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.

Lead (Pb) is a toxic metal in industrial production, which can seriously threat to human health and food safety. Thus, it is particularly crucial to reduce the content of Pb in the environment. In this study, raw fly ash (FA) was used to synthesise a new active silicate materials (IM) employing the low-temperature-assisted alkali (NaOH) roasting approach. The IM was further synthesised to form zeolite-A (ZA) using the hydrothermal method. The physicochemical characteristics of IM and ZA amendments before and after Pb²⁺ adsorption were analysed using the Scanning electron microscope-Energy Dispersive Spectrometer (SEM-EDS), Fourier Transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD) apparatuses. The results revealed the considerably change in the microstructure and functional groups of IM and ZA amendments, conducive to Pb²⁺ removal. Moreover, a 3-year field experiment revealed that the IM and ZA significantly improved the growth of rice and reduced available Pb by 21%–26.8% and 9.7%–16.9%, respectively. After 3 years of remediation, the Pb concentration of the rice grain reached the national edible standard (≤0.2 mg kg⁻¹) of 0.171 mg kg⁻¹ and 0.179 mg kg⁻¹, respectively. Meanwhile, the concentration of acid-exchangeable Pb reduced, while those of reducible and residual fractions of Pb increased. There was no significant difference between the IM and ZA treatments. The potential mechanisms of remediation by the amendments were ion-exchange, complexation, precipitation, and electrostatic attraction. Overall, the results indicate that IM is suitable for the remediation of contaminated soil and promotes safe food production, and develops an environmentally friendly and cost-effective amendment for the remediation of polluted soil.

Cadmium (Cd) contamination in paddy soil often results in elevated Cd concentrations in rice grain, which is a serious concern threatening food safety. Most of the Cd accumulated in rice grain is derived from its remobilization in paddy soil during the grain filling period when paddy water is drained. We have previously shown that the voltaic cell effect controls the oxidative release of cadmium sulfide (CdS) during the drainage period. Metal sulfides with lower electrochemical potentials than CdS can suppress the oxidation of CdS. In the present study, we tested whether amendments of ZnSO₄ or MnSO₄ could enhance the suppressive voltaic effect on Cd release and subsequent accumulation in rice grain. The one-time addition of ZnSO₄ (75 kg/ha Zn) decreased CaCl₂-extractable Cd concentrations in soils by 32–64% in pot experiments and by 16–30% in field trials during the drainage period. Consequently, Cd concentrations in brown rice were reduced by 74–87% and 60–72% in pot experiments and field trials, respectively. Importantly, this effect persisted in the second year without further addition. The amendment of MnSO₄ had similar effects in decreasing soil extractable Cd and Cd concentrations in brown rice. These effects were not attributed to the addition of sulfate. A single application of such doses of ZnSO₄ or MnSO₄ (e.g. 75–150 kg/ha Zn or Mn) only caused a marginal increase in soil Zn or Mn concentrations and had no significant impact on grain yield. Taken together, amendments of ZnSO₄ and/or MnSO₄ (at the rate of 75–150 kg/ha Zn and or Mn) formed a protective voltaic cell partner against the oxidative dissolution of CdS and thus were highly effective in reducing Cd accumulation in rice grain. This work provides a simple but effective method to decrease soil Cd availability during soil drainage and mitigate Cd accumulation in rice to ensure food safety.

Biochar is often applied to paddy soils as a soil improver, as it retains nutrients and increases C sequestration; as such, it is a tool in the move towards C-neutral agriculture. Nitrogen (N) fertilizers have been excessively applied to rice paddies, particularly in small farms in China, because N is the major limiting factor for rice production. In paddy soils, dynamic changes in iron (Fe) continuously affect soil emissions of methane (CH₄) and carbon dioxide (CO₂); however, the links between Fe dynamics and greenhouse gas emissions, dissolved organic carbon (DOC), and rice yields following application of biochar remain unclear. The aims of this study were to examine the effects of two rates of nitrogen (N)-enriched biochar (4 and 8 t ha⁻¹ y⁻¹) on paddy soil C emissions and storage, rice yields, and Fe dynamics in subtropical early and late rice growing seasons. Field application of N-enriched biochar at 4 and 8 t ha⁻¹ increased C emissions in early and late rice, whereas application at 4 t ha⁻¹ significantly increased rice yields. The results of a culture experiment and a field experiment showed that the application of N-enriched biochar increased soil Fe²⁺concentration. There were positive correlations between Fe²⁺concentrations and soil CO₂, CH₄, and total C emissions, and with soil DOC concentrations. On the other way around, these correlations were negative for soil Fe³⁺concentrations. In the soil culture experiment, under the exclusion of plant growth, N-enriched biochar reduced cumulative soil emissions of CH₄ and CO₂. We conclude that moderate inputs of N-rich biochar (4 t ha⁻¹) increase rice crop yield and biomass, and soil DOC concentrations, while moderating soil cumulative C emissions, in part, by the impacts of biochar on soil Fe dynamics. We suggest that water management strategies, such as dry-wet cycles, should be employed in rice cultivation to increase Fe²⁺ oxidation for the inhibition of soil CH₄ and CO₂ production. Overall, we showed that application of 4 t ha⁻¹ of N-enriched biochar may represent a potential tool to improve sustainable food production and security, while minimizing negative environmental impacts.

