Multifunctional Roles of Zinc in Cadmium Transport in Soil-Rice Systems: Novel Insights from Stable Isotope Fractionation and Gene Expression.

The effect of Zn on Cd accumulation in rice varies under flooding and drainage conditions, and the underlying mechanism during uptake and transport from the soil to grains remains unclear. Isotope fractionation and gene expression were investigated using pot experiments under distinct water regimes and with Zn addition to gain a deeper understanding of the molecular effects of Zn on Cd uptake and transport in rice. The higher OsHMA2 expression but constitutively lower expression of zinc-regulated, iron-regulated transporter-like protein (ZIP) family genes in roots under the drainage regime than the flooding regime caused the enrichment of nonheavy Zn isotopes in the shoots relative to roots but minimally affected Cd isotopic fractionation. Drainage regime seem to exert a striking effect on the root-to-shoot translocation of Zn rather than Cd, and increased Zn transport via OsHMA2. The changes in expression patterns in response to Zn addition were similar to those observed upon switching from the flooding to drainage regime, except for OsNRAMP1 and OsNRAMP5. However, soil solution-to-rice plants and root-to-shoot fractionation toward light Zn isotopes with Zn addition (Δ66Znrice plant-soil solution = -0.49 to -0.40‰, Δ66Znshoot-root = -0.36 to -0.27‰) indicated that Zn transport occurred via nonspecific uptake pathways and OsHMA2, respectively. Accordingly, the less pronounced and minimally varied Cd isotope fractionation suggested that OsNRAMP5 and OsHMA2 are crucial for Cd uptake and root-to-shoot transport, respectively, facilitating Cd accumulation in grains. This study demonstrated that a high Zn supply promotes Cd uptake and root-to-shoot transport in rice by sharing distinct pathways, and by utilizing a non-Zn-sensitive pathway with a high affinity for Cd.

Impact of Flooding-Drainage Alternation on Fe Uptake and Transport in Rice: Novel Insights from Iron Isotopes.

Iron (Fe) isotopes were utilized to provide insights into the temporal changes underlying Fe uptake and translocation during rice growth (tillering, jointing, flowering, and maturity stages) in soil-rice systems under typical flooding-drainage alternation. Fe isotopic composition (δ56Fe values) of the soil solution generally decreased at vegetative stages in flooding regimes but increased during grain-filling. Fe plaques were the prevalent source of Fe uptake, as indicated by the concurrent increase in the δ56Fe values of Fe plaques and rice plants during rice growth. The increasing fractionation magnitude from stem/nodes I to flag leaves can be attributed to the preferred phloem transport of light isotopes toward grains, particularly during grain-filling. This study demonstrates that rice plants take up heavy Fe isotopes from Fe plaque and soil solution via strategy II during flooding and the subsequent drainage period, respectively, thereby providing valuable insights into improving the nutritional quality during rice production.

Effects of zero-valent iron added in the flooding or drainage process on cadmium immobilization in an acid paddy soil.

Zero-valent iron (ZVI) is a promising material for the remediation of Cd-contaminated paddy soils. However, the effects of ZVI added during flooding or drainage processes on cadmium (Cd) retention remain unclear. Herein, Cd-contaminated paddy soil was incubated for 40 days of flooding and then for 15 days of drainage, and the underlying mechanisms of Cd immobilization coupled with Fe/S/N redox processes were investigated. The addition of ZVI to the flooding process was more conducive to Cd immobilization. Less potential available Cd was detected by adding ZVI before flooding, which may be due to the increase in paddy soil pH and newly formed secondary Fe minerals. Moreover, the reductive dissolution of Fe minerals promoted the release of soil colloids, thereby increasing significantly the surface sites and causing Cd immobilization. Additionally, the addition of ZVI before flooding played a vital role in Cd retention after soil drainage. In contrast, the addition of ZVI in the drainage phase was not conducive to Cd retention, which might be due to the rapid decrease in soil pH that inhibited Cd adsorption and further immobilization on soil surfaces. The findings of this study demonstrated that Cd availability in paddy soil was largely reduced by adding ZVI during the flooding period and provide a novel insight into the mechanisms of ZVI remediation in Cd-contaminated paddy soils.

Roles of Chloride and Sulfate Ions in Controlling Cadmium Transport in a Soil-Rice System as Evidenced by the Cd Isotope Fingerprint.

