Organic-mineral colloids regulate the migration and fractionation of rare earth elements in groundwater systems impacted by ion-adsorption deposits mining in South China.

Ion-adsorption rare earth element (REE) deposits distributed in the subtropics provide a rich global source of REEs, but in situ injection of REEs extractant into the mine can result in leachate being leaked into the surrounding groundwater systems. Due to the lack of understanding of REE speciation distribution, particularly colloidal characteristics in a mining area, the risks of REEs migration caused by in situ leaching of ion-adsorption REE deposits has not been concerned. Here, ultrafiltration and asymmetric flow field-flow fractionation coupled with inductively coupled plasma mass spectrometry (AF4-ICP-MS) were integrated to characterize the size and composition of REEs in leachate and groundwater from mining catchments in South China. Results show that REEs were associated with four fractions: 1) the <1 kDa fraction including dissolved REEs; 2) the 1 - 100 kDa nano-colloidal fraction containing organic compounds; 3) the 100 kDa - 220 nm fine colloids including organic-mineral (Fe, Mn and Al (oxy)hydroxides and clay minerals); 4) the >220 nm coarse colloids and acid soluble particles (ASPs) comprising minerals. Influenced by the ion exchange effect of in situ leaching, REEs in leachate were mostly dissolved (79 %). The pH of the groundwater far from the mine site was increased (5.8 - 7.3), the fine organic-mineral colloids (46 % - 80 %) were the main vectors of transport for REEs. Further analysis by AF4 revealed that the fine colloids can be divided into mineral-rich (F1, 100 kDa - 120 nm) and organic matter-rich (F2, 120 - 220 nm) populations. The main colloids associated with REEs shifted from F1 (64 % ∼ 76 %) to F2 (50 % ∼ 52 %) away from the mining area. For F1 and F2, the metal/C molar ratio decreased away from the mining area and middle to heavy REE enrichment was presented. According to the REE fractionation, organic matter was the predominant component capable of binding REEs in fine colloids. Overall, our results indicate that REEs in the groundwater system shifted from the dissolved to the colloidal phase in a catchment affected by in situ leaching, and organic-mineral colloids play an important role in facilitating the migration of REEs.

Novel Phosphate Transporter-B PvPTB1;1/1;2 Contribute to Efficient Phosphate Uptake and Arsenic Accumulation in As-Hyperaccumulator Pteris vittata.

Arsenic (As) contamination in soil poses a potential threat to human health via crop uptake. As-hyperaccumulator Pteris vittata serves as a model plant to study As uptake and associated mechanisms. This study focuses on a novel P/AsV transport system mediated by low-affinity phosphate transporter-B 1 family (PTB1) in P. vittata. Here, we identified two plasma-membrane-localized PTB1 genes, PvPTB1;1/1;2, in vascular plants for the first time, which were 4.4-40-fold greater in expression in P. vittata than in other Pteris ferns. Functional complementation of a yeast P-uptake mutant and enhanced P accumulation in transgenic Arabidopsis thaliana confirmed their role in P uptake. Moreover, the expression of PvPTB1;1/1;2 facilitated the transport and accumulation of As in both yeast and A. thaliana shoots, demonstrating a comparable AsV uptake capacity. Microdissection-qPCR analysis and single-cell transcriptome analysis collectively suggest that PvPTB1;1/1;2 are specifically expressed in the epidermal cells of P. vittata roots. PTB1 may play a pivotal role in efficient P recycling during phytate secretion and hydrolysis in P. vittata roots. In summary, the dual P transport mechanisms consisting of high-affinity Pht1 and low-affinity PTB1 may have contributed to the efficient P/As uptake in P. vittata, thereby contributing to efficient phytoremediation for As-contaminated soils.

Fe(III) transporter OsYSL15 may play a key role in the uptake of Cr(III) in rice (Oryza sativa L.).

