), the concentration of Sb in brown grain was reduced by 72% compared with the control, but As concentrations increased by around 77%. These findings provide a new perspective in that straw-returning could affect the behavior of both Sb and As in soil and reduce the Sb accumulation in brown grain and some guidance in the use of straw-returning in Sb-contaminated paddy soil.

Trace elements and Hg isotopic composition were investigated in mineralized rocks, barren rocks, and mineral soils in the Xianfeng prospect, a shallow buried epithermal gold deposit in northeastern China, to understand whether this deposit has left a diagnostic geochemical fingerprint to its weathered horizon. All the rocks and soils display congruent patterns for immobile elements (large ion lithophile elements, high field strength elements, and rare earth elements), which reflect the subduction-related tectonic setting. Both mineralized rocks and soils showed common enrichment of elemental suite As–Ag–Sb–Hg, suggesting that the Xianfeng gold deposit has released these elements into its weathered horizon. Similar mercury isotopic composition was observed between mineralized rocks (δ²⁰²Hg: −0.21 ± 0.70‰; Δ¹⁹⁹Hg: −0.02 ± 0.12‰; 2SD) and barren rocks (δ²⁰²Hg: −0.46 ± 0.48‰; Δ¹⁹⁹Hg: 0.00 ± 0.10‰; 2SD), suggesting that mercury in the Xianfeng deposit is mainly derived from the magmatic rocks. Mineralized soils (δ²⁰²Hg: −0.44 ± 0.60‰; −0.03 ± 0.14‰; 2SD) and barren soils (δ²⁰²Hg: −0.54 ± 0.68‰; Δ¹⁹⁹Hg: −0.05 ± 0.14‰; 2SD) displayed congruent Hg isotopic signals to the underlying rocks, suggesting limited Hg isotope fractionation during the release of Hg from ore deposit to soils via weathering. This study reveals evidence of a simple and direct geochemical link between this shallow buried hydrothermal deposit and its weathered horizon, and highlights that the weathering of shallow-buried hydrothermal gold deposits can release a substantial amount of heavy metals (e.g. Hg, As and Sb) to surface soil.

Antimonite [Sb(III)] and antimonate [Sb(V)] are known to have different toxicity to plants, but the corresponding mechanisms are not fully understood. This study was conducted to investigate reactive oxygen species (ROS), antioxidant systems, and levels of certain essential elements in response to exposure to Sb(III) and Sb(V). Results showed that exposure to Sb(V) caused oxidative stress in a rice plant (Yangdao No.6). Sb(III) was shown to be more toxic than Sb(V) as judged from a lower shoot biomass, a higher loss of essential elements, and higher production of superoxide anion free radicals (O₂⁻). The toxicity of Sb(III) might partially be due to the disturbance of the O₂ˉ dismutation reaction, which resulted in root cell membrane damage under exposure to 20 mg L⁻¹ Sb(III). Sb(V) stimulated the shoot fresh weight and the shoot uptake of many essential elements. Moreover, Sb(V) and Sb(III) both stimulated the accumulation of calcium in the shoots and roots, and calcium was found to significantly correlate with the concentrations of many essential elements and with some parameters correlated to antioxidant systems, suggesting a Ca-induced regulatory mechanism. The activity of glutathione peroxidase was significantly enhanced by Sb(V) and Sb(III), suggesting a role in scavenging hydrogen peroxide. Catalase was activated by exposure to 20 mg L⁻¹ Sb(III) in the roots and by exposure to 20 mg L⁻¹ Sb(V) both in the shoots and roots. However, peroxidase was activated by exposure to 5 mg L⁻¹ Sb(III) in the shoots and by exposure to 5 mg L⁻¹ Sb(V) in the roots. This study, for the first time, showed the differences between Sb(V) and Sb(III) toxicity when looking at the antioxidant response and essential element uptake.

Soil organic matter (SOM) affects arsenic (As) and antimony (Sb) mobility in soils under waterlogged conditions by acting as an electron donor, by catalyzing redox–cycling through electron shuttling and by acting as a competing ligand. This study was set up to disentangle these different effects of SOM towards As and Sb sorption in anaerobic soils. Nine samples were taken at different depths in an agricultural soil profile to collect samples with a natural SOM gradient (<1–40 g soil organic carbon kg⁻¹). The samples were incubated either or not under waterlogged conditions in an anaerobic chamber for 63–70 days, and glucose (5 g C kg⁻¹) was either or not added to the anaerobic incubated samples as an electron donor that neither acts as an electron shuttle nor as a competing ligand. The solid-liquid distribution coefficients (KD) of As and Sb were measured at trace levels. The KD values of As decreased ∼2 orders of magnitude upon waterlogging the SOM rich topsoil, while no additional changes were observed when glucose was added. In contrast, smaller changes in the As KD values were found in the low SOM containing subsoil samples, unless glucose was added that mobilised As. The Sb KD values increased upon reducing conditions up to factor 20, but again only in the high SOM topsoil samples. Surprisingly, the Sb immobilisation during waterlogging only occurred in Sb amended soils whereas the geogenic Sb was mobilised upon reducing conditions, although total dissolved Sb concentrations remained low (<10 nM). The change in As and Sb sorption upon waterlogging was similar in the SOM rich topsoil as in the low SOM subsoil amended with glucose. This suggests that the SOM dependent changes in As and Sb mobility in response to soil waterlogging are primarily determined by the role of SOM as electron donor.

Exposure to environmental metals has been reported to be associated with airway inflammation. Fractional exhaled nitric oxide (FeNO) is an important inflammatory biomarker of the airway. However, the associations between metal exposures and FeNO change and the underlying mechanisms remain unclear. To investigate the associations between urinary metals and FeNO, and the potential role of Club cell secretory protein (CC16), a lung epithelial biomarker, in these associations. We conducted a cross-sectional study from the Wuhan-Zhuhai cohort and measured eight urinary metals, plasma CC16 and FeNO among 3067 subjects by using inductively coupled plasma-mass spectrometry, enzyme-linked immunosorbent assay kit and Nano Coulomb Nitric Oxide Analyzer, respectively. Mixed linear models were used to quantify dose-relationships between urinary metals and FeNO, as well as urinary metals and plasma CC16. The potential role of plasma CC16 in the associations between urinary metals and FeNO was estimated using mediationanalyses. After adjusting for covariates, one percent increase in urinary vanadium, nickel or antimony was associated with a respective 6.60% (95% CI: 3.52%, 9.68%), 2.18% (0.45%, 3.91%), 4.87% (1.47%, 8.27%) increase in FeNO level. The adverse associations were much stronger among participants with low concentration of plasma CC16 than those with high CC16 level. Moreover, plasma CC16 decreased monotonically with increasing quartiles of urinary vanadium, nickel or antimony. Mediation analyses found that CC16 mediated the associations between urinary metals and FeNO by 5.64%, 39.06% and 25.18% for vanadium, nickel and antimony respectively. CC16 plays an important role in airway inflammation. General population with lower plasma CC16 concentration is more likely to suffer from airway inflammation when exposed to high levels of vanadium, nickel or antimony.