International audience | Aided phytostabilization using a combination of compost, zerovalent iron grit and coal fly ash (CZA) amendments and revegetation effectively promoted the biological recovery of mining spoils generated at a gold mine in Portugal. Selective dissolution of spoil samples in combination with solid phase characterization using microbeam X-ray absorption near edge structure (μXANES) spectroscopy and microbeam X-ray fluorescence (μXRF) mapping were used to assess As associations in spoils ten years after CZA treatment. The results show that As preferentially associates with poorly crystalline Fe-oxyhydroxides as opposed to crystalline Fe-(oxyhydr)oxide phases. The crystalline Fe(III)-phases dominated in the treated spoil and exceeded those of the untreated spoil three-fold, but only 2.6–6.8% of total As was associated with this fraction. Correlation maps of As:Fe reveal that As in the CZA-treated spoils is primarily contained in surface coatings as precipitates and sorbates. Arsenic binding with poorly crystalline Fe-oxyhydroxides did not inhibit As uptake by plants.

Physicochemical and biological characterisation of different dredged sediment deposit sites in France

Fluoride (F) is an emerging pollutant that originates from multiple sources and adversely affects plant growth and nutrient bioavailability in soil. This greenhouse study investigated the effects of soil F (0, 10, 20, 50, 100, 200 mg kg⁻¹) on morpho-physiological growth characteristics of wheat, soil F contents, and bioavailability and uptake of F, phosphorus (P), sulphur (S), potassium (K), calcium (Ca), magnesium (Mg), aluminium (Al), iron (Fe), manganese (Mn), silicon (Si) and zinc (Zn) by wheat. Higher F significantly reduced plant height and number of leaves particularly at early growth stages and increased visible leaf injury index. Powdery mildew infestation coincided with leafy injury and was higher in elevated soil F treatments. Fluoride treatments (>50 mg kg⁻¹) significantly increased water (H₂O)- and calcium chloride (CaCl₂)-extractable F contents in soil. Water-extractable soil F contents from soil in all concentration were higher than CaCl₂-extractable F. This increased F bioavailability resulted in significantly higher F uptake and accumulation in live leaves, dead leaves and grains of wheat which followed order: live leaves > dead leaves > grains. Leaf injury index and number of dead leaves correlated significantly positively with soil H₂O- and CaCl₂-extractable F contents. Patterns of nutrient (P, K, S) and trace metals (Al, Ca, Mg, Fe, Mn, Si, Zn) varied significantly with F concentrations and between live and dead leaves, and grains except for Zn. Dead leaves generally had higher nutrients and trace metals than live leaves and grains. Fluoride contents in live leaves, dead leaves and grains showed positive correlations with nutrient elements but negative with trace metals. Number of dead leaves correlated negatively with Al, Ca, Fe, Mg, S and Si but positively with P and Zn contents in dead leaves whereas leaf injury index showed positive correlation with Fe, K, P, Si, Zn, S but negative with Al, Ca and Mg contents. These observations provided evidence of higher F uptake and associated impairment in nutrient and trace metal accumulation which caused leaf injury accompanied by powdery mildew infestation in wheat. However, further research in the region is required to confirm the relationship between F pollution, leaf injury and trace metal accumulation in crops under field conditions.

Inhalation of respirable silica particles can cause serious lung diseases (e.g., silicosis and lung cancer), and the toxicity of respirable silica is highly dependent on its crystal form. Common combustion processes such as coal and biomass burning can provide high temperature environments that may alter the crystal forms of silica and thus affect its toxic effects. Although crystalline silica (i.e., quartz, tridymite, and cristobalite) were widely found at different temperatures during the burning processes, the sources and crystal transformation pathways of silica in the burning processes are still not well understood. Here, we investigate the crystal transformation of silica in the coal and biomass combustion processes and clarify the detailed transformation pathways of silica for the first time. Specifically, in coal burning process, amorphous silica can transform into quartz and cristobalite starting at 1100 °C, and quartz transforms into cristobalite starting at 1200 °C; in biomass burning process, amorphous silica can transform into cristobalite starting at 800 °C, and cristobalite transforms into tridymite starting at 1000 °C. These transformation temperatures are significantly lower than those predicted by the classic theory due to possibly the catalysis of coexisting metal elements (e.g., aluminum, iron, and potassium). Our results not only enable a deeper understanding on the combustion-induced crystal transformation of silica, but also contribute to the mitigation of population exposure to respirable silica.

