The biogeochemical cycling of sulfur in soil is closely associated with the mobility and bioavailability of heavy metals; however the influence of sulfur on the behavior of metal-based nanoparticles has not yet been studied. The influence of S fertilizer (S⁰ and Na₂SO₄) applied in paddy soils on CuO NPs behavior in soil pore water was explored in the present study. Synchrotron-based techniques were applied to investigate the migration and speciation transformation of CuO NPs in soil pore water colloids. The application of sulfur fertilizer increased the zeta potential of soil colloids from the rice rhizosphere region and reduced the size of the colloids. Sulfur fertilization decreased the concentration of Cu in soil pore water in the rice rhizosphere region. S⁰ fertilizer reduced the Cu concentration in soil colloids (by 55.8%–73.5%), while Na₂SO₄ increased the Cu concentration in soil colloids (by 173.8%–265.1%). Sulfur fertilization changed the spatial distribution of Fe³⁺ and Cu²⁺ in colloids, making these ions more likely to be aggregated on the edges of soil colloids. Speciation transformation of CuO NPs happened during the process of migration. The main Cu speciation in the soil colloids were CuO NPs, Cu-Cysteine, Cu₂S and Cu-Citrate. Sulfur fertilization increased the proportion of Cu₂S (by 40.5%) in soil pore water colloids from the rice rhizosphere region, while the proportion of CuO NPs was reduced (by 18.4%). Sulfur fertilization changed the morphology and elementary composition of colloids in soil pore water, thus influencing the migration of CuO NPs in the soil column through soil colloids.

Pharmacologically active compounds found in reclaimed wastewater irrigation or animal manure fertilizers pose potential risks for agriculture. The mechanism underlying the effects of ketoprofen on rice (Oryza sativa L.) seedlings was investigated. The results showed that low concentrations (0.5 mg L⁻¹) of ketoprofen slightly stimulate growth of rice seedlings, while high concentrations can significantly inhibit growth by reducing biomass and causing damage to roots. Ketoprofen affects photosynthetic pigment content (Chla, Chlb, and carotenoids) and chlorophyll synthesis gene (HEMA, HEMG, CHLD, CHLG, CHLM, and CAO) expression. Fluorescence parameters such as minimum fluorescence (F₀), maximum fluorescence (Fₘ), variable fluorescence (Fᵥ), potential photosynthetic capacity (Fᵥ/F₀), maximum quantum efficiency of PSII photochemistry (Fᵥ/Fₘ), electron transfer rate (ETR), and Y(II), Y(NPQ), Y(NO) values were affected, showing photosynthetic electron transfer was blocked. Active oxygen radical (O₂•−and H₂O₂), malondialdehyde and proline content increased. Superoxide dismutase, catalase and ascorbate peroxidase activities, glutathione content and antioxidant-related gene (FSD1, MSD1, CSD1, CSD2, CAT1, CAT2, CAT3, APX1, APX2) expression were induced. Higher integrated biomarker response values of eight oxidative stress response indexes were obtained at higher ketoprofen concentrations. Ultrastructure observation showed that ketoprofen causes cell structure damage, chloroplast swelling, increase in starch granules, and reduction in organelles. This study provides some suggested toxicological mechanisms and biological response indicators in rice due to stress from pharmacologically active compounds.

Periphyton plays a significant role in heavy metal transfer in wetlands, but its contribution to cadmium (Cd) bioavailability in paddy fields remains largely unexplored. The main aim of this study was to investigate the effect of periphyton on Cd behavior in paddy fields. Periphyton significantly decreased Cd concentrations in paddy waters. Non-invasive micro-test technology analyses indicated that periphyton can absorb Cd from water with a maximum Cd²⁺ influx rate of 394 pmol cm⁻² s⁻¹ and periphyton intrusion significantly increased soil Cd concentrations. However, soil Cd bioavailability declined significantly due to soil pH increase and soil redox potential (Eh) decrease induced by periphyton. With periphyton, more Cd was adsorbed and immobilized on organic matter, carbonates, and iron and manganese oxides in soil. Consequently, Cd content in rice decreased significantly. These findings give insights into Cd biogeochemistry in paddy fields with periphyton, and may provide a novel strategy for reducing Cd accumulation in rice.