Anions accompanying inorganic fertilizers, such as chloride and sulfate ions, potentially affect the solubility, uptake, and transport of Cd to rice grains. However, the role of anions in controlling Cd transport in the soil-soil solution-Fe plaque-rice plant continuum remains poorly understood. Cd isotope ratios were applied to Cd-contaminated soil pots, hydroponic rice, and adsorption experiments with or without KCl and K2SO4 treatments to decipher transport processes in the complex soil-rice system. The chloride and sulfate ions increased the Cd concentrations in the soil solution, Fe plaque, and rice plants. Accordingly, the magnitude of positive fractionation from soil to the soil solution was less pronounced, but that between soil and Fe plaque or rice plant is barely varied. The similar isotope composition of Fe plaque and soil, and the similar fractionation magnitude between Fe plaque and the solution and between goethite and the solution, suggested that desorption-sorption between iron oxides and the solution could be important at the soil-soil solution-Fe plaque continuum. This study reveals the roles of chloride and sulfate ions: (i) induce the mobility of light Cd isotopes from soil to the soil solution, (ii) chloro-Cd and sulfato-Cd complexes contribute to Cd immobilization in the Fe plaque and uptake into roots, and (iii) facilitate second leaves/node II-to-grain Cd transport within shoots. These results provide insights into the anion-induced Cd isotope effect in the soil-rice system and the roles of anions in facilitating Cd migration and transformation.

Transformation kinetics of exogenous nickel in a paddy soil during anoxic-oxic alteration: Roles of organic matter and iron oxides.

Nickel is generally released from flooded soils; however, the key Ni transformation processes in soils that are freshly contaminated by Ni2+ during anoxic-oxic alteration remain unclear. We developed a kinetic model to investigate the Ni transformation in paddy soils under anoxic and oxic conditions based on the results of the seven-step sequential extraction, determination of dissolved and soil organic matter, and surface site quantification, which provide the kinetic data of different Ni fractions, organic matter, and reactive sites for modeling. The dissolved, exchangeable, and specifically adsorbed Ni was gradually transferred to fulvic complex, humic complex, Fe-Mn oxide bound, and sulfide bound Ni after 40 d of anoxic incubation due to the increase in pH and soil surface sites, which were mainly induced by Fe(III) oxide reduction and soil organic matter release. The introduction of oxygen triggered a rapid release of Ni, which was ascribed to the decrease in pH and soil surface sites caused by Fe(II) oxidation and carbon re-immobilization. Kinetic modeling demonstrated that complexation with soil organic matter dominated Ni immobilization under anoxic conditions, while organic matter and Fe-Mn oxides contributed similarly to Ni release under oxic conditions, although the majority of Ni remained complexed with soil organic matter. These findings are important for the evaluation and prediction of Ni behavior in paddy soils with exogenous Ni during flooding-drainage practices.

Cadmium isotope fractionation and gene expression evidence for tracking sources of Cd in grains during grain filling in a soil-rice system.

Grain filling is the key period that causes excess cadmium (Cd) accumulation in rice grains. Nevertheless, uncertainties remain in distinguishing the multiple sources of Cd enrichment in grains. To better understand the transport and redistribution of Cd to grains upon drainage and flooding during grain filling, Cd isotope ratios and Cd-related gene expression were investigated in pot experiments. The results showed that the Cd isotopes in rice plants were much lighter than those in soil solutions (∆114/110Cdrice-soil solution = -0.36 to -0.63 ‰) but moderately heavier than those in Fe plaques (∆114/110Cdrice-Fe plaque = 0.13 to 0.24 ‰). Calculations revealed that Fe plaque might serve as the source of Cd in rice (69.2 % to 82.6 %), particularly upon flooding at the grain filling stage (82.6 %). Drainage at the grain filling stage yielded a larger extent of negative fractionation from node I to the flag leaves (∆114/110Cdflag leaves-node I = -0.82 ± 0.03 ‰), rachises (∆114/110Cdrachises-node I = -0.41 ± 0.04 ‰) and husks (∆114/110Cdrachises-node I = -0.30 ± 0.02 ‰), and significantly upregulated the OsLCT1 (phloem loading) and CAL1 (Cd-binding and xylem loading) genes in node I relative to that upon flooding. These results suggest that phloem loading of Cd into grains and transport of Cd-CAL1 complexes to flag leaves, rachises and husks were simultaneously facilitated. Upon flooding of grain filling, the positive fractionation from the leaves, rachises and husks to the grains (∆114/110Cdflag leaves/rachises/husks-node I = 0.21 to 0.29 ‰) is less pronounced than those upon drainage (∆114/110Cdflag leaves/rachises/husks-node I = 0.27 to 0.80 ‰). The CAL1 gene in flag leaves is down-regulated relative to that upon drainage. Thus, the supply of Cd from the leaves, rachises and husks to the grains is facilitated during flooding. These findings demonstrate that the excess Cd was purposefully transported to grain via xylem-to-phloem within nodes I upon the drainage during grain filling, and the expression of genes responsible for encoding ligands and transporters together with isotope fractionation could be used to tracking the source of Cd transported to rice grain.