Due to the widely discharge of chromium (Cr) by mining and smelting industries, etc., contamination of paddy soils and rice has become serious problems. Therefore it is crucial to explore how rice takes up Cr. Cr(III) is the most common Cr form in the long-term water flooding paddy soils. Here, we demonstrate that OsYSL15, a key gene for Fe(III) uptake, is equally applicable for Cr(III) uptake in rice. Firstly, the antagonistic effect of Cr(III) and Fe(III) in the uptake process was found. Rice could accumulate more Cr(III) under Fe-deficient conditions. And the Fe(III) content in the protoplasts of rice root cells gradually decreased with the increase exposure of Cr(III). Knockdown of OsYSL15 in rice significantly reduced the Cr(III) uptake rate. Compared with wild type rice, the accumulation of Cr(III) in OsYSL15 mutant was decreased by 40.7%- 70.6% after gene editing. These results indicate that OsYSL15 is a key gene responsible for Cr(III) uptake in rice, which can guide the screening or genetic modification for low-Cr-accumulation rice varieties.

Biogenic manganese oxides promote metal(loid) remediation by shaping microbial communities in biological aqua crust.

Biological aqua crust (biogenic aqua crust-BAC) is a potentially sustainable solution for metal(loid) bioremediation in global water using solar energy. However, the key geochemical factors and underlying mechanisms shaping microbial communities in BAC remain poorly understood. The current study aimed at determining the in situ metal(loid) distribution and the key geochemical factors related to microbial community structure and metal(loid)-related genes in BAC of a representative Pb/Zn tailing pond. Here we showed that abundant metal(loid)s (e.g. Pb, As) were co-distributed with Mn/Fe-rich minerals (e.g. biogenic Mn oxide, FeOOH) in BAC. Biogenic Mn oxide (i.e. Mn) was the most dominant factor in shaping microbial community structure in BAC and source tailings. Along with the fact that keystone species (e.g. Burkholderiales, Haliscomenobacter) have the potential to promote Mn ion oxidization and particle agglomeration, as well as Mn is highly associated with metal(loid)-related genes, especially genes related to As redox (e.g. arsC, aoxA), and Cd transport (e.g. zipB), biogenic Mn oxides thus effectively enhance metal(loid) remediation by accelerating the formation of organo-mineral aggregates in biofilm-rich BAC system. Our study indicated that biogenic Mn oxides may play essential roles in facilitating in situ metal(loid) bioremediation in BAC of mine drainage.

Mitigation effects of foliar supply of different sulfur forms on uptake, translocation and grain accumulation of Cd and As by paddy rice on basis of liming.

Co-contamination of Cd and As in strongly acidic paddy soil has posed great challenges for remediation practice due to their distinct properties. Liming is a necessary but inadequate measure for normal growth of paddy rice and for Cd and As remediation in strongly acidic paddy soils rich in iron minerals. A greenhouse rice pot cultivation experiment was conducted to explore the efficiency and mechanisms of how foliar supply of different sulfur forms (K2S, K2SO4) could further mediate the uptake, translocation and grain accumulation of Cd and As by paddy rice on basis of liming. Results showed that compared to liming alone (CK), co-application of liming and foliar supply of K2S (L + FK2S) significantly reduced contents of Cd and As in brown rice by 44.4 % and 24.7 %, respectively. Contrastingly, co-application of liming and foliar supply of K2SO4 (L + FK2SO4) decreased Cd content of brown rice by 55.5 %, but had no effect on As content. Foliar supply of K2S and K2SO4 dramatically facilitated Cd upward transfer from roots to shoots by enhancing root Cd transfer from cell wall into trophoplast. On the other hand, both sulfur forms remarkably elevated sulfur contents in leaves and significantly inhibited Cd translocation from leaves to grain by enhancing vacuolar sequestration of Cd in leaves. Compared to CK and L + FK2SO4 treatment, it was by enhancing glutathione synthesis, cell wall deposition in roots and vacuolar sequestration of As in leaves that L + FK2S showed greater inhibiting effects on transfer of As from roots, stems and leaves to grain. Foliar supply of either sulfate or sulfide could efficiently decrease grain Cd of paddy rice, but only foliar supply of sulfide is effective in reducing grain As.

