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.

The alkaline mineral amendment is a practical means of alleviating Cd concentration in rice grain (CdR) in the short-term; however, the long-term remediation effect of mineral amendment on the CdR and the eco-environmental controls remains unknown. Here a mineral (Si–Ca–Mg) amendment, calcined primarily from molybdenum tailings and dolomite, was applied biannually over 6 years (12 seasons) to acidic and moderately Cd-contaminated double-rice cropping ecosystems. This study investigated the inter-annual variation of Cd in the rice-soil ecosystem and the eco-environmental controls in subtropical rice ecosystems. CdR was reduced by 50%–86% following mineral amendment. The within-year reduction in CdR was similar between early rice (50%–86%, mean of 68%) and late rice (68%–85%, mean of 74%), leading to CdR in all early rice and in 83% of late rice samples below the upper limit (0.2 mg kg⁻¹) of the China National Food Safety Standards. In contrast, the inter-annual reduction in CdR was moderately variable, showing a greater CdR reduction in the later 3 years (73%–86%) than in the former 3 years (54%–79%). Three years continuous mineral amendment was required to guarantee the safety rice production. The concentrations of DTPA-extractable and exchangeable Cd fractions in soil were reduced, while the concentration of oxides-bound Cd was increased. In addition, the soil pH, concentrations of Olsen-P and exchangeable Ca and Mg were elevated. These imply a lower apparent phytoavailability of Cd in the soil following mineral amendment. An empirical model of the 3-variable using soil DTPA-Cd, soil Olsen-P, and a climatic factor (precipitation) effectively predicted temporal changes in CdR. Our study demonstrates that Cd phytoavailability in soil (indexed by DTPA-extractable Cd) and climatic factors (e.g., temperature and precipitation) may directly/indirectly control the inter-annual reduction in CdR following mineral amendment in slightly and moderately Cd-contaminated paddy ecosystems.

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.

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.

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.

Arsenic (As) behavior in paddy soils couples with the redox process of iron (Fe) minerals. When soil is flooded, Fe oxides are transformed to soluble ferrous ions by accepting the electrons from Fe reducers. This process can significantly affect the fate of As in paddy fields. In this study, we show a novel technique to manipulate the Fe redox processes in paddy soils by deploying soil microbial fuel cells (sMFC). The results showed that the sMFC bioanode can significantly decrease the release of Fe and As into soil porewater. Iron and As contents around sMFC anode were 65.0% and 47.0% of the control respectively at day 50. The observed phenomenon would be explained by a competition for organic substrate between sMFC bioanode and the iron- and arsenic-reducing bacteria in the soils. In the vicinity of bioanode, organic matter removal efficiencies were 10.3% and 14.0% higher than the control for lost on ignition carbon and total organic carbon respectively. Sequencing of the 16S rRNA genes suggested that the influence of bioanodes on bulk soil bacterial community structure was minimal. Moreover, during the experiment a maximum current and power density of 0.31 mA and 12.0 mWm−2 were obtained, respectively. This study shows a novel way to limit the release of Fe and As in soils porewater and simultaneously generate electricity.

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.

The rapid expansion of organic rice cultivation areas have been accompanied by increased application of organic fertilizers. The high prevalence of soil antibiotic resistance caused by organic fertilizer application poses a severe threat to the agricultural and soil ecosystems. To date, research efforts and understanding of the effects and mechanism of action of the various organic fertilizers on antibiotic resistance in paddy soils remain poorly investigated. Tetracycline resistance genes (TRGs, including tetB, tetC, tetL, tetZ, tetM, tetO, tetT, and tetX), class 1 integron-integrase gene (intI1) and bacterial communities were characterized using quantitative-PCR and Illumina MiSeq sequencing, in paddy soils exposed to inorganic fertilizer (NPK), animal-derived organic fertilizer (AOF, composted swine and/or chicken manure), plant-derived organic fertilizer (POF, rapeseed cake and/or astragalus) and commercial organic fertilizer (COF, composted of animal manure mix with crop residues) applications. Compared with NPK, AOF applications significantly increased the relative abundance of TRGs, which was predominantly expressed in the increase of the relative abundance of tetC, tetM, tetO, tetT, and tetX, while POF and COF had no significant effect on the relative abundance of TRGs. Principal coordinate analysis revealed that AOF and POF significantly altered bacterial communities in paddy soils relative to NPK, while COF had no significant change of bacterial communities. Variation partitioning analysis indicated that soil physicochemical properties were the decisive factors for the changes of TRGs in organic paddy fields. Furthermore, redundancy analysis and the Mantel test showed that TRG profiles in AOF applied paddy soils were strongly influenced by electrical conductivity (EC). Total nitrogen (TN) and organic matter (OM) affected the distribution of TRGs in COF and POF applied paddy soils through a different mechanism. This study provides insights into the impacts of different types of organic fertilizer on the profiles of TRGs in paddy soils.

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.

Biogas slurry (BS) and bio-waste hydrothermal carbonization aqueous phase (HP) are nutrient-rich wastewater. To prevent environment contamination, transforming BS and HP into synthetic fertilizers in the agricultural field can potentially realize resource utilization. We hypothesized that acidic HP could neutralize alkaline BS, adjusting floodwater pH from 6.88 to 8.00 and mitigating ammonia (NH₃) volatilization from the paddy soil. In this soil column study, the mixture of BS and HP was applied to paddy soil to substitute 50%, 75%, and 100% to urea. With a low (L) or high (H) ratio of HP, treatments were labeled as BCL50, BCL75, BCL100, BCH50, BCH75, and BCH100. Results showed that microbial byproduct- and fulvic acid-like substance were the main components in BS and HP using 3D-EEM analysis, respectively. Co-application of BS and HP mitigated the NH₃ volatilization by 4.2%–65.5% compared with CKU. BCL100 and BCH100 treatments significantly (P < 0.05) mitigated NH₃ volatilization by 65.5% and 56.8%, which also significantly (P < 0.05) mitigated the yield-scale NH₃ volatilization by 49.6% and 42.3%, compared with CKU. The low NH₄⁺-N concentration and pH value in floodwater were the main reason explained the NH₃ mitigation. Therefore, this study demonstrated that BS and HP co-application can substitute the urea as a valuable N fertilizer in a rational rate and meanwhile mitigate the NH₃ volatilization. This study will provide new ideas for the utilization of BS and HP resources in the context of ammonia mitigation.