Chromium transformation driven by iron redox cycling in basalt-derived paddy soil with high geological background values.

The flooding and drainage of paddy fields has great effects on the transformation of heavy metals, however, the transformation of Cr in basalt-derived paddy soil with high geological background values was less recognized. The typical basalt-derived paddy soil was incubated under alternating redox conditions. The Cr fractions and the dynamics of Fe/N/S/C were examined. The HCl-extractable Cr increased under anaerobic condition and then decreased during aerobic stage. The UV-vis spectra of the supernatant showed that amounts of colloids were released under anaerobic condition, and then re-aggregated during aerobic phase. The scanning transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) revealed that Fe oxides were reduced and became dispersed during anaerobic stage, whereas Fe(II) was oxidized and recrystallized under aerobic condition. Based on these results, a kinetic model was established to further distinguish the relationship between the transformation of Cr and Fe. During anaerobic phase, the reduction of Fe(III) oxides not only directly released the structurally bound Cr, but also enhanced the breakdown of soil aggregation and dissolution of organic matter causing indirect mobilization of Cr. During aerobic phase, the oxidation of Fe(II) and further recrystallization of newly formed Fe(III) oxides might induce the re-aggregation of soil colloids and further incorporation of Cr. In addition, the kinetic model of Cr and Fe transformation was further verified in the pot experiment. The model-based findings demonstrated that the Cr transformation in the basalt-derived paddy soil with high geological background values was highly driven by redox sensitive iron cycling.

Seawater intrusion induced cadmium activation via altering its distribution and transformation in paddy soil.

Seawater intrusion can cause environmental risks to paddy soils around estuaries, but the impacts on the availability of heavy metals are still unclear. River water and sea water were collected along the river of an estuary. A stirred-flow experiment was conducted to examine the Cd desorption behavior in Cd-contaminated paddy soil. While the pH increased with increasing salinity levels, more Cd was released with increasing salinity, suggesting that Cd competition by cations and complexation by anions, but not pH, dominated the release of Cd from soils. Moreover, paddy soil was incubated at different salinities under alternating redox conditions. The availability of Cd, as indicated by the diffusive gradients in thin film (DGT), became relatively high with increasing salinity levels during the initial anaerobic and later aerobic stages. The available Cd fractions substantially decreased under anaerobic condition, and then rapidly increased under aerobic condition. When oxygen was introduced into the system, Cd associated with organic matter and Fe-Mn oxides were released, and oxidative dissolution of Cd sulfides was observed, especially in the high salinity treatment. Seawater intrusion affects biogeochemical cycles and can promote rapid export of NH4+, Fe2+, and SO42- in paddy soils, especially in soils with high salinity. Our findings demonstrated that the high salinity content in paddy soil significantly enhanced the availability of Cd, especially during the drainage stage.

Effects of water salinity on cadmium availability at soil-water interface: implication for salt water intrusion.

Low-lying paddy fields in estuaries can be affected by salt water intrusion; however, it remains unclear how salt water intrusion influences the availability of heavy metals in paddy soil. In this study, batch adsorption and incubation experiments of soil were conducted with different salt water sampled along the estuary to investigate the effects of salt water intrusion on cadmium (Cd) availability. The surface complexation model (SCM) was established to assess the effects of pH on Cd adsorption behavior, which presented typical pH-dependent characteristics. The results of SCM also showed that Cd-chloro complexes became the dominant species when the ionic strength increased. The results of Cd fractions in the incubation experiments revealed a significant increase in dissolved Cd with increasing ionic strength. This may be attributed to the increased point of zero charge (pHpzc) in the presence of salt water with higher salinity, which likely formed more positive charges on soil surfaces, causing an inhibition of Cd adsorption via electrostatic repulsion. Moreover, higher concentrations of Cl- in salt water favored the formation of Cd-chloro complexes, facilitating Cd release from soil particles. This study provides mechanistic insights into the impact of salt water intrusion on Cd availability at the soil-water interface of paddy soil along the estuary.

