The adsorption-diffusion model and biomimetic simulation reveal the switchable roles of silicon in regulating toxic metal uptake in rice roots.

Soil contamination by heavy metals has become a serious threat to global food security. The application of silicon (Si)-based materials is a simple and economical method for producing safe crops in contaminated soil. However, the impact of silicon on the heavy-metal concentration in plant roots, which are the first line in the chain of heavy-metal entering plants and causing stress and the main site of heavy-metal deposition in plants, remains puzzling. We proposed a process-based model (adsorption-diffusion model) to explain the results of a collection of 28 experiments on alleviating toxic metal stress in plants by Si. Then we evaluated the applicability of the model in Si-mitigated trivalent chromium (Cr[III]) stress in rice, taking into account variations in experimental conditions such as Cr(III) concentration, stress duration, and Si concentration. It was found that the adsorption-diffusion model fitted the experimental data well (R2 > 0.9). We also verified the binding interaction between Si and Cr in the cell wall using SEM-EDS and XPS. In addition, we designed a simplified biomimetic device that simulated the Si in cell wall to analyze the dual-action switch of Si from increasing Cr(III) adsorption to blocking Cr(III) diffusion. We found that the adsorption of Cr(III) by Si decreased from 58% to 7% as the total amount of Cr(III) increased, and finally the diffusion blocking effect of Si dominated. This study deepens our understanding of the role of Si in mitigating toxic metal stress in plants and is instructive for the research and use of Si-based materials to improve food security.

Transcriptomics, proteomics, and metabolomics interventions prompt crop improvement against metal(loid) toxicity.

The escalating challenges posed by metal(loid) toxicity in agricultural ecosystems, exacerbated by rapid climate change and anthropogenic pressures, demand urgent attention. Soil contamination is a critical issue because it significantly impacts crop productivity. The widespread threat of metal(loid) toxicity can jeopardize global food security due to contaminated food supplies and pose environmental risks, contributing to soil and water pollution and thus impacting the whole ecosystem. In this context, plants have evolved complex mechanisms to combat metal(loid) stress. Amid the array of innovative approaches, omics, notably transcriptomics, proteomics, and metabolomics, have emerged as transformative tools, shedding light on the genes, proteins, and key metabolites involved in metal(loid) stress responses and tolerance mechanisms. These identified candidates hold promise for developing high-yielding crops with desirable agronomic traits. Computational biology tools like bioinformatics, biological databases, and analytical pipelines support these omics approaches by harnessing diverse information and facilitating the mapping of genotype-to-phenotype relationships under stress conditions. This review explores: (1) the multifaceted strategies that plants use to adapt to metal(loid) toxicity in their environment; (2) the latest findings in metal(loid)-mediated transcriptomics, proteomics, and metabolomics studies across various plant species; (3) the integration of omics data with artificial intelligence and high-throughput phenotyping; (4) the latest bioinformatics databases, tools and pipelines for single and/or multi-omics data integration; (5) the latest insights into stress adaptations and tolerance mechanisms for future outlooks; and (6) the capacity of omics advances for creating sustainable and resilient crop plants that can thrive in metal(loid)-contaminated environments.

Unveiling mechanisms of silicon-mediated resistance to chromium stress in rice using a newly-developed hierarchical system.

Silicon (Si) has been well-known to enhance plant resistance to heavy-metal stress. However, the mechanisms by which silicon mitigates heavy-metal stress in plants are not clear. In particular, information regarding the role of Si in mediating resistance to heavy-metal stress at a single cell level is still lacking. Here, we developed a hierarchical system comprising the plant, protoplast, and suspension cell subsystems to investigate the mechanisms by which silicon helps to alleviate the toxic effects of trivalent chromium [Cr(III)] in rice. Our results showed that in whole-plant subsystem silicon reduced shoot Cr(III) concentration, effectively alleviating Cr(III) stress in seedlings and causing changes in antioxidant enzyme activities similar to those observed at lower Cr(III) concentrations without silicon added. However, in protoplast subsystem lacking the cell wall, no silicon deposition occurred, leading to insignificant changes in cell survival or antioxidation processes under Cr(III) stress. Conversely, in suspension cell subsystem, silicon supplementation substantially improved cell survival and changes in antioxidant enzyme activities under Cr(III) stress. This is due to the fact that >95% of silicon was on the cell wall, reducing Cr(III) concentration in cells by 7.7%-10.4%. Collectively, the results suggested that the silicon deposited on the cell wall hindered Cr(III) bio-uptake, which consequently delayed Cr(III)-induced changes in antioxidant enzyme activities. This research emphasizes the significance of cell walls in Si-alleviated heavy-metal stress and deepens our understanding of silicon functioning in plants. Furthermore, the hierarchical system has great potential for application in studying the functioning of other elements in plant cell walls.

