Iron oxides and microorganisms are important soil components that profoundly affect the transformation and bioavailability of heavy metals in soils. Here, batch and pot experiments were conducted to investigate the immobilization mechanisms of Cd by Cd-loving Bacillus sp. N3 and ferrihydrite (Fh) as well as their impacts on Cd uptake by wheat and bacterial community composition in wheat rhizospheric soil. The results showed that the combination of strain N3 with Fh could immobilize more Cd compared to strain N3 and Fh, respectively. Furthermore, strain N3 facilitated Cd retention on Fh, which synergistically reduced the concentration of DTPA extracted Cd in the soil and decreased Cd content (57.1%) in wheat grains. Moreover, inoculation with strain N3 increased the complexity of the co-occurrence network of the bacterial community in rhizospheric soil, and the abundance of beneficial bacteria with multipel functions including heavy metal immobilization, dissimilatory iron reduction, and plant growth promotion. Overall, this study demonstrated the enrichment of strain N3 and iron oxides, together with increased soil pH, synergistically immobilized soil Cd, which strongly suggested inoculation with Cd-loving strains could be a promising approach to immobilize Cd and reduce wheat uptake of Cd, particular for soils rich in iron oxides.

In the current investigation, we presented the success of the modified hydrothermal method for synthesizing the iron-oxide nanoparticles (Fe₂O₃-NPs) efficiently. These NPs were further characterized by using different techniques such as X-ray diffraction (XRD), scanning electron microscope (SEM) micrographs, energy-dispersive X-ray spectroscopy (EDAX)/Mapping pattern, Raman Spectroscopy Pattern, ultra violet (UV) and Photoluminescence (PL). All these analyses revealed highly pure nature of Fe₂O₃-NPs with no internal defects, and suggested its application for plant growth improvement. Therefore, we further investigated the separate as well as combined effects of the Fe₂O₃-NPs and citric acid (CA) in the alleviation of arsenic (As) toxicity in the soybean (Glycine max L.), by evaluating the different plant growth and metabolic attributes. Results of our study revealed that As-induced growth inhibition, reduction of photosynthesis, water use efficiency (WUE), and reactive oxygen species (ROS) accumulation whereas application of the Fe₂O₃-NPs and CA significantly reversed all these adverse effects in soybean plants. Moreover, the As-stress induced malondialdehyde (MDA) and hydrogen peroxide (H₂O₂) production were partially reversed by the Fe₂O₃-NPs and CA in the As-stressed plants by 16% and 10% (MDA) and 29% and 12% (H₂O₂). This might have resulted due to the Fe₂O₃-NPs and CA induced activities of the antioxidant defense in plants. Overall, the Fe₂O₃-NPs and CA supplementation separately and in combination positively regulated the As tolerance in soybean; however, the effect of the combined application on the As tolerance was more profound relative to the individual application. These results suggested the synergetic effect of the Fe₂O₃-NPs and CA on the As-tolerance in soybean. However, in-depth mechanism underlying the defense crosstalk between the Fe₂O₃-NPs and CA needs to be further explored.

In this study, we assessed the impact of zinc oxide (ZnO) and iron oxide (FeO) (<36 nm) nanoparticles (NPs) as well as their sulphate salt (bulk) counterpart (0, 25, 100 mg/kg) on rice growth and seed quality as well as the microbial community in the rhizosphere environment of rice. During the rice growing season 2021–22, all experiments were conducted in a greenhouse (temperature: day 30 °C; night 20 °C; relative humidity: 70%; light period: 16 h/8 h, day/night) in rice field soil. Results showed that low concentrations of FeO and ZnO NPs (25 mg/kg) promoted rice growth (height (29%, 16%), pigment content (2%, 3%)) and grain quality parameters such as grains per spike (8%, 9%), dry weight of grains (12%, 14%) respectively. As compared to the control group, the Zn (2%) and Fe (5%) accumulations at their respective low concentrations of NP treatments showed stimulation. Interestingly, our results showed that at low concentration of both the NPs the soil microbes had more diversity and richness than those in the bulk treated and control soil group. Although a number of phyla were affected by the presence of NPs, the strongest effects were observed for change in the abundance of the three phyla for Proteobacteria, Actinobacteria, and Planctomycetes. The rhizosphere environment was notably enriched with potential streptomycin producers, carbon and nitrogen fixers, and lignin degraders with regard to functional groups of microorganisms. However, microbial communities mainly responsible for chitin degradation, ammonia oxidation, and nitrite reduction were found to be decreased. The results from this study highlight significant changes in several plant-based endpoints, as well as the rhizosphere soil microorganisms. It further adds information to our understanding of the nanoscale-specific impacts of important micronutrient oxides on both rice and its associated soil microbiome.