Source and Strategy of Iron Uptake by Rice Grown in Flooded and Drained Soils: Insights from Fe Isotope Fractionation and Gene Expression.

Rice can simultaneously absorb Fe2+ via a strategy I-like system and Fe(III)-phytosiderophore via strategy II from soil. Still, it remains unclear which strategy and source of Fe dominate under distinct water conditions. An isotope signature combined with gene expression was employed to evaluate Fe uptake and transport in a soil-rice system under flooded and drained conditions. Rice of flooded treatment revealed a similar δ56Fe value to that of soils (Δ56Ferice-soil = 0.05‰), while that of drained treatment was lighter than that of the soils (Δ56Ferice-soil = -0.41‰). Calculations indicated that 70.4% of Fe in rice was from Fe plaque under flooded conditions, while Fe was predominantly from soil solution under drained conditions. Up-regulated expression of OsNAAT1, OsTOM2, and OsYSL15 was observed in the root of flooded treatment, while higher expression of OsIRT1 was observed in the drained treatment. These isotopic and genetic results suggested that the Fe(III)-DMA uptake from Fe plaque and Fe2+ uptake from soil solution dominated under flooded and drained conditions, respectively.

Cadmium uptake and transport processes in rice revealed by stable isotope fractionation and Cd-related gene expression.

Multiple processes are involved in Cd transfer in rice plants, including root uptake, xylem loading, and immobilization. These processes can be mediated by membrane transporters and can alter Cd speciation by binding Cd to different organic ligands. However, it remains unclear which processes control Cd transport in rice in response to different watering conditions in soil. Herein, Cd isotope fractionation and Cd-related gene expression were employed to investigate the key regulatory mechanisms during uptake, root-to-shoot, and stem-to-leaf transport of Cd in rice grown in pot experiments with Cd-contaminated soil under flooded and non-flooded conditions, respectively. The results showed that soil flooding decreased the Cd concentration in soil porewater and, thereby, Cd uptake and transport in rice. Cd isotopes fractionated negatively from soil porewater to the whole rice (flooded: ∆114/110Cdrice-porewater = -0.15‰, non-flooded: ∆114/110Cdrice-porewater = -0.39‰), suggesting that Cd transporters preferentially absorbed light Cd isotopes. The non-flooded treatment revealed an upregulated expression of OsNRAMP1 and OsNRAMP5 genes compared to the flooded treatment, which may partially contribute to its more pronounced porewater-to-rice fractionation. Cd isotopes fractionated positively from roots to shoots under flooded conditions (∆114/110Cdshoot-root = 0.19‰). However, a reverse direction of fractionation was observed under non-flooded conditions (∆114/110Cdshoot-root = -0.67‰), which was associated with the substantial upregulation of CAL1 in roots, facilitating xylem loading of Cd-CAL1 complexes with lighter isotopes. After being transported to the shoots, the majority of Cd were detained in stems (44%-55%), which were strongly enriched in lighter isotopes than in the leaves (∆114/110Cdleaf-stem = 0.77 to 1.01‰). Besides the Cd-CAL1 transported from the roots, the expression of OsPCS1 and OsHMA3 in the stems could also favor the enrichment of Cd-PCs with lighter isotopes, leaving heavier isotopes to be transported to the leaves. The higher expression levels of OsMT1e in older leaves than in younger leaves implied that Cd immobilization via binding to metallothioneins like OsMT1e may favor the enrichment of lighter isotopes in older leaves. The non-flooded treatment showed lighter Cd isotopes in younger leaves than the flooded treatment, suggesting that more Cd-CAL1 in the stems and Cd-PCs in the older leaves might be transported to the younger leaves under non-flooded conditions. Our results demonstrate that isotopically light Cd can be preferentially transported from roots to shoots when more Cd is absorbed by rice under non-flooded conditions, and isotope fractionation signature together with gene expression quantification has the potential to provide a better understanding of the key processes regulating Cd transfer in rice.

Water Management Alters Cadmium Isotope Fractionation between Shoots and Nodes/Leaves in a Soil-Rice System.

