To develop more green, practical and efficient biochar amendments for acidic soils, chitosan-modified biochar (CRB) and alginate-modified biochar (ARB) were prepared, and their effects on promoting soil pH buffering capacity (pHBC) and immobilizing cadmium (Cd) in the paddy soils were investigated through indoor incubation experiments. The results of Fourier transform infrared spectroscopy and Boehm titration indicated that the introduction of chitosan and sodium alginate effectively amplified the functional groups of the biochar, and improved acid buffering capacity of the biochar. Since there was a plateau region between pH 4.5 and 5.5 in acid-base titration curve of the CRB, adding this biochar to acidic paddy soils apparently improved the pHBC and enhanced the acidification resistance of the paddy soils. The addition of ARB enhanced the reduction reactions during submerging and weakened the oxidation reactions during draining, thus retarded the decline of paddy soil pH during drainage. Furthermore, the pH of the paddy soils with ARB addition was higher at the end of draining, which reduced the activity of soil Cd. Considering the environmental sustainability of chitosan and sodium alginate and convenience of preparation method, biochars modified with these two materials provided alternatives for acidic paddy soil amelioration and heavy metal immobilization. However, the additional experiments should be conducted under field conditions to confirm practical application effects in the future.

Arsenic (As) has been recognized as one of the most toxic metalloids present in the surface soil contaminating food chain and posing threat to human life. Sulfur (S) fertilizer is often supplied in paddy soil for rice growth, but its impact on As mobility and related bacteria remains poorly understood. In this study, a pot experiment was set up with two different types of sulfur treatments (element sulfur and Na₂SO₄) to evaluate the effect of sulfur fertilizers on As speciation in porewater, As fractions in soil, As accumulation in rice plants. Besides, rhizosphere bacterial composition and functional genes that might influence As mobility were also studied. The results revealed that the addition of 150 mg/kg Na₂SO₄ decreased As(III) and As(V) concentrations in soil porewater at maturation stage by 77% and 64%, respectively. With the same sulfur content, Na₂SO₄ was more effective than element sulfur. The addition of sulfur fertilizers promoted rice growth and reduced As accumulation in shoots, further reduced As translocation from root to above-ground parts by 39–59%. The addition of sulfur fertilizers had little effect on genes involved in As metabolism. However, the relative abundance of Fe(III) and sulfate reduction related genera increased with the addition of 150 mg/kg Na₂SO₄, consistent with the increase of Fe(III) reducing bacteria Geobacteraceae and sulfate reducing gene dsrA. The phenomenon likely influenced the decrease of As concentrations in soil porewater and rice uptake. The outcomes indicate that promoting Fe- and S- reducing bacteria in the rhizosphere by sulfur fertilizers may be one way to reduce As risk in the soil-rice system.

In situ immobilization of heavy metals in contaminated soils using industrial by-products is an attractive remediation technique. In this work, titanium gypsum (TG) was applied at two levels (TG-L: 0.15% and TG-H: 0.30%) to simultaneously reduce the uptake of cadmium (Cd), lead (Pb) and arsenic (As) in rice grown in heavy metal contaminated paddy soils. The results showed that the addition of TG significantly decreased the pH and dissolved organic carbon (DOC) in the bulk soil. TG addition significantly improved the rice plants growth and reduced the bioavailability of Cd, Pb and As. Particularly, bioavailable Cd, Pb and As decreased by 35.2%, 38.1% and 38.0% in TG-H treatment during the tillering stage, respectively. Moreover, TG application significantly reduced the accumulation of Cd, Pb and As in brown rice. Real-time PCR analysis demonstrated that the relative abundance of sulfate-reducing bacteria increased with the TG application, but not for the iron-reducing bacteria. In addition, 16S rRNA sequencing analysis revealed that the relative abundances of heavy metal-resistant bacteria such as Bacillus, Sulfuritalea, Clostridium, Sulfuricella, Geobacter, Nocardioides and Sulfuricurvum at the genus level significantly increased with the TG addition. In conclusion, the present study implied that TG is a potential and effective amendment to immobilize metal(loid)s in soil and thereby reduce the exposure risk of metal(loid)s associated with rice consumption.

Water management such as drainage for creating aerobic conditions is considered to be an adequate method for reducing the accumulation of arsenic (As) in rice grains; however, it is difficult to conduct drainage operations in some areas that experience a lengthy rainy season as well as in soils with poor drainage. In this regard, application of oxygen-releasing compounds (ORCs) may be an alternative method for maintaining aerobic conditions even under flooding in paddy soils. Therefore, a pot experiment was conducted to investigate the effects of application of an ORC, calcium peroxide (CaO₂), on the growth and accumulation of As in rice plants grown in As-contaminated paddy soils. The rice plants were grown in two soils with different characteristics and As levels, and all of the tested soils were treated with 0, 5, 10, and 20 g CaO₂ kg⁻¹. Results revealed that the concentration of As and the distribution of arsenite in the pore water of all tested soils was reduced by CaO₂ application. In addition, the grain yields increased and the concentration of inorganic As in brown rice decreased by 25–45% upon CaO₂ treatment of low-As-level soils (<16 mg kg⁻¹). However, the effect of CaO₂ application on the accumulation of inorganic As in brown rice in As-enriched soils (>78 mg kg⁻¹) could not found in this study, due to the rice plant suffered from serious As phytotoxicity. It suggests that CaO₂ amendment may be suitable for reducing the As concentration of rice grains grown in low-As-level paddy soils, but for As-enriched soils, the proposed CaO₂ application method is not feasible.

