Foliar Application of Nanoparticles Reduced Cadmium Content in Wheat (Triticum aestivum L.) Grains via Long-Distance "Leaf-Root-Microorganism" Regulation.

Foliar application of beneficial nanoparticles (NPs) exhibits potential in reducing cadmium (Cd) uptake in crops, necessitating a systematic understanding of their leaf-root-microorganism process for sustainable development of efficient nano-enabled agrochemicals. Herein, wheat grown in Cd-contaminated soil (5.23 mg/kg) was sprayed with different rates of four commonly used NPs, including nano selenium (SeNPs)/silica (SiO2NPs)/zinc oxide/manganese dioxide. SeNPs and SiO2NPs most effectively reduced the Cd concentration in wheat grains. Compared to the control, Cd concentration in grains was significantly decreased by 35.0 and 33.3% by applying 0.96 mg/plant SeNPs and 2.4 mg/plant SiO2NPs, and the grain yield was significantly increased by 33.9% with SeNPs application. Down-regulated gene expression of Cd transport proteins (TaNramp5 and TaLCT1) and up-regulated gene expression of vacuolar Cd fixation proteins (TaHMA3 and TaTM20) were observed with foliar SeNPs and SiO2NPs use. SeNPs increased the levels of leaf antioxidant metabolites. Additionally, foliar spray of SeNPs resulted in lower abundances of rhizosphere organic acids and reduced Cd bioavailability in rhizosphere soil, and soil microorganisms related to carbon and nitrogen (Solirubrobacter and Pedomicrobium) were promoted. Our findings underscore the potential of the foliar application of SeNPs and SiO2NPs as a plant and rhizosphere soil metabolism-regulating approach to reduce Cd accumulation in wheat grains.

Key role of hydrogen atoms in the preparation of sulfidated zero valent iron.

Sulfidated zero valent iron (ZVI) is a popular material for the reductive degradation of halogenated organic pollutants. Simple and economic synthesis of this material is highly demanded. In this study, sulfidated micro/nanostructured ZVI (MNZVI) particles were prepared by simply heating MNZVI particles and sulfur elements (S0) in pure water (50℃). The iron oxides on the surface of MNZVI particles were conducive to sulfidation reaction, indicating the formation of iron-sulphide minerals (FeSx) on the surface of MNZVI particles might not be from the direct reaction of Fe0 with S0 (Fe0 and S0 acted as reductant and oxidant, respectively). As an important reductant, hydrogen atom (H•) can be generated from the reduction of H+ by MNZVI particles and participate in the formation of FeSx. Quenching experiment and cyclic voltammetry analysis proved the existence of H• on the surface of MNZVI particles. DFT calculation found that the potential barrier of H•/S0 and Fe0/S0 were 1.91 and 7.24 eV, respectively, indicating that S0 would preferentially react with H• instead of Fe0. The formed H• can quickly react with S0 to generate hydrogen sulfide (H2S), which can further react with iron oxides such as α-Fe2O3 on the surface of MNZVI particles to form FeSx. In addition, the H2 partial pressure in water significantly affected the amount of H• generated, thereby affecting the sulfidation efficiency. For TCE degradation, as the sulfur loading of sulfidated MNZVI particles increased, the contribution of H• significantly decreased while the contribution of direct electron transfer increased. This study provided new insights into the synthesis mechanism of sulfidated ZVI in water.

Activated Carbon Application Simultaneously Alleviates Paddy Soil Arsenic Mobilization and Carbon Emission by Decreasing Porewater Dissolved Organic Matter.

Flooding of paddy fields during the rice growing season enhances arsenic (As) mobilization and greenhouse gas (e.g., methane) emissions. In this study, an adsorbent for dissolved organic matter (DOM), namely, activated carbon (AC), was applied to an arsenic-contaminated paddy soil. The capacity for simultaneously alleviating soil carbon emissions and As accumulation in rice grains was explored. Soil microcosm incubations and 2-year pot experimental results indicated that AC amendment significantly decreased porewater DOM, Fe(III) reduction/Fe2+ release, and As release. More importantly, soil carbon dioxide and methane emissions were mitigated in anoxic microcosm incubations. Porewater DOM of pot experiments mainly consisted of humic-like fluorophores with a molecular structure of lignins and tannins, which could mediate microbial reduction of Fe(III) (oxyhydr)oxides. Soil microcosm incubation experiments cospiking with a carbon source and AC further consolidated that DOM electron shuttling and microbial carbon source functions were crucial for soil Fe(III) reduction, thus driving paddy soil As release and carbon emission. Additionally, the application of AC alleviated rice grain dimethylarsenate accumulation over 2 years. Our results highlight the importance of microbial extracellular electron transfer in driving paddy soil anaerobic respiration and decreasing porewater DOM in simultaneously remediating As contamination and mitigating methane emission in paddy fields.

Coupling of Dissolved Organic Matter Molecular Fractionation with Iron and Sulfur Transformations during Sulfidation-Reoxidation Cycling.