Release of chromium from Cr(III)- and Ni(II)-substituted goethite in presence of organic acids: Role of pH in the formation of colloids and complexes.

High levels of Cr(III) are hosted in Fe (oxyhydr)oxides in soils derived on (ultra)mafic rocks, which can pose potential risks to the environment. Organic acids can cause the solubilization of Fe (oxyhydr)oxides and the release of Cr(III). However, the release behaviors of Cr(III) from Fe (oxyhydr)oxides by organic acids and its main factors remain unclear. This study investigates the speciation of Cr released from Cr(III)-substituted goethite in the presence of citrate and oxalate and the effects of pH (3-7). Batch experiments showed that Fe(III) and Cr(III) dissolution were significantly enhanced by citrate and oxalate, and the extent of dissolution was negatively correlated with pH. When at relatively high pH (5-7), AF4-ICP-MS results revealed that large proportions of dissolved Fe (>58 %) and Cr (18 %-73 %) were presented in the form of Cr(III)-citrate colloids in the sizes of 1-125 nm and 125-350 nm. Further, FTIR and cryogenic XPS characterization demonstrated that the formation of·Cr(III)-citrate colloids was attributed to the adsorption and complexation of citrate on the substituted goethite surface. However, Cr was mainly released as soluble Cr(III)-organic complexes when presented at pH 3. While low pH inhibited the formation of Cr(III)-organic colloids, it promoted the release of Cr by facilitating the dissociation of surface Cr(III)-organic complexes. In addition, the incorporation of Ni(II) in Cr(III)-substituted goethite weakened the adsorption of organic acid by shortening the crystal size of goethite, thus significantly inhibiting the formation of Cr(III)-organic complexes and colloids. This study confirms the formation of Cr(III)-organic acid colloids and highlights the importance of pH on Cr release behavior, which is essential for evaluating Cr transport and fate in soils with high background values.

New Insights into the Role of Natural Organic Matter in Fe-Cr Coprecipitation: Importance of Molecular Selectivity.

Coprecipitation of Fe/Cr hydroxides with natural organic matter (NOM) is an important pathway for Cr immobilization. However, the role of NOM in coprecipitation is still controversial due to its molecular heterogeneity and diversity. This study focused on the molecular selectivity of NOM toward Fe/Cr coprecipitates to uncover the fate of Cr via Fourier transform-ion cyclotron resonance-mass spectrometry (FT-ICR-MS). The results showed that the significant effects of Suwannee River NOM (SRNOM) on Cr immobilization and stability of the Fe/Cr coprecipitates did not merely depend on the adsorption of SRNOM on Fe/Cr hydroxides. FT-ICR-MS spectra suggested that two pathways of molecular selectivity of SRNOM in the coprecipitation affected Cr immobilization. Polycyclic aromatics and polyphenolic compounds in SRNOM preferentially adsorbed on the Fe/Cr hydroxide nanoparticles, which provided extra binding sites and promoted the aggregation. Notably, some specific compounds (i.e., polyphenolic compounds and highly unsaturated phenolic compounds), less unsaturated and more oxygenated than those adsorbed on Fe/Cr hydroxide nanoparticles, were preferentially incorporated into the insoluble Cr-organic complexes in the coprecipitates. Kendrick mass defect analysis revealed that the insoluble Cr-organic complexes contained fewer carbonylated homologous compounds. More importantly, the spatial distribution of insoluble Cr-organic complexes was strongly related to Cr immobilization and stability of the Fe/Cr-NOM coprecipitates. The molecular information of the Fe/Cr-NOM coprecipitates would be beneficial for a better understanding of the transport and fate of Cr and exploration of the related remediation strategy.

The effectiveness of sewage sludge biochar amendment with Boehmeria nivea L. in improving physicochemical properties and rehabilitating microbial communities in mine tailings.