Hydroponic experiments were conducted to study the effects of microplastic particles of polystyrene (PS) and polytetrafluoroethylene (PTFE) on arsenic (As) content in leaves and roots of rice seedlings, and the changes in root vigor and physiological and biochemical indicators under single or combined PS and PTFE with As(III) treatment. Rice biomass decreased with increasing concentrations of PS, PTFE, and As(III) in the growth medium. The highest root (leaf) biomass decreases were 21.4% (10.2%), 25.4% (11.8%), and 26.2% (16.2%) with the addition of 0.2 g L⁻¹ PS, 0.2 g L⁻¹ PTFE, and 4 mg L⁻¹ As(III), respectively. Microplastic particles and As(III) inhibited biomass accumulation by inhibiting root activity and RuBisCO activity, respectively. The addition of As(III) and microplastic particles (PS or PTFE) inhibited photosynthesis through non-stomatal and stomatal factors, respectively; furthermore, net photosynthetic rate, chlorophyll fluorescence, and the Chl a content of rice were reduced with the addition of As(III) and microplastic particles (PS or PTFE). Microplastic particles and As(III) induced an oxidative burst in rice tissues through mechanical damage and destruction of the tertiary structure of antioxidant enzymes, respectively, thereby increasing O₂⁻ and H₂O₂ in roots and leaves, inducing lipid peroxidation, and destroying cell membranes. When PS and PTFE were added at 0.04 and 0.1 g L⁻¹, respectively, the negative effects of As(III) on rice were reduced. Treatment with 0.2 g L⁻¹ PS or PTFE, combined with As(III), had a higher impact on rice than the application of As(III) alone. PS and PTFE reduced As(III) uptake, and absorbed As decreased with the increasing concentration of microparticles. The underlying mechanisms for these effects may involve direct adsorption of As, competition between As and microplastic particles for adsorption sites on the root surface, and inhibition of root activity by microplastic particles.

Rice is the world’s most consumed and in-demand grain. Ecuador is one of the main rice-consuming countries in Latin America, with an average per capita consumption of 53.2 kg per year. Rice cultivation takes place under flooding conditions, which favors the mobilization and subsequent accumulation of heavy metals in the plant. This study’s principal objective was to evaluate the contamination of cadmium (Cd) and lead (Pb) in the rice cultivation system in the province of Guayas. To this end, extensive sampling of water, soil and rice grains was carried. Water samples were analyzed to determine physicochemical properties and concentrations of dissolved Cd and Pb. Physicochemical properties, total organic carbon (TOC), total content of nitrogen (N), iron (Fe), manganese (Mn), phosphorus (P), bioavailable phosphorus (P mehlich), Cd and Pb were determined in soil samples. In addition, to understand the dynamics of Cd and Pb mobility and bioavailability, an extraction of six randomly selected soil samples was carried out. The concentration values of the total Cd and Pb content in the rice cultivation system did not exceed the maximum recommended limit for soil, water and rice grains. However, 85% of the total Cd was in the soluble or exchangeable fraction of the soil, while the Pb was strongly bound to crystalline iron oxyhydroxides. It was established that the TOC, N, Fe, and P mehlich have a significant correlation (p < 0.05) with the overall concentration of Cd and Pb in the rice farming soil. The Cd and Pb present in rice do not represent a dietary health risk to the population of Ecuador.

Pollution by antimony (Sb) and arsenic (As) in soil can pose a great threat to human health. Straw-returning is widely applied to paddy fields for improving and remediating soil. A pot experiment was conducted to investigate the effect of straw-returning on Sb and As transformation and translocation in a soil–rice system. In this study, Sb and As co-contaminated soil was thoroughly mixed with different proportions (0, 0.5, 1, and 2%) of straw and used for growing rice plants through the entire growing stage in a pot experiment and 4 weeks in a microcosm experiment. The straw application significantly increased Sb and As mobility. The concentrations of total Sb and As in soil-pore water increased after the application of straw in most growing stages. The Sb volatilization in the pot and microcosm experiments was also stimulated by straw application. With the high dose of straw application (2%), the concentration of Sb in brown grain was reduced by 72% compared with the control, but As concentrations increased by around 77%. These findings provide a new perspective in that straw-returning could affect the behavior of both Sb and As in soil and reduce the Sb accumulation in brown grain and some guidance in the use of straw-returning in Sb-contaminated paddy soil.

Cadmium (Cd) concentration was investigated in parent rocks, surrounding soil of black shales outcrop, stream water, stream sediments, paddy soil as well as rice plants. Leaching test and sequential extraction procedure were applied to evaluate Cd mobility and bioavailability in soil samples. This study aims to emphasize ecological risk of Cd induced by black shales by combining various natural medias in black shales area and control area. The black shales parent rocks have elevated Cd concentration and act as a source of Cd. The liberated Cd from black shales outcrop temporarily accumulated in the acidized surrounding soil and could arise potential adverse impacts on environment due to rainfall. Although high concentration of Cd was not detected in stream water, Cd concentrated stream sediment was a hidden toxin for surface water system. Cd in paddy soil was primarily from geogenic source and effected little by anthropogenic source. The concentration as well as mobility and bioavailability of Cd were high in paddy soil in black shales area, which lead to elevated Cd concentration in roots, shoots and grains of rice. As a result, residents in black shales area suffer increased non-carcinogenic risk of Cd via food chain.