Inhibition of reductive transformation of arsenic (As) in flooded paddy soils is of fundamental importance for mitigating As transfer into food chain. Anaerobic arsenite (As(III)) oxidizers maintain As in less mobile fraction under nitrate-reducing conditions. In this study, we explored the dynamic profile of As speciation in porewater and As distribution among the pools of differential bioavailability in soil solid phase with and without nitrate treatment. In parallel, the abundance and diversity of As(III) oxidase gene (aioA) in flooded paddy soil with nitrate amendment was examined by quantitative PCR and aioA gene clone library. Furthermore, the impact of nitrate on As accumulation and speciation in rice seedlings was unraveled. With nitrate addition (25 mmol NO₃⁻ kg⁻¹ soil), porewater As(III) was maintained at a consistently negligible concentration in the flooded paddy soil and the reductive dissolution of As-bearing Fe oxides/hydroxides was significantly restrained. Specifically, nitrate amendment kept 81% of total soil As in the nonlabile fraction with arsenate (As(V)) dominating after 30 days of flooding, compared to only 61% in the unamended control. Nitrate treatment induced 4-fold higher abundance of aioA gene, which belonged to domains of bacteria and archaea under the classes α-Proteobacteria (6%), ß-Proteobacteria (90%), ɣ-Proteobacteria (2%), and Thermoprotei (2%). By nitrate addition, As accumulation in rice seedlings was decreased by 85% with simultaneously elevated As(V) ratio in rice plant relative to control after 22 days of growth under flooded conditions. These results highlight that nitrate application can serve an efficient method to inhibit reductive dissolution of As in flooded paddy soils, and hence diminish As uptake by rice under anaerobic growing conditions.

The research was conducted to investigate the accumulation, distribution and availability of Cd in paddy soil and their relation to Cd in rice plants under 30-year fertilization regimes. Six treatments were involved in the study: control without fertilization (CK), chemical fertilizer (NPK), high nitrogen chemical fertilizer (HN), rice straw incorporation (ST), low and high dosage of manure fertilizer (LM and HM). Total and DTPA extractable concentration of Cd (T-Cd and DTPA-Cd) in bulk soils (20 cm topsoil), profiles (0–60 cm) and aggregates (>2, 1–2, 0.5–1, 0.25–0.5, 0.053–0.25 and < 0.053 mm) were investigated. The Cd concentration in relevant rice plant (roots, stems, leaves, husks and grains) were also analyzed. Manure fertilizers caused T-Cd accumulation in bulk soil with a significant increase of 36.2% in LM and 81.2% in HM. Similar impacts of manure fertilizers were observed in DTPA-Cd in the bulk soil. Further, the HM generated a further accumulation in deeper soil layers, presenting a remarkable increase of T-Cd (28.3%–225%) in 10–40 cm and DTPA-Cd (116%–158%) in 10–30 cm profiles. Moreover, the continuous application of manure fertilizers enhanced the availability of Cd in all aggregate size classes with an increase of 17.3%–87.8% in DTPA-Cd. Organic fertilizers (LM, HM and ST) heightened the content of Cd (38.0%–152%) in all parts of rice plant. The accumulation of Cd in rice plants was directly affected by fertilization regimes and Cd availability in the 10–20 cm soil layers and 0.25–0.5 mm aggregates. In conclusion, long-term application of manures resulted in increasing availability of Cd in aggregates and in topsoil and subsoil layers, which accordingly enhanced the accumulation of Cd in rice plants.

Adequate silicon (Si) can greatly boost rice yield and improve grain quality through alleviating stresses associated with heavy metals and metalloids such as arsenic (As) and cadmium (Cd). The soil plant-available Si is relatively low in South China due to severe desilicification and allitization of the soils in this region. Conversely, pollution of heavy metals and metalloids in the soils of this region occurs widely, especially As and Cd pollution in paddy soil. Therefore, evaluating the plant availability of Si in paddy soil of South China and examining its correlation with the availability of heavy metals and metalloids are of great significance. Accordingly, in our study, 107 pairs of soil and rice plant samples were collected from paddy fields contaminated by As and Cd in South China. Significantly positive correlations between Si in rice plants and Si fractions in soils extracted with citric acid, NaOAc-HOAc buffer, and oxalate-ammonium oxalate buffer suggest that these extractants are more suitable for use in extracting plant-available Si in the soils of our present study. Significantly negative correlations between different Si fractions and As or Cd in rice plant tissues and negative exponential correlations between the molar ratios of Si to As/Cd in rice roots, straws, husks or grains and As/Cd in rice grains indicate that Si can significantly alleviate the accumulation of As/Cd from soils to the rice plants. Finally, a contribution assessment of soil properties to As/Cd accumulation in rice grains based on random forest showed that in addition to Si concentrations in soil or rice plants, other factors such as Fe fractions and total phosphorus also contributed largely to As/Cd accumulation in rice grains. Overall, Si exhibited its unique role in mitigating As or Cd stress in rice, and our study results provide strong field evidence for this role.