Biochar amendment can be adopted to improve soil substrate, in turn facilitated phytoremediation. However, improvements to the properties of tailings following different feedstocks of biochar amendment in phytoremediation, particularly the impacts on nitrogen cycle and the related nitrogen-fixing microorganisms remain unclear. In this study, a 100-day pot experiment was designed to determine the co-effects of different combinations of woody and non-woody biochar, namely hibiscus cannabinus core biochar (HB), sewage sludge biochar (SB), chicken manure biochar (MB) and two crops (Cassia alata L., Boehmeria nivea L.). It was found that, on the one hand, biochar amendment directly immobilized heavy metal (loid) contamination in the tailings; on the other hand, biochar amendment, particularly non-woody SB, improved soil properties (i.e., the combination of SB with crops increased the total nitrogen content by 4.7-7.5 times). This indirectly improved phytostabilization (i.e., SB increased crop height 1.5-1.8 fold, root length 3.3-3.7 fold, decreased NH4NO3-extractable Pb, Cu, Cd and also increased the relative abundance of nitrogen-fixing bacteria such as Mesorhizobium, Bradyrhizobium, and Rhizobium). Besides this, redundant analysis shown that the carbon, nitrogen sources, and pH provided by the biochar were identified as the key factors associated with the nitrogen-fixing bacteria. Through the comprehensive evaluation of different biochar amendment in phytoremediation, it was found that the non-woody SB got higher comprehensive score (3.1-3.6) in biochar amendment in phytoremediation, especially in Boehmeria nivea L. Thus, the combination of non-woody SB and Boehmeria nivea L. improved microbial function, while the microorganisms in turn promoted crop growth. Our results revealed the prospect of using non-woody SB assisted Boehmeria nivea L. for phytoremediation in multi-metal mine tailings.

As-hyperaccumulator Pteris vittata and non-hyperaccumulator Pteris ensiformis under low As-exposure: Transcriptome analysis and implication for As hyperaccumulation.

Soil contamination by arsenic (As) poses potential health risks to humans. As-hyperaccumulator P. vittata has been used in As-contaminated soils for phytoremediation. Clarifying the mechanisms of its As-hyperaccumulation is critical to enhance its efficiency in phytoremediation. Here, based on transcriptome analysis, we determined the concentration-dependent patterns of As-related gene families by comparing As-hyperaccumulator P. vittata and non-hyperaccumulator P. ensiformis after exposing to 20 µM arsenate (AsV). As expected, arsenic induced more stress in P. ensiformis than P. vittata. Based on gene ontology, differences in transporter activity are probably responsible for their differential As accumulation. Though As exposure induced expression of phosphate transporter PvPht1;4 for AsV absorption in both plants, stronger AsV reduction, AsIII transport, and AsIII-GSH complexation were found in P. ensiformis roots. Unlike P. ensiformis, As metabolism processes occurred mainly in P. vittata fronds. Notably, tonoplast-localized ACR3s were only present in P. vittata, making it more effective in sequestrating AsIII into frond vacuoles. Further, vesicle As transformation via PvGAPC1 (glyceraldehyde 3-phosphate dehydrogenase), PvOCT4 (organic cation transporter 4), and PvGSTF1 (glutathione S-transferase) contributed little to As-hyperaccumulation. This study provides information on critical genes responsible for As-hyperaccumulation by P. vittata, which can be applied to construct As-hyperaccumulating plants by genetic engineering to enhance their phytoremediation efficiency in As-contaminated soils.

Increasing soil Mn abundance promotes the dissolution and oxidation of Cr(III) and increases the accumulation of Cr in rice grains.