Arsenic (As) is a toxic metalloid that is ubiquitous in paddy soils, where passivation is the most widely used method for remediating As contamination. Recently, anaerobic methane oxidation coupled with arsenate (As(V)) reduction (AOM-AsR) has been shown to act as a critical driver for As release in paddy fields. However, the effect and mechanism of the passivators on the AOM-AsR process remain unclear. In this study, we incubated arsenate-contaminated paddy soils under anaerobic conditions. Using isotopically labelled methane and different passivators, we found that an iron-based passivator containing calcium sulfate and iron oxide (9:1, m/m) named IBP showed a much better performance than the other passivators. Adding IBP decreased the arsenite (As(III)) concentration in the soil solution by 78% and increased the AOM rate by 55%. Furthermore, we employed high-throughput sequencing and real-time quantitative polymerase chain reaction (qPCR) to investigate the ability of IBP to control As release mediated by AOM-AsR in paddy fields, as well as its underlying mechanism. Our results showed that IBP addition significantly increased anaerobic methanotrophic (ANME) archaea (ANME-2a-c, ANME-2d, and ANME-3) by 91%, and increased the methane-oxidizing bacterium Methylobacter by 262%. Similarly, IBP addition significantly increased the Fe(III) concentration in soil solution by 39% and increased the absolute abundance of Fe(III)-reducing bacteria (Geobacteraceae) by 21 times in soil. Adding IBP may significantly promote AOM coupled with Fe(III) reduction, significantly reducing electron transfer from AOM to As(V) reduction. Hence, IBP may be used as an efficient passivator to remediate As-contaminated soil using an active AOM-AsR process. These results provide a novel insight into controlling soil As release by regulating an active and critical As mobilization pathway in the environment.

Colloid-sized microplastics (MPs) are ubiquitous in aquatic environments and can share the same transport route together with various crystalline, poorly crystalline and freshly formed iron oxides. However, the colloidal interactions between these colloid constituents are not fully understood. This study was designed to investigate the colloidal properties of polystyrene microplastics (PSMPs) under the influence of haematite, goethite, ferrihydrite and freshly formed Fe oxide (FFFO). Dynamic light scattering was coupled with a test tube method to observe changes in the surface charge and colloidal dynamics of suspensions of PSMPs and Fe oxides. The overall effects on the aggregation of PSMPs are found to decrease in the following order: FFFO > ferrihydrite > goethite > haematite. The effects of these Fe oxides are found to strongly depend on pH. While the crystalline oxides play a dominant role in the acidic environment, poorly crystalline oxides show greater effects on PSMP aggregation in an alkaline environment. Heteroaggregation due to decreasing electrostatic interactions is the major mechanism that governs the colloidal dynamics of PSMPs and Fe oxides. It can be inferred that the copresence of Fe oxides and MPs can delay the transport of MPs or even change the destination for MPs.

The excessive arsenic (As) accumulation in plant tissues enforced toxic impacts on growth indices. So, the utilization of As-contaminated food leads to risks associated with human health. For the reduction of As concentrations in foods, it is obligatory to fully apprehend the take up, accretion, transportation and toxicity mechanisms of As within plant parts. This metalloid impairs the plant functions by disturbing the metabolic pathways at physio-biochemical, cellular and molecular levels. Though several approaches were utilized to reduce the As-accumulation and toxicity in soil-plant systems. Recently, engineered nanoparticles (ENPs) such a zinc oxide (ZnO), silicon dioxide or silica (SiO₂), iron oxide (FeO) and copper oxide (CuO) have emerged new technology to reduce the As-accumulation or phytotoxicity. But, the mechanistic approaches with systematic explanation are missing. By knowing these facts, our prime focus was to disclose the mechanisms behind the As toxicity and its mitigation by ENPs in higher plants. ENPs relives As toxicity and its oxidative damages by regulating the transporter or defense genes, modifying the cell wall composition, stimulating the antioxidants defense, phytochelatins biosynthesis, nutrients uptake, regulating the metabolic processes, growth improvement, and thus reduction in As-accumulation or toxicity. Yet, As-detoxification by ENPs depends upon the type and dose of ENPs or As, exposure method, plant species and experimental conditions. We have discussed the recent advances and highlight the knowledge or research gaps in earlier studies along with recommendations. This review may help scientific community to develop strategies such as applications of nano-based fertilizers to limit the As-accumulation and toxicity, thus healthy food production. These outcomes may govern sustainable application of ENPs in agriculture.

Hydroxyapatite (HAP) can effectively immobilize soil heavy metals, but excess phosphate would be released to aquatic ecosystem, resulting in eutrophication. This study investigated the effects of ferrihydrite (FH) on the HAP immobilization of copper (Cu) and cadmium (Cd) and their reduction of phosphorus release under flooding-drainage alternation conditions. Results showed that the incorporation of HAP and FH significantly increased soil solution pH and decreased Cu²⁺ and Cd²⁺ concentrations. Applications of FH, HAP, and FH-HAP (FH and HAP combination) can all enhance soil pH and reduce CaCl₂-extractable and exchangeable Cu and Cd, but HAP addition increased soluble phosphate by 6.60–7.77 times compared to control. However, FH-HAP application can significantly reduce phosphate release by 92.7–99.7% compared to HAP application. FH-HAP was the most effective to reduce exchangeable Cu and Cd by 49.8–93.4% and 50.9–88.8% and decreased labile and moderately labile phosphorus by 34.0–74.4% and 13.5–18.6%, respectively, while increased stable phosphorus by 22–45.1% than single HAP. All FH treatments significantly increased amorphous iron oxides by the factors of 4.66–20.8, but only 3% and 5% of FH applications slightly enhanced crystal iron oxides by the factors of 0.81–1.27. The major implication is that the combination of FH and HAP can not only immobilize of Cu and Cd, but also reduce the risk of phosphate release by HAP addition.