Multi-imaging platform for rhizosphere studies: Phosphorus and oxygen fluxes.

Rhizosphere is a soil volume of high spatio-temporal heterogeneity and intensive plant-soil-microbial interactions, for which visualization and process quantification is of highest scientific and applied relevance, but still very challenging. A novel methodology for quick assessment of two-dimensional distribution of available phosphorus (P) in rhizosphere was suggested, tested, and development up to the application platform. Available P was firstly trapped by an in-situ diffusive gradients in thin-films (DGT) sampler with precipitated zirconia as the binding gel, and subsequently, the loaded gel was analyzed with an optimized colorimetric imaging densitometry (CID). The imaging platform was established linking: i) DGT, ii) planar optode, and iii) soil zymography techniques to simultaneously determine available P, oxygen, and acid phosphatase in rhizosphere at sub-millimeter spatial scales. The DGT identified available P level in rice rhizosphere were spatially overlapping to the localized redox hotspots and phosphatase activity. The spatial relationship between available P and acid phosphatase activity was dependent on root development. The root radial oxygen loss (ROL) remained active during the experimental observations (2-3 days), while a flux of available P of 10 pg cm-2 s-1 was visualized within 2-3 mm of roots, confirming the correlative response of rice roots to oxygen secretion and P uptake. Summarizing, the established imaging platform is suitable to capture spatial heterogeneity and temporal dynamics of root activities, nutrient bioavailability, ROL and enzyme activities in rhizosphere.

Total contents, fractionation and bioaccessibility of nine heavy metals in household dust from 14 cities in China.

The potential health risk caused by long-term exposure to heavy metals in household dust is not only depended on their total content, but also bioaccessibility. In this study, twenty-one dust samples were collected from residential buildings, schools, and laboratories in 14 provincial-capital/industrial cities of China, aiming to evaluate the total contents, fractionation, bioaccessibility and health risks of nine heavy metals (As, Cd, Cr, Ni, Pb, Mn, Zn, Fe, and Cu). Results showed that the highest levels of Cd, Cr, Ni and Zn were found in laboratory dust, As, Pb and Mn in school dust, and Fe and Cu in residential dust, indicating different source profiles of the heavy metals. The mean bioaccessibility of the heavy metals across all samples as evaluated using SBRC (Solubility Bioavailability Research Consortium), IVG (In Vitro Gastrointestinal), and PBET (Physiologically Based Extraction Test) assays was 58.4%, 32.4% and 17.2% in gastric phase (GP), and 24.9%, 21.9% and 9.39% in intestinal phase (IP), respectively. Cadmium had the highest content in the fractions of E1+C2 (43.7%), as determined by sequential extraction, and Pb, Mn, and Zn had a higher content in E1+C2+F3 (64.2%, 67.2%, 78.8%), resulting in a higher bioaccessibility of these heavy metals than others. Moreover, the bioaccessibility of most heavy metals was inversely related to dust pH (R = -0.18 in GP; -0.18 in IP; P < 0.01) and particle size, while a positive correlation was observed with total organic carbon (R = 0.40 in GP; 0.38 in IP; P < 0.01). The exposure risk calculated by the highest bioaccessibility was generally lower than that calculated by the total content. However, Pb in one school dust sample had an unacceptable carcinogenic risk (adult risk = 1.19 × 10-4; child risk = 1.08 × 10-4). This study suggests that bioaccessibility of heavy metals in household dust is likely related to geochemical fractions and physical/chemical properties. Further research is needed to explore the sources of bioaccessible heavy metals in household dust.

High-resolution chemical imaging to understand Cd activation in rice rhizosphere of karstic soils.