Hexavalent chromium (Cr(VI)) is more readily taken up by plants than trivalent chromium (Cr(III)) due to its similar chemical structure to phosphate and sulfate. In paddy soils, Cr(VI) of natural origin are mainly produced from Cr(III) oxidized by O2 and Mn(III/IV) oxides, which are affected by rice radial oxygen loss (ROL) and Mn(II)-oxidizing microorganisms (MOM). However, little is known about the effect of ROL and Mn abundance on rice Cr uptake. Here, we investigated the effects on Cr(VI) generation and the subsequent Cr uptake and accumulation with the involvement of two rice cultivars with distinct ROL capacities by increasing soil Mn abundance. Results showed that Mn(II) addition to the soil led to more Cr(III) being released into the pore water, and the dissolved Cr(III) was oxidized to Cr(VI) by ROL and biogenic Mn(III/IV) oxides. The concentration of Cr(VI) in soil and pore water increased linearly with the addition of Mn(II) doses. Mn(II) addition promoted the root-to-shoot translocation and grain accumulation of Cr derived mainly from newly generated Cr(VI) in the soil. These results emphasize that rice ROL and MOM promote the oxidative dissolution of Cr(III) at a high level of soil Mn, resulting in more Cr accumulation in rice grains and increasing dietary Cr exposure risks.

The interplay between microalgae and toxic metal(loid)s: mechanisms and implications in AMD phycoremediation coupled with Fe/Mn mineralization.

Acid mine drainage (AMD) is low-pH with high concentration of sulfates and toxic metal(loid)s (e.g. As, Cd, Pb, Cu, Zn), thereby posing a global environmental problem. For decades, microalgae have been used to remediate metal(loid)s in AMD, as they have various adaptive mechanisms for tolerating extreme environmental stress. Their main phycoremediation mechanisms are biosorption, bioaccumulation, coupling with sulfate-reducing bacteria, alkalization, biotransformation, and Fe/Mn mineral formation. This review summarizes how microalgae cope with metal(loid) stress and their specific mechanisms of phycoremediation in AMD. Based on the universal physiological characteristics of microalgae and the properties of their secretions, several Fe/Mn mineralization mechanisms induced by photosynthesis, free radicals, microalgal-bacterial reciprocity, and algal organic matter are proposed. Notably, microalgae can also reduce Fe(III) and inhibit mineralization, which is environmentally unfavorable. Therefore, the comprehensive environmental effects of microalgal co-occurring and cyclical opposing processes must be carefully considered. Using chemical and biological perspectives, this review innovatively proposes several specific processes and mechanisms of Fe/Mn mineralization that are mediated by microalgae, providing a theoretical basis for the geochemistry of metal(loid)s and natural attenuation of pollutants in AMD.

Coalescence of As(II) with •OH: The pivot for co-processing of As(III) and butyl xanthate.

Although water metalloid pollution is widely studied, the effect of the combined pollution of organic matter and metalloids in mining water and, especially, the possible interaction mechanisms between metalloids and flotation reagents, are both poorly understood. Existence of mixed pollution of metalloids and organic compounds tends to cause more serious harm to natural organisms. In this study, a synergistic removal of arsenite (As(III)) and butyl xanthate (Bx) in an advanced oxidation system was reported using biochar-based catalyst loaded with nano-zero-valent iron from an inexpensive iron source (iron slag) to activate peroxodisulfate. The removal efficiencies were improved by 30 % in the co-existence of As(III) and Bx compared to those of the single pollutant. The theoretical calculations, especially frontier molecular orbital theory, revealed the generation of [AsO2-OH]•- by the combination of As(II) with •OH. This [AsO2-OH]•- participated in the oxidative degradation of Bx with high activity and combined with the sulfur falling off Bx after the reaction to form a novel Fe-As-S complex as indicated by X-ray absorption +fine structure analysis. Overall, this study reports the generation of low-valent arsenic active substances of [AsO2-OH]•- and their effect on the removal of organic pollution containing S atoms in advanced oxidation systems under typical mining water conditions with the coexistence of As(III) and expands the understanding and application of traditional free radicals.

Novel biological aqua crust enhances in situ metal(loid) bioremediation driven by phototrophic/diazotrophic biofilm.