Hydrochar (HC), an environment-friendly material, enhances soil carbon sequestration and mitigate greenhouse gases (GHGs) emissions in croplands. In this study, the water-washed HC (WW-HC) was applied to paddy soil to investigate effects on nitrous oxide (N₂O) and methane (CH₄) emissions during rice growth period. Four treatments, namely control (without N fertilizer and WW-HC), N fertilizer (WW-HC00), N fertilizer with 0.5 wt% WW-HC (WW-HC05) and N fertilizer with 1.5 wt% WW-HC (WW-HC15), were established. Results showed the WW-HC addition reduced N₂O and CH₄ emissions, global warming potential (GWP) and greenhouse gas intensity (GHGI) during the growing season. Moreover, the WW-HC application reduced N₂O cumulative emission (P < 0.05) (by 28.6% and 23.8% for WW-HC05 and WW-HC15, respectively). It was mainly due to the reduced ratio of (nirK + nirS) to nosZ under WW-HC15 (P < 0.05). Compared with WW-HC00, the WW-HC05 reduced CH₄ cumulative emissions by 14.8%, while the WW-HC15 increased by 9.7%. This might be ascribed to the significantly reduced expression of the methanogenic mcrA gene and ratio of mcrA to pmoA by WW-HC (P < 0.05). The WW-HC05 amendment decreased GWP and GHGI by 18.6% and 32.5%, respectively. Furthermore, the WW-HC application greatly improved nitrogen use efficiency by 116–145% compared with the control. Our study indicates the WW-HC application is a promising GHGs mitigation practice in paddy fields.

Diethyl phthalate (DEP), as a kind of universally used plasticizer, has aroused considerable public concern owing to its wide detection, environmental stability, and potential health risks. In this work, the highly efficient removal of DEP by ferrate (VI) (Fe(VI)) was systematically explored in soil environment. The effects of the oxidant dosages, soil types, as well as the presence of coexisting cations and anions in tested soil on DEP removal were evaluated. When the dosage of Fe(VI) was 20 mM, complete removal of DEP (50 μg/g) was achieved in the tested soil after 2 min of reaction. Furthermore, the removal rate of DEP was closely related to the soil types, and the degradation rates were decreased obviously in red soil (RS), black soil (BS) and paddy soil (PS), probably due to the acidic condition and high content of organic matters. Moreover, the presence of Ca²⁺, Mg²⁺ and Al³⁺ in soil can inhibit the removal of DEP by Fe(VI), while SO₄²⁻ has an slightly promotion effect. Six oxidation intermediates were detected in the reaction process of DEP, product analysis revealed that the transformation of DEP was mainly through two pathways, including hydrolysis and hydroxylation reactions, which were probably mediated by oxygen atom transfer process of Fe(VI). Based on the frontier electron density theory calculation, two ester groups of DEP were prone to be attacked by Fe(VI), and the hydroxyl addition tended to occur at the para-position of one of the ester groups on the benzene ring. This study provides a novel approach for phthalate esters removal from soil using Fe(VI) oxidation and shows new insights into the oxidation mechanisms.

Mixed pollution due to heavy metals (HMs), especially cadmium (Cd), lead (Pb), and arsenic (As), seriously endangers the safety of food produced in paddy soil. In the field experiments, foliar application of 2,3-dimercaptosuccinic acid (DMSA) at the flowering stage was found to significantly reduce the levels of Cd, Pb, total As, and inorganic As (iAs) in rice grains by 47.95%, 61.76%, 36.37%, and 51.24%, respectively, without affecting the concentration of metallonutrients, including Mn, K, Mg, Ca, Fe, and Zn. DMSA treatment significantly reduced the concentrations of Cd, Pb, and As in the panicle node, panicle neck, and rachis, while those in the flag leaves were significantly increased by up to 20.87%, 49.40%, and 32.67%, respectively. DMSA application promoted the transport of HM from roots and lower stalks to flag leaves with a maximum increase of 34.55%, 52.65%, and 46.94%, respectively, whereas inhibited the transport of HM from flag leaves to panicle, rachis, and grains. Therefore, foliar application of DMSA reduced Cd, Pb, and As accumulation in rice grains by immobilizing HMs in flag leaves. Thus, this strategy could act as a promising agronomic measure for the remediation of mixed HM contamination in paddy fields.

