Cadmium (Cd) is a major pollutant in farmland, which not only greatly restricts crop production, but also brings a serious threat to human health through entering the food chain. Our previous study showed that hemin treatment could reduce the accumulation of Cd in pak choi seedlings. However, the underlying mechanism remains unclear. In this study, we used non-invasive micro-test technology (NMT) to detect the real-time Cd²⁺ flux from pak choi roots and demonstrated that hemin treatment decreased Cd uptake rather than its translocation within plants. Moreover, through comparing the responses of different chemical treatments in pak choi seedlings and Arabidopsis wild-type and heme oxygenase-1 (HO-1) mutant, we provided evidence that hemin-decreased Cd uptake was HO-1 dependent. Furthermore, analyses of hemin degradation products suggested that the hemin-derived suppression of Cd uptake suppression was probably relying on its degradation by-products, ferrous iron (Fe²⁺) and carbon monoxide (CO), via repressing the expression of a Fe²⁺/Cd²⁺ transporter BcIRT1 in pak choi roots.

The feasibility and effectiveness of iron turning waste as low cost and sustainable permeable reactive barrier (PRB) media for remediating dieldrin, endrin, dichlorodiphenyltrichloroethane (DDT), and lindane individually (batch system) and combined (continuous flow column) in water were investigated. After 10 min of reaction in a batch system, removal of endrin, dieldrin, and DDT was higher (86–91 %) than lindane (41 %) using 1 g of iron turning waste in 200 mL of pesticide solution (20 μg/L for each pesticide). Among the studied pesticides, only lindane removal decreased substantially in the presence of nitrate (37 %) and magnesium (18 %). Acidic water environment (pH = 4) favored the pesticide removal than neutral and basic environments. For the column experiments, sand alone as PRB media was ineffective for remediating the pesticides in water. When only iron turning was used, the removal efficiencies of lindane, endrin, and dieldrin were 83–88 % and remained stable during 60 min of the experiments. DDT removal was less than other pesticides (58 %). Sandwiching the iron turning waste media between two sand layers improved DDT removal (79 %) as well as limited the iron content below a permissible level in product water. In a long-term PRB column performance evaluation, iron turning waste (150 g) removed all pesticides in water (initial concentration of each pesticide = 2 μg/L) effectively (≥94 %) at a hydraulic retention time of 1.6 h. Iron turning waste, which was mainly in the form of zerovalent iron (Fe⁰), was oxidized to ferrous (Fe²⁺) and ferric (Fe³⁺) iron during its reaction with pesticides, and electrons donated by Fe⁰ and Fe²⁺ were responsible for complete dechlorination of all the pesticides. Therefore, it can be used as inexpensive and sustainable PRB media for groundwater remediation especially in developing countries where groundwater contamination with pesticides is more prevalent.

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.

Phosphorus (P) cycling present in sediments associated with iron (Fe), manganese (Mn) and sulfur (S) geochemical processes may cause secondary pollution in overlying water. Understanding the mechanisms of P release from sediments should help to restore water quality. This study used the diffusive gradients in thin film (DGT) technique to investigate the seasonal variation in the lability, remobilization mechanisms, and release characteristics of sediment P in the uncontaminated Xizhi River and the severely contaminated Danshui River, South China. P accumulation in sediments contributed to higher DGT-labile P concentrations in contaminated reaches, and the highest labile P concentrations were generally observed in summer season at each site. The significant positive relationships (p < 0.05) between labile Fe and P confirmed the Fe–P coupling release mechanism in uncontaminated sediments. Stronger relationships between labile Mn and P at contaminated sites indicated that Mn oxides played an important role in P remobilization. However, sulfate reduction associated with microbial activities (crucial genera: Desulfobulbus, Desulfomicrobium and Desulforhabdus) was considered to decouple the Fe & Mn–P cycling relationship, promoting P release at contaminated sites. The effluxes of sediment P were much higher in the Danshui River (mean 0.132 mg cm⁻²·d⁻¹) than in the Xizhi River (mean 0.038 mg cm⁻²·d⁻¹). And hot season led to growth in P effluxes that was much greater in contaminated river.