Iron (oxyhydr)oxides and organic matter (OM) are intimately associated in natural environments, and their fate might be linked to sulfur during sulfidation-reoxidation cycling. However, the coupling of DOM molecular fractionation with Fe and S transformations following a full sulfidation-reoxidation cycle remains poorly understood. Here, we reacted Fh and Fh-OM associations with S(-II) anaerobically and then exposed the sulfidic systems to air. S(-II) preferentially reacted with Fh to form inorganic S (e.g., mackinawite, S0, and S22-) over being incorporated into OM as organic S and therefore indirectly affected OM fate by altering Fe speciation. Fh sulfidation was inhibited by associated OM, and the main secondary Fe species were mackinawite, Fe(II)-OM compounds, and lepidocrocite. Concomitantly, organic molecules high in unsaturation, aromaticity, and molecular weight were detached from solid-phase Fe species due to their lower affinities for secondary Fe species than for Fh. During the reoxidation stage, the previously formed Fe(II) species were reoxidized to Fh with a stronger aggregation, which recaptured formerly released OM with higher selectivity. Additionally, •OH was generated from Fe(II) oxygenation and degraded a portion of the DOM molecules. Overall, these results have significant implications for Fe, C, and S cycling in S-rich environments characterized by oscillating redox conditions.

Alcohols radicals can efficiently reduce recalcitrant perfluorooctanoic acid.

Alcohols are commonly used as eluents for the regeneration of per/poly-fluoroalkyl substances (PFASs) adsorbents, but their potential effects on the subsequent treatment of these eluates have not been fully explored. This work investigated the effect of alcohols on perfluorooctanoic acid (PFOA) degradation by persulfate (PS) based advanced oxidation processes. The results showed that ethanol significantly promoted PFOA degradation in thermal/PS system. Under anoxic conditions, 25.5±1.4% or 91.2±1.6% of PFOA was degraded within 48 h in the absence or presence of ethanol. Electron paramagnetic resonance (EPR) detection, free radical quenching experiments, and chemical probe studies clearly demonstrated that the sulfate radicals (SO4•-) generated from PS activation would react with ethanol to form alcohol radicals, which could efficiently degrade PFOA. The transformation pathways of PFOA were proposed based on degradation products analysis and density function theory (DFT) calculation. The reaction between SO4•- and other alcohols could also induce the formation of alcohol radicals and facilitate to the degradation of PFOA. This work represents the positive roles of alcohols in the degradation of PFASs, providing new insights into developing simple and efficient treatments for PFASs eluate or PFAS-contaminated water.

Nano-biochar uptake and translocation by plants: Assessing environmental fate and food chain risk.

Nano-biochar (N-BC) is an emerging nanomaterial with potential applications in various fields. Understanding its behavior in the environment and its interaction with plants is crucial for assessing its ecological implications and potential risks to the food chain. In this study, we investigated the absorption and transportation of N-BC by wheat and Chinese cabbage plants using microscopy techniques and stable isotope analysis. Our results revealed that N-BC particles were readily absorbed by the plants through their root systems and transported to the aboveground tissues. Scanning electron microscopy and transmission electron microscopy provided visual evidence of N-BC particles inside the plants, predominantly located in the xylem and cell walls of the cortical tissue. Stable isotope analysis confirmed the uptake and transportation of N-BC, with elevated isotopic values observed in the plant tissues exposed to 13C-N-BC. Our results demonstrated that around 50.2 %-52.4 % of the absorbed N-BC by plants was accumulated in the roots of wheat and Chinese cabbage, and the remaining fraction was transferred to the shoots including steam (31.0 %-32.1 %) and leaf (16.5 %-17.6 %). Importantly, we observed significant accumulation of N-BC in the edible parts of Chinese cabbage, raising concerns about its potential entry into the food chain and associated health risks. These findings highlight the need for further research to explore the specific pathways and modes of N-BC uptake and transport in plants. Monitoring the presence of N-BC in the environment and its potential impact on the food chain is crucial for ensuring food security and safeguarding human health.

Sulfurization alters phenol-formaldehyde resin microplastics redox property and their efficiency in mediating arsenite oxidation.

Microplastics weathering by various types of oxidants in the oxic environment and their interaction with environmental contaminants have drawn numerous scientific attention. However, the environmental fate of microplastics under a reducing environment has been largely unresolved. Herein, the change of physicochemical and redox properties of microplastics during the weathering under a sulfate-reducing environment and the interaction with arsenite were addressed. The sulfurization of phenol-formaldehyde resin microplastics under a sulfate-reducing environment generated smooth and porous particles with the induction of organic S species. Multiple spectroscopic results demonstrated thioether and thiophene groups formed by the substitute removal of O-containing functional groups. Moreover, the sulfurization process induced the reduction of carbonyl groups and oxidation of phenolic hydroxyl groups and resulted in the formation of semiquinone radicals. The O-containing functional groups contributed to microplastics redox property and As(III) oxidation while S-containing functional groups showed no obvious effect. The sulfurized microplastics had lower efficiency in mediating arsenite oxidation than the unsulfurized counterparts due to the decreased electron donating capacity. Producing hydrogen peroxides by electron-donating phenol groups and semiquinone radicals and the direct semiquinone radicals oxidation could mediate arsenite oxidation. The findings of this study help us understand the fate of microplastics in redox fluctuation interfaces.