BACKGROUND: Understanding the ecological and environmental functions of phototrophic biofilms in the biological crust is crucial for improving metal(loid) (e.g. Cd, As) bioremediation in mining ecosystems. In this study, in combination with metal(loid) monitoring and metagenomic analysis, we systematically evaluated the effect of biofilm in a novel biological aqua crust (biogenic aqua crust-BAC) on in situ metal(loid) bioremediation of a representative Pb/Zn tailing pond. RESULTS: We observed strong accumulation of potentially bioavailable metal(loid)s and visible phototrophic biofilms in the BAC. Furthermore, dominating taxa Leptolyngbyaceae (10.2-10.4%, Cyanobacteria) and Cytophagales (12.3-22.1%, Bacteroidota) were enriched in biofilm. Along with predominant heterotrophs (e.g. Cytophagales sp.) as well as diazotrophs (e.g. Hyphomonadaceae sp.), autotrophs/diazotrophs (e.g. Leptolyngbyaceae sp.) in phototrophic biofilm enriched the genes encoding extracellular peptidase (e.g. family S9, S1), CAZymes (e.g. CBM50, GT2) and biofilm formation (e.g. OmpR, CRP and LuxS), thus enhancing the capacity of nutrient accumulation and metal(loid) bioremediation in BAC system. CONCLUSIONS: Our study demonstrated that a phototrophic/diazotrophic biofilm constitutes the structured communities containing specific autotrophs (e.g. Leptolyngbyaceae sp.) and heterotrophs (e.g. Cytophagales sp.), which effectively control metal(loid) and nutrient input using solar energy in aquatic environments. Elucidation of the mechanisms of biofilm formation coupled with metal(loid) immobilization in BAC expands the fundamental understanding of the geochemical fate of metal(loid)s, which may be harnessed to enhance in situ metal(loid) bioremediation in the aquatic ecosystem of the mining area. Video Abstract.

Water Management Impacts on Chromium Behavior and Uptake by Rice in Paddy Soil with High Geological Background Values.

Chromium (Cr) is an expression toxic metal and is seriously released into the soil environment due to its extensive use and mining. Basalt is an important Cr reservoir in the terrestrial environment. Cr in paddy soil can be enriched by chemical weathering. Therefore, basalt-derived paddy soils contain extremely high concentrations of Cr and can enter the human body through the food chain. However, the water management conditions' effect on the transformation of Cr in basalt-derived paddy soil with high geological background values was less recognized. In this study, a pot experiment was conducted to investigate the effects of different water management treatments on the migration and transformation of Cr in a soil-rice system at different rice growth stages. Two water management treatments of continuous flooding (CF) and alternative wet and dry (AWD) and four different rice growth stages were set up. The results showed that AWD treatment significantly reduced the biomass of rice and promoted the absorption of Cr in rice plants. During the four growth periods, the root, stem and leaf of rice increased from 11.24-16.11 mg kg-1, 0.66-1.56 mg kg-1 and 0.48-2.29 mg kg-1 to 12.43-22.60 mg kg-1, 0.98-3.31 mg kg-1 and 0.58-2.86 mg kg-1, respectively. The Cr concentration in roots, stems and leaves of AWD treatment was 40%, 89% and 25% higher than CF treatment in the filling stage, respectively. The AWD treatment also facilitated the potential bioactive fractions conversion to the bioavailable fraction, compared with the CF treatment. In addition, the enrichment of iron-reducing bacteria and sulfate-reducing bacteria with AWD treatment also provided electron iron for the mobilization of Cr, thus affecting the migration and transformation of Cr in the soil. We speculated that the reason for this phenomenon may be the bioavailability of Cr was affected by the biogeochemical cycle of iron under the influence of alternating redox. This indicates that AWD treatment may bring certain environmental risks in contaminated paddy soil with high geological background, and it is necessary to be aware of this risk when using water-saving irrigation to plant rice.

Differential Effects of Senescence on the Phloem Exports of Cadmium and Zinc from Leaves to Grains in Rice during Grain Filling.