The drainage of rice soils increases Cd solubility and results in high Cd concentrations in rice grains. However, plant Cd uptake is limited by sorption to iron plaques, and Cd redistribution in the plant is regulated by the nodes. To better understand the interplay of Cd uptake and redistribution in rice under drained and flooded conditions, we determined stable Cd isotope ratios and the expression of genes coding transporters that can transport Cd into the plant cells in a pot experiment. In soil, both water management practices showed similar patterns of isotope variation: the soil solution was enriched in heavy isotopes, and the root Fe plaque was enriched in light isotopes. In rice, the leaves were heavier (Δ114/110Cdleaf-shoot = 0.17 to 0.96‰) and the nodes were moderately lighter (Δ114/110Cdnode-shoot = -0.26 to 0.00‰) relative to the shoots under flooded conditions, indicating preferential retention of light isotopes in nodes and export of heavy isotopes toward leaves. This is generally reversed under drained conditions (Δ114/110Cdleaf-shoot = -0.25 to -0.04‰, Δ114/110Cdnode-shoot = 0.10 to 0.19‰). The drained treatment resulted in significantly higher expression of OsHMA2 and OsLCT1 (phloem loading) but lower expression of OsHMA3 (vacuolar sequestration) in nodes and flag leaves relative to the flooded treatment. It appeared that OsHMA2 and OsLCT1 might preferentially transport isotopically heavier Cd, and the excess Cd was purposefully retranslocated via the phloem under drained conditions when the vacuoles could not retain more Cd. Cd in seeds was isotopically heavier than that in stems under both water management practices, indicating that heavy isotopes were preferentially transferred toward seeds via the phloem, leaving light isotopes retained in stems. These findings demonstrate that the Fe plaque preferentially adsorbs and occludes light Cd isotopes on the root surface, and distinct water management practices alter the gene expression of key transporters in the nodes, which corresponds to a change in isotope fractionation between shoots and nodes/leaves.

Fulvic Acid-Mediated Interfacial Reactions on Exposed Hematite Facets during Dissimilatory Iron Reduction.

Although the dual role of natural organic matter (NOM) as an electron shuttle and an electron donor for dissimilatory iron (Fe) reduction has been extensively investigated, the underlying interfacial interactions between various exposed facets and NOM are poorly understood. In this study, fulvic acid (FA), as typical NOM, was used and its effect on the dissimilatory reduction of hematite {001} and {100} by Shewanella putrefaciens CN-32 was investigated. FA accelerates the bioreduction rates of hematite {001} and {100}, where the rate of hematite {100} is lower than that of hematite {001}. Secondary Fe minerals were not observed, but the HR-TEM images reveal significant defects. The ATR-FTIR results demonstrate that facet-dependent binding mainly occurs via surface complexation between the surface iron atoms and carboxyl groups of NOM. The spectroscopic and mass spectrometry analyses suggest that organic compounds with large molecular weight, highly aromatic and unsaturated structures, and lower H/C ratios are easily adsorbed on Fe oxides or decomposed by bacteria in FA-hematite {001} treatment after iron reduction. Due to the metabolic processes of cells, a significant number of compounds with higher H/C and medium O/C ratios appear. The Tafel curves show that hematite {100} possessed higher resistance (4.1-2.6 Ω) than hematite {001} (3.5-2.2 Ω) at FA concentrations ranging from 0 to 500 mg L-1, indicating that hematite {100} is less conductive during the electron transfer from reduced FA or cells to Fe oxides than hematite {001}. Overall, the discrepancy in the iron bioreduction of two exposed facets is attributed to both the different electrochemical activities of the Fe oxides and the different impacts on the properties and composition of OM. Our findings shed light on the molecular mechanisms of mutual interactions between FA and Fe oxides with various facets.

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.

Quinone-mediated dissimilatory iron reduction of hematite: Interfacial reactions on exposed {001} and {100} facets.