Cadmium (Cd) activation, especially at a high spatial resolution, in paddy soils with a high geogenic Cd background is yet to be understood. To investigate the temporal and spatial patterns of Cd activation in rice rhizosphere, pot and rhizotron experiments were conducted using four paddy soils with high geogenic Cd (0.11-3.70 mg kg-1) from Guangxi, southwestern China. The pot experiment results showed that porewater Cd concentrations initially decreased and then increased over the complete rice growth period, reaching its lowest value during the late-tillering and early-filling stages. Besides, correlation analysis identified organic matter and root manganese (Mn) content as the main factors affecting rice Cd uptake, with Mn having a negative effect and organic matter having a positive effect. Sub-millimeter two-dimensional chemical imaging revealed that the distribution of labile Cd in the rhizosphere (by diffusive gradients in thin-films, or DGT) was influenced by the root system and soil properties, such as pH (by planar optode) and acid phosphatase activity (by soil zymography). Soil acid phosphatase activity increased under Cd stress. The overall pH at rice rhizosphere decreased. Moreover, a close relationship was found between the spatial distributions of soil labile Mn and Cd at the rhizosphere, with higher Mn being associated with lower Cd lability. This study highlights Mn as a key element in regulating rice Cd uptake and enlightens future Mn-based strategies for addressing Cd pollution in rice paddy soils, especially in karst areas with high geochemical background.

Insight into the availability and desorption kinetics of Se and Cd in naturally-rich soils using diffusive gradients in thin-films technique.

Cadmium (Cd) contamination of selenium (Se)-rich soils may jeopardize the nutritional benefits of Se-biofortified crops. This study employed diffusive gradients in thin-films (DGT) technique and DIFS (DGT-induced fluxes in soils) model to understand the interdependency and driving factors of Se and Cd distribution and desorption kinetics across 50 soils from south China with naturally elevated levels. DGT-labile Se was the highest (up to 2.66 µg L-1) in non-carbonate/shale-derived soils, while Cd was maximal (5.53 µg L-1) in carbonate-based soils, reflecting soil background concentrations and soil characteristics. Over one-third of the soils showed labile Se:Cd molar ratio below 0.7, suggesting Cd phytotoxicity risks. The DIFS-derived response times (Tc) and desorption rate constants (k-1) suggested that Se was resupplied to the soil solution faster than Cd in soils with higher pH and SOM level, but Se resupply was still restricted due to the rapid depletion of its labile pool. As the first study of Se and Cd release kinetics in soils, our results reveal dependence on soil parent materials, with low labile Se:Cd soils presenting greater Cd hazards. By elucidating Se and Cd lability and interactions in soils, our findings help to inform management strategies to balance reduced Cd risk with adequate Se availability.

Enhanced lead phytoextraction and soil health restoration through exogenous supply of organic ligands: Geochemical modeling".

Phytoremediation of lead (Pb) contaminated soil is a green technology to reduce Pb exposure and root exudates-derived organic acids play a vital role in this treatment process. In this study, Pb hyperaccumulator Pelargonium hortorum was chosen to investigate root-induced organic acid secretions and their subsequent role in Pb phytoextraction. In the first step, root exudation of P. hortorum was investigated in hydroponic experiments (0.2X Hoagland solution) under control and Pb stress conditions. Possible chemical interactions between Pb and the observed root exudates were then analyzed using Visual MINTEQ modeling. In the next step, the effects of the exogenous application of organic acids on Pb phytoextraction and soil enzymatic activities were studied in a pot experimental setup. Results indicated significant exudation of malic acid > citric acid > oxalic acid > tartaric acid in root exudates of P. hortorum under 50 mg L-1 Pb. Visual MINTEQ modeling results revealed that organic acids directly affect Pb dissolution in the nutrient solution by modulation of solution pH. Experimental results revealed that malic acid and citric acid significantly increased available Pb contents (7.2- and 6.7-folds) in the soil with 1500 mg kg-1 Pb contamination. Whereas, in shoot and root, the highest increase in Pb concentration was observed with citric acid (2.01-fold) and malic (3.75-fold) supplements, respectively. Overall, Pb uptake was notably higher when malic acid was applied (2.8-fold) compared to other organic acids, followed by citric acid (2.7-fold). In the case of soil enzymatic activities, oxalic acid significantly improved dehydrogenase, alkaline phosphatase, and microbial biomass by 1.6-, 1.4- and 1.3-folds, respectively. The organic acids were successful in reviving enzyme activity in Pb-contaminated soil, and might thus be used for long-term soil regeneration.