Almost 81% of nitrogen fertilizers are applied in form of urea but most of it is lost due to volatilization and leaching leading to environmental pollution. In this regard, slow-release nano fertilizers can be an effective solution. Here, we have synthesized different Fe₃O₄-urea nanocomposites with Fe₃O₄ NPs: urea ratio (1:1, 1:2, 1:3) ie. NC-1, 2, and 3 respectively, and checked their efficacy for growth and yield enhancement. Oryza sativa L. cv. Swarna seedlings were treated with different NCs for 14 days in hydroponic conditions and significant up-regulation of photosynthetic efficiency and nitrogen metabolism were observed due to increased availability of nitrogen and iron. The discriminant functional analysis confirmed that the NC3 treatment yielded the best results so further gene expression studies were performed for NC-3 treated seedlings. Significant changes in expression profiles of ammonia and nitrate transporters indicated that NC-3 treatment enhanced nitrogen utilization efficiency (NUE) due to sustained slow release of urea. From pot experiments, we found significant enhancement of growth, grain nutrient content, and NUE in NC supplemented sets. 1.45 fold increase in crop yield was achieved when 50% N was supplemented in form of NC-3 and the rest in form of ammonium nitrate. NC supplementation can also play a vital role in minimizing the use of bulk N fertilizers because, when 75% of the recommended N dose was supplied in form of NC-3, 1.18 fold yield enhancement was found. Thus our results highlight that, slow-release NC-3 can play a major role in increasing the NUE of rice.

The effectiveness and feasibility of the three biochar materials for remediation of arsenic (As) and lead (Pb) contaminated soil were explored in this study. Significant reduction of bioaccessibility and migration risks of both heavy metals have been explained mechanistically by incubation, column experiments and numerical simulation. Langmuir equation fitted As and Pb sorption isotherms better in the control and biochar (BC) amended soils, while Freundlich model was more suitable for iron modified biochar (Fe-BC) and sulfur/iron modified biochar (S/Fe-BC) amended soils, indicating that modified biochar promoted chemical adsorption process for As and Pb. For the three biochar materials, S/Fe-BC showed the best effects on reducing the bioavailability of As and Pb, with a decrease of 40.42%–64.21%. The reduction in bioaccessibility by metal portioning into available and non-available fractions was better for illustrating the mechanisms including adsorption, precipitation/coprecipitation and As(III) oxidation behind S/Fe-BC efficacy. Moreover, S/Fe-BC can effectively inhibit the leaching behavior of As and Pb under acid rain, which increased by 99.89% and 90.18%, respectively, compared with the control. The HYDRUS-1D modeling indicated that S/Fe-BC could continuously treat As (100 mg/L) and Pb (1000 mg/L) contaminated water for 16.22 years and 40.86 years, respectively, and ensure the groundwater quality criteria being met. Based on these insights, we believe that our study will provide meaningful information about the potentials of biochar derived materials for soil heavy metals’ remediation.

Metal oxide-modified biochar showed excellent adsorption performance in wastewater treatment. Iron nitrate and potassium permanganate were oxidative modifiers through which oxygen-containing groups and iron–manganese oxides could be introduced into biochar. In this study, iron–manganese (Fe–Mn) oxide-modified biochar (BC-FM) was synthesized using rice straw biochar, and the adsorption process, removal effect, and the mechanism of cadmium (Cd) adsorption on BC-FM in wastewater treatment were explored through batch adsorption experiments and characterization (SEM, BET, FTIR, XRD, and XPS). Adsorption kinetics showed that the maximum adsorption capacity of BC-FM for Cd(II) was 120.77 mg/g at 298 K, which was approximately 1.5–10 times the amount of adsorption capacity for Cd(II) by potassium-modified or manganese-modified biochar as mentioned in the literature. The Cd(II) adsorption of BC-FM was well fit by the pseudo-second-order adsorption and Langmuir models, and it was a spontaneous and endothermic process. Adsorption was mainly controlled via a chemical adsorption mechanism. Moreover, BC-FM could maintain a Cd removal rate of approximately 50% even when reused three times. Cd(II) capture by BC-FM was facilitated by coprecipitation, surface complexation, electrostatic attraction, and cation-π interaction. Additionally, the loaded Fe–Mn oxides also played an important role in the removal of Cd(II) by redox reaction and ion exchange in BC-FM. The results suggested that BC-FM could be used as an efficient adsorbent for treating Cd-contaminated wastewater.