Growing applications of nanoagrichemicals have resulted in their increasing accumulation in agricultural soils, which could modify soil properties and affect soil health. A greenhouse pot trial was conducted to determine the effects of three metallic nanoagrichemicals on several fundamental chemical properties of a rice paddy soil, including zinc oxide nanoparticles (ZnO NPs) and copper oxide nanoparticles (CuO NPs) at 100 mg/kg, and silicon oxide nanoparticles (SiO₂ NPs) at 500 mg/kg, as well as their bulk and ionic counterparts. The investigated soil amendments displayed significant and distinctive impact on the examined soil chemical properties relevant to agricultural production, including soil pH, redox potential, soil organic carbon (SOC), cation exchange capacity (CEC), and plant available As. For example, all amendments increased the bulk soil pH at day 47 to some extent, but the increase was substantially higher for SiO₃²⁻ (37.7%) than other amendments (5.8%–13.7%). Soil Eh was elevated markedly at day 47 after the addition of soil amendments in both the bulk soil (45.9%–74.4%) and rice rhizosphere soil (20.3%–68.9%). CuO NPs and Cu²⁺ generally exhibited greater impact on soil chemical properties than other agrichemicals. Significantly different responses to soil amendments were observed between bulk and rhizosphere soils, suggesting the essential role of plants in affecting soil properties and their responses to environmental disturbance. Overall, our results confirmed that the tested amendments could have remarkable impacts on the fundamental chemical properties of rice paddy soils.

The contamination of arsenic (As) and cadmium (Cd) in paddy soils is widely reported and these two metals are difficult to be co-remediated due to the contrasting chemical behaviors. This poses a challenge to simultaneously decrease their availability in soil and accumulation in rice via immobilization by amendments, especially in in-situ fields. This study compared the effects of carbide slag, lodestone and biochar on the bioavailability of As and Cd in soil and their accumulation in rice tissues and root Fe–Mn plaque at tillering and mature stages in a paddy field. The addition of three amendments significantly limited the mobilization of As and Cd in soil and decreased their accumulations in brown rice by 30–52% and 9–21%, respectively. Carbide slag was most whereas lodestone least effective in As and Cd immobilization in the tested contaminated soils. Community Bureau of Reference (BCR) sequential extraction analysis showed that the amendments changed the forms of As and Cd to less-available. Activated functional groups of the amendments (e.g. –OH, C–O, OC–O, OH⁻ and CO₃²⁻) sequestered metals by precipitation, adsorption, ion exchange or electrostatic attributes contributed greatly to the As and Cd immobilization in soil. Furthermore, the amendments promoted the formation of Fe–Mn plaque in rice roots, which further limited the mobility of As and Cd in soil and prevented their transport from soil to rice roots. The application of carbide slag and biochar but not lodestone increased rice yield compared to the unamended control, indicating their applicability in situ remediation. Our study gives a strong reference to select immobilizing amendments for food safe production in co-contaminated paddy soils.

Urbanization and industrialization have elevated metal concentrations in soils. However, systematic investigation on their availability in regional soils under industrial impacts is lacking. In this study, 230 paired soil-rice samples were collected from two areas in Southeast China, with low and high industrial impacts. Classic equilibrium-based CaCl₂ and EDTA extraction methods, and dynamic-based diffusive gradients in thin-films (DGT) technique were used to study metal availability in soils, with the results being compared with metal concentrations in soils and rice grains. Generally, Cd, Ni, Cu, Zn, Cr and Pb concentrations in soils exceeded the Chinese Soil Quality Standard (GB15618-2018), whereas only Cd and Ni in some rice grains exceeded the Chinese Safety Guidelines. CaCl₂ and EDTA extractions, DGT method and soil total metal concentrations provided good predication of grain Cd (R = 0.51–0.66, p < 0.01), whereas only CaCl₂ and DGT tests provided good predication of grain Ni (R = 0.36–0.47, p < 0.01). Overall, CaCl₂ extraction best predicted Cd and Ni accumulation in rice grains, explaining 66% of grain Cd and 47% of grain Ni. The extraction rate of available Cd was higher than that of Ni, indicating higher Cd availability than Ni, consistent with the parameters (response time, Tc, and desorption rate, k–₁) from DIFS (DGT-induced flux in soils) model and bioconcentration factor values. This study showed that, at regional scale, CaCl₂ extraction method is efficient in predicting Cd and Ni accumulation in rice grains from contaminated soils.