In rice, non-essential toxic cadmium (Cd) and the essential nutrient zinc (Zn) share similar transport pathways, which makes it challenging to differentially regulate the allocation of these elements to the grain. The phloem is the main pathway for the loading of these elements into rice grains. It has long been accepted that tissue senescence makes the nutrients (e.g., Zn) stored in leaves available for further phloem export toward the grain. Whether senescence could drive the phloem export of Cd remains unclear. To this end, the stable isotopes 111Cd and 67Zn were used to trace the phloem export and the subsequent allocation of Cd and Zn from the flag leaves, where senescence was accelerated by spraying abscisic acid. Furthermore, changes upon senescence in the distribution of these elements among the leaf subcellular fractions and in the expression of key transporter genes were investigated. Abscisic acid-induced senescence enhanced the phloem export of Zn but had no impact on that of Cd, which was explained by the significant release of Zn from the chloroplast and cytosol fractions (concentrations decreased by ~50%) but a strong allocation of Cd to the cell wall fraction (concentration increased by ~90%) during senescence. Nevertheless, neither Zn nor Cd concentrations in the grain were affected, since senescence strengthened the sequestration of phloem-exported Zn in the uppermost node, but did not impact that of phloem-exported Cd. This study suggests that the agronomic strategies affecting tissue senescence could be utilized to differentially regulate Cd and Zn allocation in rice during grain filling.

Characterizing the remobilization flux of cadmium from pre-anthesis vegetative pools in rice during grain filling using an improved stable isotope labeling method.

A clear understanding of the allocation of Cd to grains is essential to manage the level of Cd in cereal diets effectively. Yet, debate remains over whether and how the pre-anthesis pools contribute to grain Cd accumulation, resulting in uncertainty regarding the need to control plant Cd uptake during vegetative growth. To this end, rice seedlings were exposed to 111Cd labeled solution until tillering, transplanted to unlabeled soils, and grown under open-air conditions. The remobilization of Cd derived from pre-anthesis vegetative pools was studied through the fluxes of 111Cd-enriched label among organs during grain filling. The 111Cd label was continuously allocated to the grain after anthesis. The lower leaves remobilized the Cd label during the earlier stage of grain development, which was allocated almost equally to the grains and husks + rachis. During the final stage, the Cd label was strongly remobilized from the roots and, less importantly, the internodes, which was strongly allocated to the nodes and, to a less extent, the grains. The results show that the pre-anthesis vegetative pools are an important source of Cd in rice grains. The lower leaves, internodes, and roots are the source organs, whereas the husks + rachis and nodes are the sinks competing with the grain for the remobilized Cd. This study provides insight into understanding the ecophysiological mechanism of Cd remobilization and setting agronomic measures for lowering grain Cd levels.

Nano zero-valent iron enhances the absorption and transport of chromium in rice (Oryza sativa L.): Implication for Cr risks management in paddy fields.

Chromium (Cr) accumulating in soil caused serious pollution to cultivated land. At present, nano zero-valent iron (nZVI) is considered to be a promising remediation material for Cr-contaminated soil. However, the nZVI impact on the behavior of Cr in the soil-rice system under high natural geological background value remains unknown. We studied the effects of nZVI on the migration and transformation of Cr in paddy soil-rice by pot experiment. Three different doses of nZVI (0, 0.001 % and 0.1 % (w/w)) treatments and one dose of 0.1 % (w/w) nZVI treatment without plant rice were set up. Under continuous flooding conditions, nZVI significantly increased rice biomass compared with the control. At the same time, nZVI significantly promoted the reduction of Fe in the soil, increased the concentration of oxalate Fe and bioavailable Cr, then facilitated the absorption of Cr in rice roots and the transportation to the aboveground part. In addition, the enrichment of Fe(III)-reducing bacteria and sulfate-reducing bacteria in soil provided electron donors for Cr oxidation, which helps to form bioavailable Cr that is easily absorbed by plants. The results of this study can provide scientific basis and technical support for the remediation of Cr -polluted paddy soil with high geological background.

