Efficient mineralization of cadmium and arsenic by poorly crystalline CaFe-layered double hydroxide in soil: Performance and mechanism.

The co-contamination of arsenic (As) and cadmium (Cd) in the environment is of most concern. In this work, poorly crystalline CaFe-layered double hydroxide (CaFe-LDH) was synthesized with a Ca-to-Fe molar ratio of 4 to ensure effective immobilization of Cd and As in soil. The application of Ca4Fe-LDH in soil remediation demonstrated that the targeted heavy metals gradually mineralized into a relatively stable oxidizable and residual state. At a soil remediation dosage of 1.6%, the availability levels of Cd and As decreased significantly, achieving stabilization efficiencies of 99% and 85.2% respectively. Cd is trapped through isomorphic substitution and dissolution-reprecipitation of calcium (Ca) laminate, resulting in the formation of CdCaFe-LDH mineralization products. As is immobilized through ion exchange with interlayer anions, redox with Fe(III), and Fe-Cd-As complexation. Moreover, the results of the characterization and density functional theoretical (DFT) calculations demonstrate that the CdCaFe-LDH formed by isomeric substitution of Ca for Cd enhanced the adsorption of As on the (110) plane of LDH, indicating that the trap mechanism of Cd and As by Ca4Fe-LDH is synergistically promoted. Overall, the above results prove that mineralization using Ca4Fe-LDH is a promising method to remediate soils combined contaminated by both Cd and As.

Cooperation of selenium, iron and phosphorus for simultaneously minimizing cadmium and arsenic concentrations in rice grains.

Cadmium (Cd) and arsenic (As), two toxic elements to humans, are ubiquitously coexisting contaminant found in paddy fields. The accumulation of Cd and As in rice, a major food source for many people around the world, can pose a serious threat to food safety and human health. Therefore, it is crucial to be aware of these contaminants and take adequate measures to reduce the accumulation of these two elements in rice. Developing an effective method to simultaneously reduce the accumulation of Cd) and As in rice is challenging. In this study, a pot experiment was conducted to investigate the synergistic effects of selenium (Se), iron (Fe) and phosphorus (P) on the uptake, transport and accumulation of cadmium and arsenic in rice by analyzing the physical and chemical properties of the soil, the elemental concentrations and their interrelationships in the rice tissues, and the composition and morphology of the iron plaque (IP). The results showed that the combined treatments of Se, Fe and P had positive effects on reducing Cd and As accumulation in rice, reducing Cd concentrations in brown rice by 3.86-51.88 % and As concentrations by 25.37-40.81 %. The possible mechanisms for the reduction of As and Cd concentrations in rice grains were: (i) Combined application of Fe, P and Se can effectively reduce the soil available Cd and As concentration. (ii) Combined application significantly improved the formation of IP at the tillering stage and increased the crystalline iron oxides in IP, promoting the deposition of SiO2 in rice roots, thereby effectively inhibiting the uptake of Cd and As by rice roots. (iii) Interplay and interaction between elements facilitated by transporter proteins could contribute to the synergistic mitigation of Cd and As by Se, Fe and P. This study provides a valuable new approach for effective control of Cd and As concentration of rice grown in co-contaminated soil.

Transformation of As and Cd associated with Fe-Mn-modified biochar during simultaneous remediation on the contaminated soil.

Here, Fe- and Mn-modified biochar (BC-Fe-Mn) was applied to simultaneously stabilize As and Cd in the contaminated soil. The removal efficiencies for NaHCO3-extractable As and DTPA-extractable Cd by BC-Fe-Mn were 60.8% and 49.6%, respectively. The speciation analyses showed that the transformation to low-crystallinity Fe-bound (F3) As, Fe-Mn oxide-bound (OX) of Cd, and residual As and Cd was primarily attributed to stabilizing the two metal(loid)s. Moreover, the correlation analyses showed that the increase of As in F3 fraction was significantly and positively associated with the increase of OX fraction Mn (r = 0.64). Similarly, OX fraction Cd was increased notably with increasing OX fraction Fe (r = 0.91) and OX fraction Mn (r = 0.76). In addition, a novel dialysis experiment was performed to separate the reacted BC-Fe-Mn from the soil for intensively investigating the stabilization mechanisms for As and Cd by BC-Fe-Mn. The characteristic crystalline compounds of (Fe0.67Mn0.33)OOH and Fe2O3 on the surface of BC-Fe-Mn were revealed by SEM-EDS and XRD. And FTIR analyses showed that α-FeOOH, R-COOFe/Mn+, and O-H on BC-Fe-Mn potentially served as the reaction sites for As and Cd. A crystalline compound of MnAsO4 was found in the soil treated by BC-Fe-Mn in the dialysis experiment. Thus, our results are beneficial to deeper understand the mechanisms of simultaneous stabilization of As and Cd by BC-Fe-Mn in soil and support the application of the materials on a large scale.