Combined application of strong alkaline materials and specific organic fertilizer accelerates nitrification process of a rare earth mining soil.

The extensive usage of ammonium sulfate as the leaching agent to extract rare earth elements led to widespread ammonia nitrogen (NH4+-N) pollution in the tailing soils of ion-adsorbed rare earth deposits in southern China. However, the cost-effective technologies to tackle with the long-term retention of NH4+-N in the rare earth mining soil have been largely unresolved. In this study, we developed a cost-effective approach to activate soil nitrification by the co-application of alkaline materials and organic fertilizer. The co-application of 0.3 % of organic fertilizer and 0.1 % âˆ¼ 0.2 % of CaO or MgO or Mg(OH)2 stimulated a soil NH4+-N decrease rate of 2.01-7.58 mg kg-1 d-1 and a soil NO3--N accumulation rate of 1.56-7.09 mg kg-1 d-1. Noting that only if the soil pH was elevated to 7.81-9.00, the NH4+-N decrease rate and NO3--N accumulation rate were dependent on the proton consumption capacity of the alkaline materials. The application of CaCO3 could not stimulate soil nitrification possibly due to the soil pH was uncapable to be elevated to above 7.68. The qPCR, amplicon sequencing, and nitrification inhibitor batch incubation results demonstrated that organic fertilizer supplied active ammonia-oxidizing bacteria Nitrosomonas europaea. The proliferation of Nitrosomonas europaea in the alkaline materials and organic fertilizer co-applied soil was responsible for the soil nitrification. Furthermore, the application of commercial denitrifying bacteria inoculum promoted the removal of accumulated NO3--N. The findings of this study provide a lost-cost technology to remove NH4+-N from the rare earth mining soil.

Activating soil nitrification by co-application of peanut straw biochar and organic fertilizer in a rare earth mining soil.

The intensive mining activities to extract rare earth elements from ion-adsorption rare earth deposits have introduced massive amounts of ammonium into the tailing soils in southern China. Compared to the ubiquitous soil nitrification in cropland, forest, and grassland soils, however, there is no feasible strategy to alleviate the ammonium contamination in tailing soil. Herein, the feasibility to remove ammonium by adding ammonium adsorbents (e.g., biochar, activated carbon, and zeolite), alkaline materials, and organic fertilizer to the rare earth mining soil was explored. The amendment of rice straw biochar, activated carbon, or zeolite in combination with CaCO3 and organic fertilizer showed no significant effect on ammonium removal due to their limited capacity to elevate soil pH. However, the co-application of peanut straw biochar (PSBC), CaCO3, and organic fertilizer activated both the ammonia volatilization and soil nitrification processes. Specifically, the three components functioned as follows: organic fertilizer supplied active ammonia-oxidizing bacteria (AOB); PSBC stimulated AOB proliferation by elevating soil pH above 7.75; CaCO3 ameliorated soil acidity and reduced the lag time for activating soil nitrification. The soil ammonium removal and nitrate accumulation rates were positively correlated to the acid neutralization capacity of PSBC prepared at 400 °C-800 °C. The qPCR and microbial community analysis results indicated that Nitrosomonas europaea was the dominant AOB that was responsible for enhanced soil nitrification. Our findings pave the way for developing cost-effective strategies to remediate ammonium contamination in rare earth mining soils.

Linking pyrogenic carbon redox property to arsenite oxidation: Impact of N-doping and pyrolysis temperature.

Pyrogenic carbon-mediated arsenite (As(III)) oxidation shows great potential as a prerequisite for the efficient removal of arsenic in groundwater. Herein, the critical role of N-containing functional groups in low and high-temperature prepared pyrogenic carbons for mediating As(III) oxidation was systemically explored from an electrochemistry perspective. The pyrogenic carbon electron donating capacity and area-normalized specific capacitance were the key parameters explained the As(III) oxidation kinetics mediated by low electrical conductive 500 °C biomass-derived pyrogenic carbons (N contents of 0.36-7.72 wt%, R2 = 0.87, p < 0.001) and high electrical conductive 800 °C pyrogenic carbons (N contents of 1.00-8.00 wt%, R2 = 0.99, p < 0.001), respectively. The production of H2O2 from the reaction between electron donating phenol groups or semiquinone radicals and oxygen, and the direct electron transfer between semiquinone radicals and As(III) contributed to these pyrogenic carbons mediated As(III) oxidation. While the electron accepting quinone, pyridinic-N, and pyrrolic-N groups did not significantly contribute to the 500 °C pyrogenic carbons mediated As(III) oxidation, the direct electron conduction by these functional groups was responsible for the facilitated As(III) oxidation by the 800 °C pyrogenic carbons. Furthermore, the pyridinic-N and pyrrolic-N groups showed higher electron conduction efficiency than that of the quinone groups. The findings help to develop robust pyrogenic carbons for As(III) contaminated groundwater treatment.