Although quinone-mediated bioreduction of iron oxides has been investigated extensively, little is known about the interfacial interactions between quinone and various exposed facets. In this study, the reduction of hematite {001} and {100} by Shewanella putrefaciens CN-32 with anthraquinone-2,6-disulfonate (AQDS) was investigated. The added AQDS can enhance the bioreduction of both hematite {001} and {100}, with hematite {001} showing a higher reduction degree than hematite {100}. No significant secondary iron oxides were found, but defects were observed in HR-TEM images. AQDS sorption was higher on hematite {001} (0.13 µM m-2) than hematite {100} (0.1 µM m-2). Electron transfer rate between hematite {001} and AQDS (19.6 s-1) was higher than hematite {100} (18.2 s-1). Tafel curves revealed that hematite {001} possesses lower resistance (3.5-2.4 Ω) than hematite {100} (4.1-2.9 Ω) with AQDS from 0 to 400 µM, indicating that hematite {001} is more favorable for electron transfer from cells or anthrahydroquinone-2,6,-disulfonate (AH2QDS) to Fe oxide. In addition to the well-known electron shuttling role of AQDS, the higher adsorption sites and electrochemical activity of hematite {001} over {100} jointly contributed to the enhanced iron bioreduction. The findings provide a mechanistic understanding of the interactions between quinone and various facets of iron oxides.

Coupled Kinetics Model for Microbially Mediated Arsenic Reduction and Adsorption/Desorption on Iron Oxides: Role of Arsenic Desorption Induced by Microbes.

The dynamic behavior of arsenic (As) species is closely associated with iron mineral dissolution/transformation in the environment. Bacterially induced As(V) desorption from iron oxides may be another important process that facilitates As(V) release from iron oxides without significant reductive dissolution of iron oxides. Under the impact of bacterially induced desorption, As kinetic behavior is controlled by both the microbial reduction of As(V) and the As(III)&As(V) reactions on iron oxide surfaces. However, there is still a lack of quantitative understanding on the coupled kinetics of these processes in complex systems. We developed a quantitative model that integrated the time-dependent microbial reduction of As(V) with nonlinear As(III)&As(V) adsorption/desorption kinetics on iron oxides under the impact of bacterially induced As(V) desorption. We collected and modeled literature data from 11 representative studies, in which microbial reduction reactions occurred with minimal iron oxide dissolution/transformation. Our model highlighted the significance of microbially induced As(V) desorption and time-dependent changes of microbial reduction rates. The model can quantitatively assess the roles and the coupling of individual reactions in controlling the overall reaction rates. It provided a basis for developing comprehensive models for As cycling in the environment by coupling with other chemical, physical, and microbial processes.

Enhanced immobilization of arsenic and cadmium in a paddy soil by combined applications of woody peat and Fe(NO3)3: Possible mechanisms and environmental implications.

Organic matter (OM) plays an important role in the mobility of heavy metal(loid)s. Peat containing abundant OM can be used as an organic fertilizer improving physical and chemical properties of soil. Previous studies indicated that the immobilization of heavy metal(loid)s by peat is affected by the presence of metal oxides and/or hydroxides and that Fe-enriched peat is very effective in immobilizing metal(loid)s. Accordingly, we hypothesize that simultaneous application of peat and Fe-containing compounds may pronouncedly immobilize heavy metal(loid)s. In this study, the effects of the combined applications of woody peat and Fe(NO3)3 on As and Cd mobilities and accumulations in rice during the whole growth period were investigated by a pot experiment. The combined applications of woody peat and Fe(NO3)3 significantly decreased As(III) and Cd in porewater due to pH increases induced by applications of Fe(NO3)3, and these decreases were enhanced with increasing Fe(NO3)3. In addition, simultaneous application of peat and Fe(NO3)3 significantly decreased mobile portions of As and Cd but significantly increased their immobile portions. Increasing Fe(NO3)3 increased the amount of As immobilized by poorly crystalline Fe oxides. The formation of Fe plaques and production of poorly crystalline Fe oxides were enhanced by Fe(NO3)3 addition, which also contributed to the immobilization of As and Cd in soil. Overall, the combined applications of woody peat and Fe(NO3)3 provided a strategy for simultaneously immobilizing As and Cd in soils and further alleviating their accumulations from soil to rice plants. In paddy soil, the frequent occurrence of iron redox activity due to the alternating wetting and drying cycles provided favorable conditions for interactions between Fe and OM, and this process and its associated metal(loid) immobilization may be more important than we thought and need further study.

Selenium reduces cadmium uptake into rice suspension cells by regulating the expression of lignin synthesis and cadmium-related genes.