Despite arsenic (As) bioavailability being highly correlated with water status and the presence of iron (Fe) minerals, limited information is currently available on how externally applied Fe nanomaterials in soil-rice systems affect As oxidation and stabilization during flooding and draining events. Herein, the stabilization of As in a paddy soil by a phytosynthesized iron oxide nanomaterials (PION) and the related mechanism was investigated using a combination of chemical extraction and functional microbe analysis in soil at both flooding (60 d) and draining (120 d) stages. The application of PION decreased both specifically bound and non-specifically bound As. The As content in rice root, stem, husk and grain was reduced by 78.5, 17.3, 8.4 and 34.4%, respectively, whereas As(III) and As(V) in root declined by 96.9 and 33.3% for the 1% PION treatment after 120 d. Furthermore, the 1% PION treatment decreased the ratio of As(III)/As(V) in the rhizosphere soil, root and stem. Although PION had no significant effect on the overall Shannon index, the distribution of some specific functional microbes changed dramatically. While no As(III) oxidation bacteria were found at 60 d in any treatments, PION treatment increased As(III) oxidation bacteria by 3–9 fold after 120 d cultivation. Structural equation model analysis revealed that the ratio of Fe(III)/Fe(II) affected As stabilization directly at the flooding stage, whereas nitrate reduction and As(III) oxidation microbial groups played a significant role in the stabilization of As at the draining stage. These results highlight that PION exhibits a robust ability to reduce As availability to rice, with chemical oxidation, reduction inhibition and adsorption dominating at the flooding stage, while microbial oxidation, adsorption and coprecipitation dominant during draining.

Novel magnetic microcomposites consisting of graphene oxide and iron oxide was synthesized to immobilize metabolically versatile Paracoccus sp. MKU1 and Leucobacter sp. AA7 and tested for the simultaneous adsorption and enhanced biological detoxification of hexavalent chromium (Cr(VI)) from tannery wastewater. This study reports highest chromium adsorption of 272.6 mg/g and 179.3 mg/g with complete reduction of Cr(VI) to Cr(III) by the microcomposites of AA7 and MKU1 from wastewater in a bioreactor (10 L) at large-scale for first time in ex situ. Furthermore, both the microcomposites displayed an enhanced detoxification of tannery wastewater by reducing various physicochemical conditions such as ammonia, nitrate, TDS, fluoride, CaCO₃, Ca, Mg, NO₃ and SO₂ under the permissible limits. Use of electromagnetic device for magnetic microcomposites recovery from bioreactor yielded a maximum of 88% and 80.6% recovery for AA7 and MKU1, respectively. The rate of chromium recuperation achieved following desorption from the microcomposites of AA7 and MKU1 was 90.71% and 93.97%, respectively. Thus, the multifarious benefits including adsorption, metabolic detoxification, recovery, and recuperation by single functional microcomposites seems to be an intriguing and profitable approach for practicing in real-time operations to effectively remove heavy metals from the contaminated wastewater for environmental protection.

The growth and development patterns of crop plants are being seriously threatened by arsenic (As) contamination in the soil, and it also acts as a major hurdle in crop productivity. This study focuses on arsenate As(V) mediated toxicity in rice plants. Further, among the different type of NPs, iron oxide nanoparticles (FeO NPs) display a dose-dependent effect but their potential role in mitigating As(V) stress is still elusive. FeO NPs (500 μM) play a role in imparting cross-tolerance against As(V) induced toxicity in rice. Growth attributes, photosynthetic performance, nutrient contents and biochemical parameters were significantly altered by As(V). But FeO NPs rescued the negative consequences of As(V) by restricting its entry with the possible involvement of NO in rice roots. Moreover, results related with gene expression of NO(OsNoA1 and OsNIA1) and proline metabolism were greatly inhibited by As(V) toxicity. But, FeO NPs reversed the toxic effect of As(V) by improving proline metabolism and stimulating NO mediated up-regulation of antioxidant enzymes particularly glutathione-S-transferase which may be possible reasons for the reduction of As(V) toxicity in rice roots. Overall, it can be stated that FeO NPs may act as an As(V) barrier to restrict the As(V) uptake by roots and have the ability to confer cross tolerance by modulating various morphological, biochemical and molecular characteristics with possible intrinsic involvement of NO.