Molecular response to the influences of Cu(II) and Fe(III) on forming biogenic manganese oxides by Pseudomonas putida MnB1.

The biogeochemical cycle of biogenic manganese oxides (BioMnOx) is closely associated with the environmental behavior and fate of various pollutants. It is significantly interfered by many metals, such as Cu and Fe. However, the bacterial molecular responses are not clear. Here, the effects of Cu(II) and Fe(III) on oxidation of manganese by Pseudomonas putida MnB1 and the bacterial molecular response mechanisms have been studied. The bacterial oxidation of manganese were promoted by both Fe(III) and Cu(II) and the final manganese oxidation rate of the Cu(II) group exceeded 16 % that of the Fe(III) group. The results of transcriptome indicated that Cu(II) promoted manganese oxidation by up-regulating the expression levels of multicopper oxidase (MCO) and peroxidase(POD), and by stimulating electron transfer, while Fe(III) promoted this process by accelerating the electron transfer and nitrogen cycling, and activating POD. The protein-protein interaction (PPI) network indicated that the MCO genes (mnxG and mcoA) were directly linked to the copper homeostasis proteins (cusA, cusB, czcC and cusF). Cytochrome c was closely related to the genes related to nitrogen cycling (glnA, glnL, and putA) and electrons transfer (cycO, cycD, nuoA, nuoK, and nuoL), which also promoted manganese oxidation. This study provides a molecular level insight into the oxidation of Mn(II) by Pseudomonas putida MnB1 with Cu(II) and/or Fe(III) ions.

Development and application of machine learning models for prediction of soil available cadmium based on soil properties and climate features.

Identifying the key influencing factors in soil available cadmium (Cd) is crucial for preventing the Cd accumulation in the food chain. However, current experimental methods and traditional prediction models for assessing available Cd are time-consuming and ineffective. In this study, machine learning (ML) models were developed to investigate the intricate interactions among soil properties, climate features, and available Cd, aiming to identify the key influencing factors. The optimal model was obtained through a combination of stratified sampling, Bayesian optimization, and 10-fold cross-validation. It was further explained through the utilization of permutation feature importance, 2D partial dependence plot, and 3D interaction plot. The findings revealed that pH, surface pressure, sensible heat net flux and organic matter content significantly influenced the Cd accumulation in the soil. By utilizing historical soil surveys and climate change data from China, this study predicted the spatial distribution trend of available Cd in the Chinese region, highlighting the primary areas with heightened Cd activity. These areas were primarily located in the eastern, southern, central, and northeastern China. This study introduces a novel methodology for comprehending the process of available Cd accumulation in soil. Furthermore, it provides recommendations and directions for the remediation and control of soil Cd pollution.

Adsorption behavior of lead, cadmium, and arsenic on manganese-modified biochar: competition and promotion.

Biochar adsorption of heavy metals has been a research hotspot, yet there has been limited reports on the effect of heavy metal interactions on adsorption efficiency in complex systems. In this study, the adsorbent was prepared by pyrolysis of rice straw loaded with manganese (BC-Mn). The interactions of Pb, Cd and As adsorption on BC-Mn were systematically studied. The results of the adsorption isotherms for the binary metal system revealed a competitive adsorption between Pb and Cd, resulting in decreased Pb (from 214.38 mg/g to 148.20 mg/g) and Cd (from 165.73 mg/g to 92.11 mg/g). A notable promotion occurred between As and Cd, showing an increase from 234.93 mg/g to 305.00 mg/g for As and 165.73 mg/g to 313.94 mg/g for Cd. In the ternary metal system, Pb inhibition did not counteract the promotion of Cd and As. Furthermore, the Langmuir isotherm effectively described BC-Mn's adsorption process in monometallic, binary, and ternary metal systems (R2 > 0.9294). Zeta and FTIR analyses revealed simultaneous competition between Pb and Cd for adsorption on BC-Mn's -OH sites. XPS analysis revealed that As adsorption by BC-Mn facilitated the conversion of MnO2 and MnO to MnOOH, resulting in increased hydroxyl radical production on BC-Mn's surface. Simultaneously, Cd combined with the adsorbed As to form ternary Cd-As-Mn complexes, which expedited the removal of Cd. These results help to provide theoretical support as well as technical support for the treatment of Pb-Cd-As contaminated wastewater.

Ferrihydrite transformation impacted by coprecipitation of lignin: Inhibition or facilitation?