2,2′,4,4′-tetrabromodiphenyl ether (BDE-47) was difficult to degrade in sediments. In this study, the environmental behavior of BDE-47 with/without the effect of benthos (Tubificidae Limnodrilus) and electron acceptors in sediments was investigated using C-14 tracer. Generally, extractable residues of BDE-47 were dominant in sediment and posed high environment risk. The amount of non-extractable residues (NERs) accounted for 39.0% of initial radioactivity in oxic sediments was significantly higher than those in anoxic sediments (17.6%). Most of NERs were localized in the humin fraction and presented as sequestrated forms. Under oxic conditions, the present of Limnodrilus significantly increased the proportion of NERs in sediment. Limnodrilus accumulated 34.2% of initial radioactivity. Under anoxic conditions, the addition of iron (Ⅲ) [Fe(III)], sulfate and nitrate reduced the environmental risk of BDE-47 with the increase of NERs formation, while manganese (IV) [Mn(IV)] addition had no effect on the formation of NERs. The present of Limnodrilus and electron acceptors promoted the production of metabolites. Meanwhile, BDE-47 changed the microbial community structure of sediments. These findings indicated that the environmental behavior and risk of BDE-47 was affected by benthos and electron acceptors, and the high proportion of sequestrated NERs posed high bioactivity and toxic threat to ecological environment.

Antarctic melt streams are important ecosystems that increasingly face contaminant pressures from anthropogenic sources. Metal contaminants are often reported in the limno-terrestrial environment but their speciation is not well characterised, making environmental risk assessments difficult. This paper characterises labile metal concentrations in five melt streams and three shallow lakes around the Casey and Wilkes research stations in East Antarctica using chemical extracts and field deployments of diffusive gradients in thin-film (DGT) samplers. An acute toxicity test with field-collected Ceratadon purpeus and taxonomic identification of diatoms in melt streams were used to infer environmental risk. Copper and zinc were the most labile metals in the melt streams. DGT-labile copper concentrations were up to 3 μg Cu L⁻¹ in melt-stream waters but not labile below the sediment-water interface. DGT-labile zinc concentrations were consistent above and below the sediment-water interface at concentrations up to 14 μg Zn L⁻¹ in four streams, but one stream showed evidence of zinc mineralisation in the sediment with a flux to overlying and pore waters attributed to the reductive dissolution of iron and manganese oxides. Other metals, such as chromium, nickel, and lead were acid-extractable from the sediments, but not labile in pore waters or overlying waters. All streams had unique compositions of freshwater diatoms, but one had particularly reduced diversity and richness, which correlated to metal contamination and sediment physico-chemical properties such as a finer particle size. In laboratory bioassays with field-collected samples of the Antarctic moss C. purpeus, there was no change in photosynthetic efficiency following 28-d exposure to 700, 900, 1060, or 530 μg L⁻¹ of cadmium, copper, nickel, and zinc, respectively. This study shows that microorganisms such as diatoms may be at greater risk from contaminants than mosses, and highlights the importance of geochemical factors controlling metal lability.

Soils containing a large proportion of industrial waste can pose a health risk due to high environmentally available concentrations of toxic metal(loid)s. Nano zero-valent iron (nZVI) and amorphous manganese oxide (AMO) were applied as immobilising amendments (1 wt%) to soils with different industrial origin of As and Sb, and leaching of As, Sb, Pb, and Zn was investigated using a single extraction with deionised water. The different industrial impact was reflected in the mineralogy, chemical composition and pH of these soils. Water-soluble As ratios positively correlated with pH in all experimental treatments. A significant decrease of water-soluble As ratios was observed in all nZVI-amended soils (~65–93% of the control) except for one sample with the lowest solution pH. Nano zero-valent iron was also successful in Sb immobilisation (~76–90% of the control). Highly variable results were obtained for AMO, which only led to a decrease of water-soluble As in soils with solution pH of ≥7 (~70–80% of the control), probably due to lower stability of AMO in acidic conditions. In each case, nZVI was more efficient at decreasing water-soluble As ratios than AMO. Dissolved Pb concentrations remained unchanged after the application of nZVI and AMO, and the decrease of Zn leaching using AMO was controlled mainly by soil pH increase induced by its application. According to the calculated saturation indices, tripuhyite (FeSbO₄) was predicted to be the key mineral controlling Sb solubility in mine soils. Secondary Fe (hydr)oxides either originally present or newly formed due to nZVI oxidation were instrumentally identified at different stages of their transformation and metal(loid) retention. To conclude, nZVI is suitable for application to contaminated soils at a wide pH range, while the use of AMO for decreasing As leaching is limited to soils with pH ≥ 7.