Antimonite [Sb(III)] and antimonate [Sb(V)] are known to have different toxicity to plants, but the corresponding mechanisms are not fully understood. This study was conducted to investigate reactive oxygen species (ROS), antioxidant systems, and levels of certain essential elements in response to exposure to Sb(III) and Sb(V). Results showed that exposure to Sb(V) caused oxidative stress in a rice plant (Yangdao No.6). Sb(III) was shown to be more toxic than Sb(V) as judged from a lower shoot biomass, a higher loss of essential elements, and higher production of superoxide anion free radicals (O₂⁻). The toxicity of Sb(III) might partially be due to the disturbance of the O₂ˉ dismutation reaction, which resulted in root cell membrane damage under exposure to 20 mg L⁻¹ Sb(III). Sb(V) stimulated the shoot fresh weight and the shoot uptake of many essential elements. Moreover, Sb(V) and Sb(III) both stimulated the accumulation of calcium in the shoots and roots, and calcium was found to significantly correlate with the concentrations of many essential elements and with some parameters correlated to antioxidant systems, suggesting a Ca-induced regulatory mechanism. The activity of glutathione peroxidase was significantly enhanced by Sb(V) and Sb(III), suggesting a role in scavenging hydrogen peroxide. Catalase was activated by exposure to 20 mg L⁻¹ Sb(III) in the roots and by exposure to 20 mg L⁻¹ Sb(V) both in the shoots and roots. However, peroxidase was activated by exposure to 5 mg L⁻¹ Sb(III) in the shoots and by exposure to 5 mg L⁻¹ Sb(V) in the roots. This study, for the first time, showed the differences between Sb(V) and Sb(III) toxicity when looking at the antioxidant response and essential element uptake.

Present study reports the laboratory and field scale application of different organic and inorganic amendments to immobilize cadmium (Cd) and lead (Pb) in a co-contaminated alluvial paddy soil. For that purpose, lime, biochar, Fe-biochar and two composite amendments (CA) composed of biochar, lime, sepiolite and zeolite (CA1: composite amendment 1) and manure, lime and sepiolite (CA2: composite amendment 2) were firstly tested in an incubation experiment to ameliorate Cd and Pb co-contaminated alluvial soil. It was observed that liming and CA2 elevated the soil pH and reduced DTPA extractable Cd and Pb in the incubated soil leading to higher metal immobilization. Therefore, efficiency of lime and CA2 was further investigated in field conditions with mid rice as the test crop to evaluate field scale immobilization and precise application rate for the tested soil type. DTPA and CaCl₂ extractable Cd (46 and 51%) and Pb (68 and 70%) in field soil were decreased with applied treatments. Speciation of Cd and Pb also promoted conversion of metal exchangeable contents to less-available forms. Activated functional groups on amendments’ surface (_OH bonding, C_O and CO, -O-H, Si–O–Si, carboxylic and ester groups) sequestered metals by precipitation, adsorption, ion exchange or electro static attributes. Application of lime at 2400 kg/acre (T4) and CA2 at 1200 kg/acre was more effective in reducing rice shoot and grains metal contents. Moreover, obtained results in terms of pH, extractable content, speciation and yield, and microanalysis of amendments highlights the remarkable efficiency of lime and composite amendment to sorb Cd and Pb providing the key evidence of these amendments for metals immobilization and environmental remediation. Considering these results, lime and CA2 are potential amendments for co-contaminated rice field especially in context of alluvial soil.

Technologies for cleaner production of rice in cadmium (Cd) contaminated field are being explored worldwide. In order to investigate the inhibition mechanism of phosphate on Cd transport in soil-plant system, controlled experiments were performed in this study. Experimental results showed that Cd levels in roots, flag leaves, rachises and grains of rice plants (Oryza sativa L.) were significantly reduced by supplement of 0.5–2.5 g kg⁻¹ calcium magnesium phosphate fertilizer (CMP). Path coefficient analysis revealed that phosphorous had significant negative direct effect on Cd, but positive indirect effect on essential and non-essential amino acids. Applying 2.5 g kg⁻¹ CMP made the Cd concentration decreased by 45.7% while free essential and non-essential amino acids increased by 28.0–28.6% in grains. Levels of the branched-chain amino acids in grains were much higher than other essential amino acids, and increased with the amount of CMP fertilization. After application of CMP, pH of soil solution and thickness of the iron plaque around roots increased significantly. Spectra from X-ray photoelectron spectrometer (XPS) showed that content of N, P and Fe increased apparently, C, O and Ca had no change, while S decreased by 74.2% in roots after application of 2.5 g kg⁻¹ CMP. Meanwhile, Cd concentration in protoplasts of root cells decreased by 39.5–80.1% with the increase of CMP. These results indicate that application of CMP can effectively inhibit Cd accumulation in root protoplasts by promoting iron plaque formation on the root surface, reduce Cd concentration and increase free amino acids in rice grains.