Mechanism of arsenic immobilization and biotransformation in the biological aqua crust of mine drainage.

Biological aqua crust (BAC), as a novel biological crust with high arsenic (As) immobilization capacity, might be an ideal nature-based solution for As removal in mine drainage. This study examined the As speciation, binding fraction and biotransformation genes in the BACs to find out the underlying mechanism of As immobilization and biotransformation. Results showed that the BACs could immobilize As from mine drainage up to 55.8 g/kg, and their As immobilization concentrations were 1.3-6.9 times higher than that of sediments. Extremely high As immobilization capacity was attributed to the processes of bioadsorption/absorption and biomineralization driven by Cyanobacteria. The high abundance of As(III) oxidation genes (27.0 %) enhanced microbial As(III) oxidation, resulting in >90.0 % of As(V) with low toxicity and mobility in the BACs. The increase in abundances of aioB, arsP, acr3, arsB, arsC and arsI with As was the key process for microbiota in the BACs for resistance to the As toxicity. In conclusion, our findings innovatively confirmed the potential mechanism of As immobilization and biotransformation mediated by the microbiota in the BACs and highlighted the important role of BACs for As remediation in mine drainage.

Adsorbed copper on urea modified activated biochar catalyzed H2O2 for oxidative degradation of sulfadiazine：Degradation mechanism and toxicity assessment.

The combined pollution of heavy metals and organic compounds usually occurs simultaneously and induces high toxicity. The technology of simultaneous removal of combined pollution is lacking and the removal mechanism is not clear. Sulfadiazine (SD), a widely used antibiotic, was used as a model contaminant. Urea modified sludge-based biochar (USBC) was prepared and used to catalyze H2O2 to remove the combined pollution of Cu2+ and sulfadiazine (SD) without causing secondary pollution. After 2 h, the removal rates of SD and Cu2+ were 100 and 64.8%, respectively. Cu2+ adsorbed on the surface of USBC accelerated the activation of H2O2 by the USBC catalyzed by CO bond to produce hydroxyl radical (•OH) and single oxygen (1O2) to degrade SD. Twenty-three intermediate products were detected, most of which were completely decomposed into CO2 and H2O. The toxicity was significantly reduced in the combined polluted system. This study highlights the potential of the low-cost technology based on sludge reuse and its inherent significance in reducing the toxic risk of combined pollution in the environment.

Plasma-Membrane-Localized Transporter NREET1 is Responsible for Rare Earth Element Uptake in Hyperaccumulator Dicranopteris linearis.

Rare earth elements (REEs) are critical for numerous modern technologies, and demand is increasing globally; however, production steps are resource-intensive and environmentally damaging. Some plant species are able to hyperaccumulate REEs, and understanding the biology behind this phenomenon could play a pivotal role in developing more environmentally friendly REE recovery technologies. Here, we identified a REE transporter NRAMP REE Transporter 1 (NREET1) from the REE hyperaccumulator fern Dicranopteris linearis. Although NREET1 belongs to the natural resistance-associated macrophage protein (NRAMP) family, it shares a low similarity with other NRAMP members. When expressed in yeast, NREET1 exhibited REE transport capacity, but it could not transport divalent metals, such as zinc, nickel, manganese, or iron. NREET1 is mainly expressed in D. linearis roots and predominantly localized in the plasma membrane. Expression studies in Arabidopsis thaliana revealed that NREET1 functions as a transporter mediating REE uptake and transfer from root cell walls into the cytoplasm. Moreover, NREET1 has a higher affinity for transporting light REEs compared to heavy REEs, which is consistent to the preferential enrichment of light REEs in field-grown D. linearis. We therefore conclude that NREET1 may play an important role in the uptake and consequently hyperaccumulation of REEs in D. linearis. These findings lay the foundation for the use of synthetic biology techniques to design and produce sustainable, plant-based REE recovery systems.