Sulfur enhances iron plaque formation and stress resistance to reduce the transfer of Cd and As in the soil-rice system.

Sulfur plays an essential role in agricultural production, but few studies have been reported on how sulfur simultaneously impacts the transformation of cadmium (Cd) and arsenic (As) in the soil-rice system. This research selected two soils co-contaminated with both Cd and As, varying in acidity and alkalinity levels, to study the impacts of elemental sulfur (S) and calcium sulfate (CaSO4) on the migration and accumulation of Cd and As by rice. Results indicated that two types of sulfur had a substantial (P < 0.05) impact on decreasing the contents of Cd (28.3-50.4 %) and As (20.1-38.6 %) in brown rice in acidic and alkaline soils. They also increased rice biomass (29.3-112.8 %) and reduced Cd transport coefficient (27.2-45.6 %) significantly (P < 0.05). Notably, sulfur augmented the generation of iron plaque on rice root surfaces, which increased the fixation of Cd (17.6-61.0 %) and As (14.0-45.9 %). SEM-EDS results also indicated that the rice root surface exhibited significant enrichment of Fe, Cd, and As. The mechanism of simultaneous Cd and As immobilization by sulfur application was mainly ascribed to the contribution of iron plaque. Additionally, sulfur reduced the contents of Cd and As in soil porewater and promoted the transformation of As(III) to As(V) to reduce the toxicity of As. The K-edge XAFS of As in iron plaque also confirmed that sulfur application significantly promoted As(III) oxidation. Sulfur also promoted the activities of antioxidant enzymes and the contents of NPT, GSH, and PCs in rice plants. In general, this study establishes a foundation for sulfur to lower As and Cd bioavailability in paddy soils, enhance iron plaque and rice resistance, and reduce heavy metal accumulation.

Cadmium, lead, and zinc immobilization in the soil using a phosphate compound with citric acid present.

Low molecular weight organic acids (LMWOAs) are common in rhizospheric soil and may impede the interaction between phosphate and metals. Thus, studying how phosphate compounds impact metal immobilization in rhizospheric soil using LMWOAs is crucial. An incubation experiment examined the effects of NaH2PO4 (a P compound) (3%), various concentrations of citric acid (CA), and combinations of P and CA, on soil cadmium (Cd), lead (Pb), and zinc (Zn) immobilization using the European Community Bureau of Reference (BCR) sequential extraction method, CaCl2 extraction method, zeta potential, fourier-transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD). The P, low CA (2 mmol kg-1 soil) (CA2), and P-CA2 treatments reduced acid-soluble and CaCl2-extractable Cd, Pb, and Zn, indicating metal immobilization, with the P-CA2 treatment being the most effective. High CA (>5-20 mmol kg-1 soil) or a P with high CA reversed prior patterns, suggesting metal mobilization. The zeta potential study indicated that when pH increased, treatments became more negative, notably P-CA2 followed by P, suggesting that electrostatic adsorption was the predominant metal immobilization mechanism, especially in P-CA2. XRD tests, however, showed that the P treatment alone produced Cd phosphate, pyromorphite, and hopeite, indicating that sorption and precipitation were the main metal immobilization processes in the P treatment alone. In conclusion, P-CA2 was found to be the most efficient metal immobilization and redistribution treatment for contaminated soils. Rhizospheric CA may alter Cd, Pb, and Zn mineral stability. Therefore, when treating Cd, Pb, and Zn-contaminated soils with a P compound, CA should be addressed.

Isotherm models for adsorption of heavy metals from water - A review.

Adsorption is a widely used technology for removing and separating heavy metal from water, attributed to its eco-friendly, cost-effective, and high efficiency. Adsorption isotherm modeling has been used for many years to predict the adsorption equilibrium mechanism, adsorption capacity, and the inherent characteristics of the adsorption process, all of which are substantial in evaluating the performance of adsorbents. This review summarizes the development history, fundamental characteristics, and mathematical derivations of various isotherm models, along with their applicable conditions and application scenarios in heavy metal adsorption. The latest progress in applying isotherm models with a one-parameter, two-parameter, and three-parameter in heavy metal adsorption using carbon-based materials, which has gained much attention in recent years as low-cost adsorbents, is critically reviewed and discussed. Several experimental factors affecting the adsorption equilibrium, such as solution pH, temperature, ionic strength, adsorbent dose, and initial heavy metal concentration, are briefly discussed. The criteria for selecting the optimum isotherm for heavy metal adsorption are proposed by comparing various adsorption models and analyzing mathematical error functions. Finally, the relative performance of different isotherm models for heavy metal adsorption is compared, and the future research gaps are identified.

Cadmium, lead, and zinc immobilization in soil by rice husk biochar in the presence of low molecular weight organic acids.