Although previous studies have indicated that selenium (Se) can reduce cadmium (Cd) uptake into rice, the mechanism at the cellular level has not been reported. Here, rice suspension cells exposed to Cd treatment in the presence or absence of Se were characterized. Compared with treatment with alone, pretreatment with Se increased the proportion of live cells by 83.1%. The levels of reactive oxygen species and mitochondrial membrane potential in the Se-pretreated rice cells were decreased by 86.6% and 76.0%, respectively. In addition, non-invasive micro-test technology suggested that the mean values of Cd2+ influx decreased significantly in the Se-pretreated rice cells in a concentration-dependent manner. The results of inductively coupled plasma-mass spectrometry (ICP-MS) showed that 67.4%-78.8% Cd accumulated onto the cell walls of the pretreated-Se rice cells. The addition of Se increased the lignin content and thickness of the cell walls, leading to an improved mechanical force of the cell walls, as determined by atomic force microscopy (AFM). Furthermore, Se pretreatment decreased the expression of genes involved in Cd uptake (OsNramp5) and transport (OsLCT1) but activated the expression of genes involved in Cd transport into vacuoles (OsHMA3) and lignin synthesis (OsPAL, OsCoMT and Os4CL3). These results indicated that supplying Se alleviates Cd toxicity by regulating the express of lignin synthesis and Cd-related genes. The present findings provide new insights on a plausible explanation of the Se-reduced Cd uptake into rice.

Microbial iron reduction as a method for immobilization of a low concentration of dissolved cadmium.

Much attention has been paid to the relationship between microbial iron reduction and the behavior of cadmium (Cd) recently, but most previous research has employed unrealistically high Cd concentrations (e.g., 2-55 mg L-1) and has failed to consider the effects of iron oxides and microbial cells together. We investigated the reduction of lepidocrocite by Shewanella oneidensis MR-1 in the presence of a low concentration of Cd using batch reactor systems. The results showed that with 422 µg L-1 added dissolved Cd2+, an initial 137 µg L-1 decrease in aqueous Cd occurred due to adsorption onto lepidocrocite and that the further removal of remaining aqueous Cd occurred only in the system containing bacteria. This further decrease in aqueous Cd was unlikely to be caused by mineral transformation because the microbial reduction of lepidocrocite resulted in particle-size-increased (thus, specific-surface-area-decreased) lepidocrocite, and unlikely to be caused by the pH increase to 7.4 induced by iron reduction either because a pH-adsorption edge suggested that at pH 7.4, less than 60% of aqueous Cd can be adsorbed by lepidocrocite in the reactors. An adsorption isotherm showed a significant Cd adsorption capacity by S. oneidensis MR-1 cells, and we therefore attributed the further Cd removal to adsorption by S. oneidensis MR-1 cells. The results suggest that a realistically low concentration of Cd can be immobilized during microbial iron reduction by adsorption on iron oxides and microbial cells.

Simultaneous alleviation of cadmium and arsenic accumulation in rice by applying zero-valent iron and biochar to contaminated paddy soils.

The fates of cadmium (Cd) and arsenic (As) in paddy fields are generally opposite; thus, the inconsistent transformation of Cd and As poses large challenges for their remediation. In this study, the impacts of zero valent iron (ZVI) and/or biochar amendments on Cd and As bioavailability were examined in pot trials with rice. Comparison with the untreated soil, both Cd and As accumulation in different rice tissues decreased significantly in the ZVI-biochar amendments and the Cd and As accumulation in rice decreased with increasing ZVI contents. In particular, the concentrations of Cd (0.15 ± 0.01 mg kg-1) and As (0.17 ± 0.01 mg kg-1) in rice grains were decreased by 93% and 61% relative to the untreated soil, respectively. A sequential extraction analysis indicated that with increasing Fe ratios in the ZVI-biochar mixtures, bioavailable Cd and As decreased, and the immobilized Cd and As increased. Furthermore, high levels of Fe, Cd, and As were detected in Fe plaque of the ZVI-biochar amendments in comparison with the single biochar or single ZVI amendments. The ZVI-biochar mixture may have a synergistic effect that simultaneously reduces Cd and As bioavailability by increasing the formation of amorphous Fe and Fe plaque for Cd and As immobilization. The single ZVI amendment significantly decreased As bioavailability, while the single biochar amendment significantly reduced the bioavailability of Cd compared with the combined amendments. Hence, using a ZVI-biochar mixture as a soil amendment could be a promising strategy for safely-utilizing Cd and As co-contaminated sites in the future.