Lignin is a common soil organic matter that is present in soils, but its effect on the transformation of ferrihydrite (Fh) remains unclear. Organic matter is generally assumed to inhibit Fh transformation. However, lignin can reduce Fh to Fe(II), in which Fe(II)-catalyzed Fh transformation occurs. Herein, the effects of lignin on Fh transformation were investigated at 75°C as a function of the lignin/Fh mass ratio (0-0.2), pH (4-8) and aging time (0-96 hr). The results of Fh-lignin samples (mass ratios = 0.1) aged at different pH values showed that for Fh-lignin the time of Fh transformation into secondary crystalline minerals was significantly shortened at pH 6 when compared with pure Fh, and the Fe(II)-accelerated transformation of Fh was strongly dependent on pH. Under pH 6, at low lignin/Fh mass ratios (0.05-0.1), the time of secondary mineral formation decreased with increasing lignin content. For high lignosulfonate-content material (lignin:Fh = 0.2), Fh did not transform into secondary minerals, indicating that lignin content plays a major role in Fh transformation. In addition, lignin affected the pathway of Fh transformation by inhibiting goethite formation and facilitating hematite formation. The effect of coprecipitation of lignin on Fh transformation should be useful in understanding the complex iron and carbon cycles in a soil environment.

A novel slow-release selenium approach for cadmium reduction and selenium enrichment in rice (Oryza sativa L.).

In this study, a novel slightly-soluble selenium (Se) fertilizer (SSF) was successfully applied to address the problems of Cd pollution in paddy soil and rice, and Se deficiency in human beings. The pot and field experiments showed that Cd content in the rice grains was reduced by 48.4%-82.89% and Se content was increased nearly by 30-fold comparing the control group. The application of SSF increased the soil pH and significantly reduced the DGT-extracted Cd in the soil. Moreover, DCB-extractable Fe content on the surface of roots was prompt by SSF, which formed a physical barrier, namely iron plaque (IP), to inhibit Cd translocation to the above-ground tissues of the rice plants. The Cd content in the IP was also decreased before the filling period, possibly contributing to the reduction in major Cd accumulation in the rice grains. In addition, the continuous Se increase and Cd reduction in the IP by the SSF gradually exceeded that of water-soluble Se during the three periods of rice plant growth. This suggests that SSF has high potential to be an effective Se fertilizer for inhibiting Cd uptake and enriching Se in rice.

Migration of spent grain-modified colloidal ferrihydrite: Implications for the in situ stabilization of arsenic, lead, and cadmium in co-contaminated soil.

The increase of metal mining, processing, and smelting activities has precipitated a substantial escalation in the contamination of soil by heavy metals. Ferrihydrite (FH) has been commonly used as an amendment for the immobilization of heavy metals in contaminated soil. However, FH suffers from drawbacks such as agglomeration and nonmigratory characteristics, which limit its practical application in soil remediation. Herein, a novel spent grain-modified ferrihydrite (FH-SG) colloidal system was developed, and the FH-SG transport mechanisms in the soil medium were fully studied, focusing in particular on the simultaneous in situ stabilization of arsenic (As), lead (Pb), and cadmium (Cd) in co-contaminated soil. The results showed that the stabilization rates of the FH-SG material reached 94.66%, 96.12%, and 95.52% for water-soluble As, Pb, and Cd, respectively, and 72.22%, 49.39%, and 25.30% for bioavailable As, Pb, and Cd, respectively. The FH-SG material demonstrates notable migration properties in porous media. Theoretical calculation results of a single collector show that the migration deposition of FH-SG material in media is primarily governed by its inherent diffusion characteristics with minimal influence by gravitational forces and media interception. It is noteworthy that the maximum migration distance in quartz sand and soil media with different particle sizes can reach 2.07-2.92 m and 0.78-1.08 m, respectively. Altogether, our findings clearly demonstrate that FH-SG exhibits better stabilization and migration than those of FH alone and most proposed FH colloidal systems. The FH-SG colloidal system holds significant promise for the remediation of various kinds of complex polluted soil.

Preparation of lignin nanoparticles via ultra-fast microwave-assisted fractionation of lignocellulose using ternary deep eutectic solvents.

Lignin separation from natural lignocellulose for the preparation of lignin nanoparticles (LNPs) is often challenging owing to the recalcitrant and complex structure of lignocellulose. This paper reports a strategy for the rapid synthesis of LNPs via microwave-assisted lignocellulose fractionation using ternary deep eutectic solvents (DESs). A novel ternary DES with strong hydrogen bonding was prepared using choline chloride, oxalic acid, and lactic acid in a 1:0.5:1 ratio. Efficient fractionation of rice straw (0.5 × 2.0 cm) (RS) was realized by the ternary DES under microwave irradiation (680 W) within only 4 min, and 63.4% of lignin could be separated from the RS to prepare LNPs with a high lignin purity (86.8%), an average particle size of 48-95 nm, and a narrow size distribution. The mechanism of lignin conversion was also investigated, which revealed that dissolved lignin aggregated into LNPs via π-π stacking interactions.