Heavy metal immobilization using biochar (BC) is different from the usual soil incubation due to the low molecular weight organic acids (LMWOAs) in the rhizosphere and is an issue worth evaluating. Therefore, the impacts of rice husk BC (5%), tartaric acid, and oxalic acid, coupled with combinations of BC and tartaric acid/oxalic acid on the transformation of cadmium (Cd), lead (Pb), and zinc (Zn) among their geochemical forms, including their bioavailability in a metal-contaminated soil, were investigated in an incubation experiment. The application of BC, low concentration of tartaric acid (2 mmol kg-1 soil) (TA2), and the combined BC plus a low level of tartaric acid (BC-TA2) markedly reduced the acid-soluble and available (CaCl2-extractable) Cd, Pb, and Zn compared to control (CK) in which BC-TA2 was found to be the most effective treatment. The trends were reversed in the case of the high concentrations of tartaric acid (>5-20 mmol kg-1 soil), all levels of oxalic acid (2-20 mmol kg-1 soil), and the combined BC plus high levels of tartaric acid/oxalic acid treatments. The BC-TA2 transformed the highest amounts of acid-soluble and reducible Cd, Pb, and Zn to the oxidizable and residual fractions with incubation time. The results suggested that the low concentration of tartaric acid enhanced Cd, Pb, and Zn immobilization, while the higher level of tartaric acid and all concentrations of oxalic acid increased their mobilization. In conclusion, BC-TA2 could immobilize the most heavy metals and serve as an amendment for metals' immobilization/redistribution in contaminated soils.

Lead immobilization in soil using new hydroxyapatite-like compounds derived from oyster shell and its uptake by plant.

Protecting the natural environment and ecological systems from the inorganic pollutants such as lead (Pb) has highlighted the urgent need to develop new and effective approaches for this substance's immobilization in soil. In this study, new, low-cost, and eco-friendly hydroxyapatite (HAp)-like compounds were prepared by reacting oyster shell (Oys) with diammonium phosphate ((NH4)2HPO4) (DAP) and calcium hydroxide (Ca(OH)2) at 25-28 °C (OyOHr) and 100 °C (OyOHh). Furthermore, OyOHr and OyOHh were assessed for their effectiveness to immobilize Pb in soil and suppress Pb uptake by Indian spinach (Basella Alba L.). Application of 0.5% OyOHr and OyOHh to soil (by weight) reduced Pb concentration in the shoots by 76.9-78.0% compared to control (CK), to a level that was slightly higher (by 15.5-21.5%) than the recommended food safety level (2 mg kg-1) suggested by WHO. The changes in Pb fractions revealed that the total contents of oxidizable and residual forms in OyOHr or OyOHh after harvest was >415.0 mg kg-1, which indicated that >92% of Pb when added to the soil, was immobilized and not able to be taken up by plants. The proposed Pb immobilization mechanism might be the dissolution of OyOHr or OyOHh followed by hydroxypyromorphite (Pb10(PO4)6(OH)2) (HP) formation. Due to their facile preparation and eco-friendly and excellent Pb immobilizing characteristics, OyOHr or OyOHh could be readily integrated into current farming systems to mitigate the risk of Pb transferring to plants. However, OyOHr seemed a better immobilizing agent correspond to OyOHh in terms of cost and efficiency.

Effects of low molecular weight organic acids on Cu accumulation by castor bean and soil enzyme activities.

Chelating agents have been considered as an important phytoremediation strategy to enhance heavy metal extraction from contaminated soil. A pot experiment was conducted to explore the effects of low molecular weight organic acids (LMWOAs) on the phytoremediation efficiency of copper (Cu) by castor bean, and soil enzyme activities. Results indicated that the addition of all the three kinds of LMWOAs (citric, tartaric, oxalic acids) did not decrease the biomass of castor bean, despite the fact they reduced the concentration of chlorophyll-a in leaves compared to the control. The Cu concentrations in the roots and shoots significantly increased by 6-106% and 5-148%, respectively, in the LMWOAs treatments so that the total accumulation of Cu by whole plants in all the LMWOAs treatments increased by 21-189% in comparison with the control. The values of the translocation factor (TF) and bio-concentration factor (BCF) of Cu in castor bean also rose following the addition of LMWOAs, indicating that the LMWOAs enhanced the uptake and transportation of Cu. Moreover, the application of LMWOAs did not significantly change the soil pH but significantly increased the activity of soil enzymes (urease, catalase, and alkaline phosphatase). The addition of exogenous LMWOAs increased the available Cu significantly in the soil, thus promoted the phytoextraction efficiency of Cu by castor bean. These results will provide some new insights into the practical use of LMWOAs for the phytoremediation of heavy-metal-contaminated soil employing castor bean.

Variations of dissolved organic matter and Cu fractions in rhizosphere soil induced by the root activities of castor bean.

The root soil interaction affects metal bioavailability in the rhizosphere, thus impacting the uptake and accumulation of metals by plants. In this study, a greenhouse experiment using a root-bag technique for castor bean plants was conducted to determine the i) rhizosphere effect on the fractions of Cu, and ii) the characteristics of dissolved organic matter (DOM) in the rhizosphere soil. Results showed that the Cu concentration in the leaves, stems, and roots was 15.41, 6.71, and 47.85 mg kg-1, respectively, in the control and reached up to 96.5, 254.9, and 3204 mg kg-1 in Cu400 treatment, respectively. After cultivating castor bean plants, the concentration of acid exchangeable Cu in rhizosphere soil was higher than that in the bulk soil for the same Cu addition, whereas the concentrations of reducible Cu, oxidizable Cu, and residual Cu in the rhizosphere soil were all lower than those in the bulk soil, respectively. In comparison to the bulk soil, the pH decreased while the total nitrogen and total carbon concentrations both increased in the rhizosphere soil. Moreover, the concentrations of total low molecular weight organic acids (LMWOAs) and total amino acids in the rhizosphere soil of the Cu treatments increased by between 15.18% to 47.17% and 36.35%-200%, respectively with respect to the control. The less complex DOM with a high LMWOAs concentration in the rhizosphere soil shifted the soil Cu from a relative stable fraction to available fractions.