Much research has considered the influence of biochars on the availability and phytoaccumulation of potentially toxic elements (PTEs) from soil. However, the vast majority of these studies use, what are arguably, unrealistic and unpractical amounts of biochar (10, 50 and even up to 100 t/ha). To offer a more realistic insight into the influence of biochar on PTE partitioning and phytoaccumulation, a field study, using modest rates of biochar application (1.5, 3.0 t/ha), was undertaken. Specifically, the research investigated the influence of sewage sludge biochar (SSBC) on the accumulation of Cd into rice (Oryza sativa L.) grown in Cd contaminated (0.82 ± 0.07 mg/kg) paddy soil. Results indicated, Cd concentrations in rice grains to significantly (p < 0.05) decrease from 1.35 ± 0.09 mg/kg in the control to 0.82 ± 0.07 mg/kg and 0.80 ± 0.21 mg/kg in the 1.5 t/ha and 3.0 t/ha treatments, respectively. Accordingly, the hazardous quotient (HQ) indices for Cd, associated with rice grain consumption, were also reduced by ∼40%. SSBC amendment significantly (p < 0.05) increased grain yields from 1.90 ± 0.08 g/plant in the control to 2.17 ± 0.30 g/plant and 3.40 ± 0.27 g/plant in the 1.5 t/ha and 3.0 t/ha treatments, respectively. Thus, the amendment of SSBC to contaminated paddy soils, even at low application rates, could be an effective approach to mitigate Cd accumulation into rice plants, to improve rice grain yields, and to thereby improve food security and protect public health.

Cadmium (Cd) and arsenic (As) are loaded into rice grain via two pathways: i) root uptake from the soil and then translocation to the grain, and ii) remobilization of Cd and As previously accumulated within the vegetative tissues to the grain. However, the relative contributions of the two pathways are not well understood in soil-grown rice plants. In this study, we used eight different water management regimes applied at different growth periods to manipulate the concentrations of Cd and As in porewater and then established a mathematical model to estimate the relative importance of the two pathways. Different water management regimes had dramatic and opposite effects on the solubility of Cd and As in soil, and their subsequent accumulation in both straw and grain. Water management applied at different growth periods had markedly different impacts on grain Cd and As concentrations. Water management during grain filling had a much greater impact on grain Cd than on grain As concentrations, whereas water treatment during the vegetative growth stage had a larger effect on grain As concentrations. Under the typical water management practice (i.e. flooding through the vegetative stage followed by drainage during grain filling), grain filling is the key period for the accumulation of Cd in the grain, with 98% of the grain Cd from root uptake during this period and the contribution of remobilization being very limited. In contrast, 95% of the grain As was remobilized from that accumulated within the plant prior to the grain filling, with the tillering, jointing, and heading period each contributing 20–40% of the grain As, whereas root uptake during grain filling contributed minor. These differences can be harnessed to design a segmented water management strategy to control grain Cd and As accumulation simultaneously.

As a redox-sensitive element, manganese (Mn) plays a critical role in Cd mobilization, especially in paddy soil. In an anoxic environment, the precipitation of Mn(II)-hydroxides specifically favors Cd retention, while draining the paddy fields results in substantial remobilization of Cd. However, how the change in Mn redox states during the periodical transit of anoxic to oxic systems affects Cd mobility remains unclear. In this study, we demonstrate that the radical effect generated during the oxidation of Mn(II)-hydroxides exerts a significant effect on the oxidative dissolution of Cd during the aeration of paddy soils. The extractable Cd concentration decreased rapidly during the reduction phases but increased upon oxidation, while Cd availability produced the opposite effect with soil pe + pH and the extractable Mn concentration. Inhibiting the oxidation of Mn(II)-containing phases by microbes suppressed the production of hydroxyl free radicals (•OH) and Cd mobilization in the drainage phase. Analysis of X-ray absorption spectroscopy and sequential extraction demonstrated that the transformation from the Mn phase of Mn(II) to Mn(III/IV) determines Cd solubility. Altogether, the oxidization of Mn(II)-hydroxides was associated with the generation of significant amounts of •OH. The dissolution of Mn(II)- incorporating phases lead to a net release of Cd into soils during soil aeration.