Ecological floating beds (EFBs) have become a superior method for treating secondary effluent from wastewater treatment plant. However, insufficient electron donor limited its denitrification efficiency. Iron scraps from lathe cutting waste consist of more than 95% iron could be used as electron donors to enhance denitrification. In this study, EFBs with and without iron scraps supplementation (EFB-Fe and EFB, respectively) were conducted to explore the impacts of iron scraps addition on nitrogen removal, nitrous oxide (N₂O) emissions and microbial communities. Results showed the total nitrogen (TN) removal in EFB-Fe improved to 79% while that in EFB was 56%. N₂O emission was 0–6.20 mg m⁻² d⁻¹ (EFB-Fe) and 1.74–15.2 mg m⁻² d⁻¹ (EFB). Iron scraps could not only improve nitrogen removal efficiency, but also reduce N₂O emissions. In addition, high-throughput sequencing analysis revealed that adding iron scraps could improve the sum of denitrification related genera, among which Novosphingobium accounted for the highest proportion (6.75% of PFe1, 4.24% of PFe2, 3.18% of PFe3). Iron-oxidizing bacteria and iron-respiring bacteria associated with and nitrate reducing bacteria mainly concentrated on the surface of iron scraps. Principal co-ordinates analysis (PCoA) indicated that iron scraps were the key factor affecting microbial community composition. The mechanism of iron scraps enhanced nitrogen removal was realized by enhanced biological denitrification process. Iron release dynamic from iron scraps was detected in bench-scale experiment and the electron transfer mechanism was that Fe⁰ transferred electrons directly to NO₃⁻-N, and biological iron nitrogen cycle occurred in EFB-Fe without secondary pollution.

Porous silicon-coated zero-valent iron (Fe⁰@p-SiO₂) is a promising material for in-situ contaminated groundwater remediation. However, investigations of factors that affect the transport of Fe⁰@p-SiO₂ remain incomplete. In the present study, Fe⁰@p-SiO₂ composites were prepared by a SiO₂-coated technology, and a series of column experiments were conducted to examine the effects of media size, ionic strength, and injection velocity and concentration on retention and transport in saturated porous media. Results showed that the obtained Fe⁰@p-SiO₂ is a core-shell composite with zero-valent iron as the core and porous silicon as the shell. Media size, injection velocity, Fe⁰ concentration, and ionic strength had a significant impact on the transport of Fe⁰@p-SiO₂. Fe⁰@p-SiO₂ effluent concentrations decreased with a smaller media size. Increasing initial particle concentration and ionic strength led to a decrease in particle transport. High particle retention was observed near the middle of the column, especially with high injection concentration. That was also observable in the condition of lower injection velocity or finer media. The results indicated that two transport behaviors during particles transport, which were “agglomeration-straining” and “detachment-re-migration”. Moreover, the dominated mechanisms for Fe⁰@p-SiO₂ transport and retention in saturated porous media are hydrodynamic dispersion and interception. Given the results, in practical engineering applications, proper injection velocity and concentration should be selected depending on the pollution status of groundwater and the geochemical environment to ensure an effective in-situ reaction zone.

The present study aimed to show that nickel and fluoride exhibited synchronized co-inhibited uptake in the aromatic rice cultivar, Gobindobhog, since bioaccumulation of the two elements was lower than that during individual stress, so that overall growth under combined stress was similar to control seedlings. On the contrary, lead and fluoride stimulated their co-uptake which triggered oxidative damages, NADPH oxidase activity, methylglyoxal accumulation, photosynthetic inhibition, membrane-protein damages, necrosis and genomic template degradation. Accumulation of proline, anthocyanins, non-protein thiols and phytochelatins was stimulated for systemic protection against reactive oxygen species (ROS) and xenobiotic-mediated injuries during lead-fluoride toxicity. ROS accumulation during nickel-fluoride stress was insignificant due to which enhanced accumulation of most antioxidants was not required. Glutathione depletion during combined lead-fluoride toxicity was due to its utilization in the glyoxalase cycle and also inhibition of glutathione reductase. However, the nickel-fluoride-treated sets maintained glutathione reserves and glyoxalase activity similar to those in control. Presence of fluoride ‘safeguarded’ the glutathione-utilizing enzymes like glutathione reductase, glutathione peroxidase and glutathione-S-transferase during dual lead-fluoride stress. This was because these enzymes showed higher activity compared to that under lead toxicity alone. Enzymatic antioxidants like superoxide dismutase, ascorbate peroxidase and guaiacol peroxidase were activated during lead-fluoride toxicity due to altered iron and copper homeostasis. Catalase activity was strongly inhibited, resulting in the inability to scavenge H₂O₂ and suppression of the fluoride-adaptable phenotype. However, none of the enzymatic antioxidants were inhibited during nickel-fluoride stress, which cumulatively allowed the seedlings to maintain normal physiology. Overall our findings holistically reveal the physiological plasticity of Gobindobhog in response to two different heavy metals under the influence of fluoride.