Fate of Cd during mineral transformation by sulfate-reducing bacteria in clay-size fractions from soils with high geochemical background.

Sulfate-reducing bacteria (SRB) can immobilize heavy metals in soils through biomineralization, and the parent rock and minerals in the soil are critical to the immobilization efficiency of SRB. To date, there is little knowledge about the fate of Cd associated with the parent rocks and minerals of soil during Cd immobilized by SRB. In this study, we created a model system using clay-size fraction of soil and SRB to explore the role of SRB in immobilizing Cd in soils from stratigraphic successions with high geochemical background. In the system, clay-size fractions (particle size < 2 µm) with concentration of Cd (0.24-2.84 mg/kg) were extracted from soils for bacteria inoculation. After SRB reaction for 10 days, the Cd fraction tended to transform into iron-manganese bound. Further, two clay-size fractions, i.e., the non-crystalline iron oxide (Fe-OX) and the crystalline iron oxide (Fe-CBD), were separated by extraction. The reaction of SRB with them verified the transformation of primary iron-bearing minerals into secondary iron-bearing minerals, which contributed to Cd redistribution. This study shows that SRB could exploit the composition and structure of minerals to induce mineral recrystallization, thereby aggravating Cd redistribution and immobilization in clay-size fractions from stratigraphic successions with high geochemical background.

Mechanistic Insights into the Biodegradation of Carbon Dots by Fungal Laccase.

While carbon dots (CDs) have the potential to support the agricultural revolution, it remains obscure about their environmental fate and bioavailability by plants. Fungal laccase-mediated biotransformation of carbon nanomaterials has received little attention despite its known capacity to eliminate recalcitrant contaminants. Herein, we presented the initial investigation into the transformation of CDs by fungal laccase. The degradation rates of CDs were determined to be first-order in both substrate and enzyme. Computational docking studies showed that CDs preferentially bonded to the pocket of laccase on the basal plane rather than the edge through hydrogen bonds and hydrophobic interactions. Electrospray ionization-Fourier transform-ion cyclotron resonance mass spectrometry (ESI-FT-ICR MS) and other characterizations revealed that the phenolic/amino lignins and tannins portions in CDs are susceptible to laccase transformation, resulting in graphitic structure damage and smaller-sized fragments. By using the 13C stable isotope labeling technique, we quantified the uptake and translocation of 13C-CDs by mung bean plants. 13C-CDs (10 mg L-1) accumulated in the root, stem, and leaf were estimated to be 291, 239, and 152 µg g-1 at day 5. We also evidenced that laccase treatment alters the particle size and surface chemistry of CDs, which could facilitate the uptake of CDs by plants and reduce their nanotoxicity to plants.

Role of iron manganese plaque in the safe production of rice (Oryza sativa L.) grains: Field evidence at plot and regional scales in cadmium-contaminated paddy soils.

The relationship between iron manganese plaque (IP) and cadmium (Cd) accumulation by rice in the microenvironment of rice rhizosphere at varying field scales needs to be further explored. In this study, we selected different rice varieties and implemented tailored amendments to ensure the safe production of rice grains in heavily Cd-contaminated farmland situated around an E-waste dismantling site. Through regional surveys, we elucidated the role of IP in facilitating safe rice production. The selection of low-Cd accumulating rice varieties and application of appropriate amendments with sufficient dosages allowed for the effective reduction of Cd transport from soil to rice, resulting in a safe concentration of Cd in rice grains. Analysis using a random forest algorithm indicated that iron (Fe) played a more pivotal role than manganese in soil-rice systems in mitigating Cd accumulation in brown rice. The presence of Fe in IP (IP-Fe) at a low loading mass was unfavorable to the Cd-safe production of rice, while at an IP-Fe loading mass of 52 g/kg, the Cd content in brown rice decreased to a safe level. Furthermore, precipitation, coprecipitation, and complexation of surface functional groups contributed to Cd fixation on IP, as indicated by scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy, electron probe microanalysis, and Fourier-transform infrared spectroscopy with attenuated total reflection. Our results highlighted the key role of IP in the production of Cd-safe rice at different field scales.

Prediction of cadmium contents in rice grains from Quaternary sediment-distributed farmland using field investigations and machine learning.