The decay of algal biomass and aquatic plants in freshwater lakes leads to the overproduction of autochthonous organic matter (OM) and the exhaustion of dissolved oxygen, impacting the microbial community and subsequent biodegradation of emerging contaminants in sediment. This study explored how the microbial processing of aquatic plant- and algal-derived OM (POM and AOM) mediates 17α-ethinylestradiol (EE2) biodegradation in the anoxic sediments of Lake Taihu in China. In four months of microcosm incubations, the increased concentrations of protein-like substances in AOM and POM exhibited temporary activation on microbial metabolic enzyme activity (fluorescein diacetate hydrolase and dehydrogenase) and significantly promoted the carbon mineralization with iron reduction (P < 0.001). These in turn increased the EE2 biodegradation efficiency to 77–90 ng g⁻¹ in the anoxic sediment. However, a higher EE2 biodegradation of 109 ng g⁻¹ was achieved with the humic acid augmentation containing more quinone-like compounds, showing a weaker substrate-priming effect but accelerated redox cycling of iron and organic substrates in the later period of incubation. The microbial analysis further revealed that the quinone-like compounds in OM were more closely associated with microbial electron transfer and strengthened their interspecies syntrophic cooperation favorable to contaminant biodegradation, even though the connective members exposed to protein-like components upregulated more functional genes related to organic carbon and xenobiotics metabolism and biodegradation. Our findings will help predict the fate of estrogens in various sedimentary environments under increasing eutrophication and further climate change scenarios.

Iron-based materials have been widely investigated because of their high surface reactivity, which has shown potential for the remediation of metal(loid)s in groundwater. However, the disadvantages of structural stability and economic feasibility always limit their application in permeable reactive barrier (PRB) technology. In this study, zeolite-supported iron particles (Zeo-Fe) were synthesized by an innovative low-cost physical preparation method that is suitable for mass production. The removal efficiency and mechanism of typical metal(loid)s (Pb²⁺, Cd²⁺, Cr⁶⁺ and As³⁺) were subsequently investigated using various kinetic and equilibrium models and characterization methods. The results of scanning electron microscopy and energy dispersive spectrometry (SEM-EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) confirmed that zero valent iron (Fe⁰) and oxidation product (Fe₃O₄) were successfully loaded and efficiently dispersed on zeolite. The synthesized Zeo-Fe exhibited excellent adsorption and redox capacities for the cations Pb²⁺, Cd²⁺ and anions Cr⁶⁺, As³⁺. The increase in the pH resulting from Fe⁰ corrosion also enhanced the precipitation of Fe-metal(loid)s. The maximum removal capacity for Pb²⁺, Cd²⁺, Cr⁶⁺ and As³⁺ was up to 70.00, 9.12, 2.35 and 0.36 mg/g, respectively. The removal processes were well described by the pseudo-second-order kinetic model for Pb²⁺ and Cd²⁺, Lagergren pseudo first-order kinetics model for As³⁺ and double phase first order kinetics model l for Cr⁶⁺. Cr⁶⁺ was rapidly reduced to Cr³⁺ by the Fe⁰ stabilized on Zeo-Fe, and the oxidation of As³⁺ to As⁵⁺ was attributed to the Fe⁰/Fe²⁺ oxidation process at the interface over time, which was further demonstrated by the mineral phase and element valence analyses of reacted Zeo-Fe. The removal mechanism for metal(loid)s was a combination of physical and chemical processes, including adsorption, co-precipitation and reduction-oxidation. Conclusively, Zeo-Fe has been shown to have potential as an effective and economical material for removing various metal(loid)s used in PRB.