The Quaternary sediment-distributed regions of South China are suitable for rice cultivation, which is crucial for ensuring food security. Spatial correlations between soil cadmium (Cd) and rice Cd contents are generally poor, making the evaluation of rice quality and associated health risks challenging. In this study, we developed machine learning algorithms for predicting rice Cd contents using 654 data pairs of soil-rice samples collected in Guangxi province, China. After a comprehensive comparison, our results showed that the random forest (RF) had the better performance than artificial neural network (ANN) based on all the data (RMSEtesting 0.066 vs. 0.099 and R2testing 0.860 vs. 0.688). The feature importance analysis showed that soil CaO, Cd, elevation, and rainfall were the four most important features affecting the rice Cd contents in the study area. Using the established RF-predicated model, the rice Cd contents were predicted at the provincial level with an additional dataset of 1176 paddy soil samples. The prediction result revealed about 23 % of farmland cultivated rice with Cd content over 0.2 mg kg-1 in the study area. Therefore, it is recommended to implement strict measures by local agricultural departments to reduce rice Cd contents and ensure food safety in these areas. Our study provides valuable insights into the prediction of rice Cd contents, thus contributing to ensuring food safety and preventing Cd exposure-associated health risks.

Geochemical fractionation, bioaccessibility and ecological risk of metallic elements in the weathering profiles of typical skarn-type copper tailings from Tongling, China.

Nonferrous metal tailings have long posed a significant threat to the surrounding environment and population. Previous studies have primarily focused on heavy metal pollution in the vicinity of sulfide tailings, while little attention was given to metal mobility and bioavailability within skarn-type tailings profile during weathering. Therefore, this study aimed to investigate the fractionation, bioaccessibility, and ecological risk associated with metallic elements (MEs, including Pb, Cd, Cr, Zn, and Cu) in two representative weathering copper-tailings profiles of Tongling mine (China). This was achieved through the use of mineralogical analyses, BCR extractions (F1: exchangeable, F2: reducible, F3: oxidizable, F4: residual fraction), in-vitro gastrointestinal simulation test (PBET) and risk assessment models. The mineral compositions of two weathering profiles were similar, with quartz and calcite being the dominant minerals, along with minor amounts of siderite, hematite and spangolite. The mean concentration in the tailings profile was approximately 0.31 (Cr), 1.8 (Pb), 12 (Zn), 33 (Cd) or 34 (Cu) times of the local background values (LBVs). The mean content of the bottom weakly-weathering layer in profile was about 0.36 (Cr), 0.91 (Pb), 1.91 (Cd), 2.73 (Zn) or 2.68 (Cu) times of the surface oxide layer, indicating a strong weathering-leaching effect. The average proportion of BCR-F1 fraction for Cd (30.94 %) was the highest among the five MEs, possibly due to its association with calcite. The PBET-extracted fractions for Cd, Zn and Cu were significantly positively correlated with the F1, F2 and F3 fractions of BCR, suggesting that these elements have higher bioavailability/bioaccessibility. The assessment results indicated that Cd posed a higher health risk, while the risk of Cu, Zn, and Pb is relatively low and Cr is safe. In conclusion, this study provides valuable insights into the environmental geochemical behavior and potential risks of MEs in skarn-type non-ferrous metal tailings ponds.

Comparison of in vitro strategies for predicting Dichlorodiphenyltrichloroethane (DDT) and its metabolites bioavailability from soils.

In vitro strategies have widely been used to assess bioaccessibility of organic pollutants in soils. However, studies for comparing in vitro models with in vivo data are still limited. In this study, Dichlorodiphenyltrichloroethane (DDT) and its metabolites (called as DDTr) bioaccessibility in nine contaminated soils were measured using physiologically based extraction test (PBET), in vitro digestion model (IVD), and Deutsches Institut für Normung (DIN) with/without Tenax as an absorptive sink, and DDTr bioavailability was assessed using an in vivo mouse model. Whether or not Tenax was added, DDTr bioaccessibility significantly varied among three methods, suggesting that DDTr bioaccessibility depended on the in vitro method employed. Multiple linear regression analysis indicated that sink, intestinal incubation time and bile content are identified to be the dominant factors in controlling DDTr bioaccessibility. Comparison of in vitro and in vivo results demonstrated that DIN assay with Tenax (TI-DIN) provided the best prediction for DDTr bioavailability (r2 = 0.66, slope=0.78). After extending intestinal incubation time to 6 h or increasing bile content to 4.5 g/L (same to DIN assay) of the TI-PBET and TI-IVD assays, the in vivo-in vitro correlation will improved significantly, with r2 = 0.76 and slope= 1.4 for TI-PBET and r2 = 0.84 and slope= 1.9 for TI-IVD under 6 h intestinal incubation, and r2 = 0.59 and slope= 0.96 for TI-PBET and r2 = 0.51 and slope= 1.0 for TI-IVD under 4.5 g/L of bile content. The results suggest that it is essential to understand these key factors influencing bioaccessibility for the development of standardized in vitro methods, which helps to refine the risk assessment of human exposure to contaminants via soil ingestion.

Qualitative and quantitative analysis for Cd2+ removal mechanisms by biochar composites from co-pyrolysis of corn straw and fly ash.

Removal of heavy metals (e.g., Cd) from contaminated water using waste-converted adsorbents is promising, but the efficiency still needs to be improved. Here, we prepared a functional biochar composite as novel Cd adsorbents by co-pyrolysis of two typical solid wastes, i.e., agricultural corn straw and industrial fly ash. The adsorption behavior and mechanism were investigated using batch and column adsorption experiments and modern characterization techniques. Results showed that alkali-modified fly ash (AMFA) was loaded onto the surface of the corn straw biochar as some fine particle forms, with quartz (SiO2) and silicate being the main mineral phases on the surface. The maximum sorption capacity fitted by Langmuir model for functionalized biochar composite (FBC700) was up to 137.1 mg g-1, which was 7.7 times higher than that of the original corn straw biochar (BC700). Spectroscopic analysis revealed that adsorption mechanisms of Cd onto the FBC700 included mainly precipitation and ion exchange, with complexation and Cd-π interaction also contributing. The AMFA could effectively improve the mineral precipitation with Cd. The adsorption columns filled with FBC700 exhibited a longer breakthrough time than that filled with BC700. The adsorption capacity calculated by Thomas model for FBC700 was also approximately 6.0 times higher than that for BC700, showing that FBC700 was more suited to practical applications. This study provided a novel perspective for recycling solid wastes and treating Cd-contaminated water.

Human nails as a valuable noninvasive alternative for estimating exposure to parabens.

Exposure of human to parabens (commonly used preservatives) is inevitable due to their extensively applied in numerous consumer products. Thus, a reliable noninvasive matrix reflecting long-term exposure to parabens is essential for human biomonitoring study. Human nails are potentially a valuable alternative for measuring intergrated exposure to parabens. In this work, we collected 100 paired nail and urine samples from university students in Nanjing, China, and measured simultaneously for six parent parabens and four metabolites. Methylparaben (MeP), ethylparaben (EtP), and propylparaben (PrP) were three predominant paraben analogue in both matrices, with the median concentrations being 12.9, 0.753, and 3.42 ng/mL in urine, and 1540, 154, and 961 ng/g in nail, respectively, while 4-hydroxybenzoic acid (4-HB) and 3,4-dihydroxybenzoic acid (3,4-DHB) were the most abundant metabolites (median values of 143 and 35.9 ng/mL, respectively) in urine. Gender-related analysis suggested that females exposed to more higher parabens than males. Significantly positive correlations were found between levels of MeP, PrP, EtP, and OH-MeP (r = 0.54-0.62, p < 0.01) in paired urine and nail samples. Our result here suggests that human nails, as an emerging biospecimen, are a potentially valuable biological matrix to evaluate human long-term exposure to parabens.

Probability of cultivating Se-rich maize in Se-poor farmland based on intensive field sampling and artificial neural network modelling.

Selenium (Se) is a necessary micronutrient for humans, and its supplementation from crop grains is important to address the ubiquitous Se deficiency in people worldwide. Se uptake by crops largely depend on soil bioavailable Se rather than soil total Se content, which provides possibilities to explore the Se-rich crops in Se-poor area. Here, the possibility of cultivating Se-rich maize grains in Se-poor farmland was tested based on intensive field sampling and mathematical modelling. Sampling was conducted at county scale, and a total of 7779 topsoil samples and 109 maize samples with paired rhizosphere soils samples were collected. Results showed that although the soil Se content in the study county from southwestern China was at a low level (0.01-2.75 mg kg-1), 54.1% of the maize grain samples satisfied the standard for Se-rich products (0.02-0.30 mg kg-1). Soil organic matter, iron oxide, and phosphorus levels were correlated negatively with Se bioconcentration factor (BCF) of maize grain. Compared with the multivariate linear regression model, the artificial neural network (ANN) model was more accurate and reliable in predicting maize Se BCF. Prediction using the ANN model showed that 22.7% of the county's farmland was suitable for cultivating naturally Se-rich maize, which increased 21.3% growing areas than that from cultivation based on simply soil total Se. This study provided a new methodological framework for natural Se-rich maize production and verified the probability of cultivating naturally Se-rich maize in Se-poor farmland.

Selenium Increased Arsenic Accumulation by Upregulating the Expression of Genes Responsible for Arsenic Reduction, Translocation, and Sequestration in Arsenic Hyperaccumulator Pteris vittata.

Selenate enhances arsenic (As) accumulation in As-hyperaccumulator Pteris vittata, but the associated molecular mechanisms are unclear. Here, we investigated the mechanisms of selenate-induced arsenic accumulation by exposing P. vittata to 50 µM arsenate (AsV50) and 1.25 (Se1.25) or 5 µM (Se5) selenate in hydroponics. After 2 weeks, plant biomass, plant As and Se contents, As speciation in plant and growth media, and important genes related to As detoxification in P. vittata were determined. These genes included P transporters PvPht1;3 and PvPht1;4 (AsV uptake), arsenate reductases PvHAC1 and PvHAC2 (AsV reduction), and arsenite (AsIII) antiporters PvACR3 and PvACR3;2 (AsIII translocation) in the roots, and AsIII antiporters PvACR3;1 and PvACR3;3 (AsIII sequestration) in the fronds. The results show that Se1.25 was more effective than Se5 in increasing As accumulation in both P. vittata roots and fronds, which increased by 27 and 153% to 353 and 506 mg kg-1. The As speciation analyses show that selenate increased the AsIII levels in P. vittata, with 124-282% more AsIII being translocated into the fronds. The qPCR analyses indicate that Se1.25 upregulated the gene expression of PvHAC1 by 1.2-fold, and PvACR3 and PvACR3;2 by 1.0- to 2.5-fold in the roots, and PvACR3;1 and PvACR3;3 by 0.6- to 1.1-fold in the fronds under AsV50 treatment. Though arsenate enhanced gene expression of P transporters PvPht1;3 and PvPht1;4, selenate had little effect. Our results indicate that selenate effectively increased As accumulation in P. vittata, mostly by increasing reduction of AsV to AsIII in the roots, AsIII translocation from the roots to fronds, and AsIII sequestration into the vacuoles in the fronds. The results suggest that selenate may be used to enhance phytoremediation of As-contaminated soils using P. vittata.

Nickel bioaccessibility in soils with high geochemical background and anthropogenic contamination.

Abnormally high concentrations of metals including nickel (Ni) in soils result from high geochemical background (HB) or anthropogenic contamination (AC). Metal bioaccessibility in AC-soils has been extensively explored, but studies in HB-soils are limited. This study examined the Ni bioaccessibility in basalt and black shale derived HB-soils, with AC-soils and soils without contamination (CT) being used for comparison. Although HB- and AC-soils had similar Ni levels (123 ± 43.0 vs 155 ± 84.7 mg kg-1), their Ni bioaccessibility based on the gastric phase of the Solubility Bioaccessibility Research Consortium (SBRC) in vitro assay was different. Nickel bioaccessibility in HB-soils was 6.42 ± 3.78%, 2-times lower than the CT-soils (12.0 ± 9.71%) and 6-times lower than that in AC-soils (42.6 ± 16.3%). Based on the sequential extraction, a much higher residual Ni fractionation in HB-soils than that in CT- and AC-soils was observed (81.9 ± 9.52% vs 68.6 ± 9.46% and 38.7 ± 16.0%). Further, correlation analysis indicate that the available Ni (exchangeable + carbonate-bound + Fe/Mn hydroxide-bound) was highly correlated with Ni bioaccessibility, which was also related to the organic carbon content in soils. The difference in co-localization between Ni and other elements (Fe, Mn and Ca) from high-resolution NanoSIMS analysis provided additional explanation for Ni bioaccessibility. In short, based on the large difference in Ni bioaccessibility in geochemical background and anthropogenic contaminated soils, it is important to base contamination sources for proper risk assessment of Ni-contaminated soils.