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

The stable stabilization of uranium (U) in iron (Fe) containing environments is restricted by the reoxidation of UO₂. In the current study, based on air reoxidation tests, we propose a novel two steps accumulation method to enrich microbial consortia from paddy soil. The constructed microbial consortia, denoted as the Fe–U bacteria, can co-precipitate U and Fe to form stable Fe–U solids. Column experiments running for 4 months demonstrated the production of U(IV)–O–Fe(II) precipitates containing maximum of 39.51% uranium in the presence of Fe–U bacteria. The reoxidation experiments revealed the U(IV)–O–Fe(II) precipitates were more stable than UO₂. 16S rDNA high throughput sequencing analysis demonstrated that Acinetobacter and Stenotrophomonas were responsible for Fe and U precipitation, while, Caulobacteraceae and Aminobacter were crucial for the formation of U(VI)-PO₄ chemicals. The proposed two steps accumulation method has an extraordinary application potential in stable immobilization of uranium in iron containing environments.

Goethite is a commonly found iron (hydr)oxide in soils and sediments that has been proven to possess abundant defects in structures. However, the underlying impact of these defects in goethite on arsenic immobilization remains unclear. In this study, goethite samples with abundant, moderate, and sparse defects were synthesized to evaluate their arsenic adsorption capacities. The characteristics of the defects in goethite were investigated by extended X-ray absorption fine structure (EXAFS), high angle annular dark field-scanning transmission electron microscopy-energy dispersion spectrum (HAADF-STEM-EDS) mapping, vibrating-sample magnetometry (VSM), and electron spin resonance (ESR). The characterization analysis revealed that the defects in as-synthesized goethite primarily existed in the form of Fe vacancies. Batch experiments demonstrated that the adsorption capacities of defect-rich goethite for As(V) and As(III) removal were 10.2 and 22.1 times larger than those of defect-poor goethite, respectively. The origin of the impact of Fe defects on arsenic immobilization was theoretically elucidated using density functional theory (DFT) calculations. The enhanced adsorption of goethite was attributed to the improvement of the arsenic affinity due to the Fe vacancy defect, thus considerably promoting arsenic immobilization. The findings of this study provide important insight into the migration and fate of arsenic in naturally occurring iron (hydr)oxides.

Geochemical cycling of iron (Fe) mediated by sediment microbes drives the remobilization of phosphorus (P). Understanding the underlying mechanism is essential for the evaluation of P retention by wetlands. The diffusive gradients in thin film (DGT) and 16S rDNA sequencing techniques were combined to explore seasonal variations in the remobilization mechanism of sediment P in a free water surface wetland in southwest China. A significantly positive correlation between labile P and Fe concentrations was found from the sediment profiles, indicating coupled remobilization of Fe and P in the sediment. Fe-reducing bacterial genera, particularly Sphingomonas and Geothermobacter, were responsible for the reductive dissolution of Fe oxides and subsequent P release in sediment. The efflux of sediment P was higher in the rainy season (95 ± 87 ng cm⁻² d⁻¹) than in the dry season (39 ± 29 ng cm⁻² d⁻¹). Based on the significantly positive relationship between the efflux and total concentration of sediment P, we propose a promising regression equation for quantifying the release risk of sediment P. The Luoshijiang Wetland exhibited a higher release potential as indicated by a greater regression slope (0.558) compared to the other water bodies (0.055), which was mainly attributed to the lower labile Fe:P molar ratio in the sediment. Based on estimations of the diffusive flux of P at the sediment-water interface, sediment contributed more than 172 and 413 g of P per day to the water column in the dry and rainy seasons, respectively, accounting for 14.0% and 1.9% of the P mass in the surface water of the wetland.

Modification of biochar by low-cost iron sources has gained increasing attention to improve pollutants removal performance and reduce production costs compared to conventional chemical modifications. While such iron sources generally have complex compositions, their effects on properties of the iron-biochar composite are not well investigated. This study produced an iron-biochar (RBC) composite from co-pyrolysis of incinerated sewage sludge ash (ISSA) and peanut shell, and examined the role of silica with widespread existence in ISSA and other low-cost iron sources on properties of the iron-biochar composite relevant to As(III)/As(V) removal. Silica was found to react with iron during the pyrolysis process at 850 °C and formed iron silicon at the expense of producing zero valent iron and Fe₃O₄ which resulted in a poorer removal efficacy for As(III) and As(V) compared to the iron-biochar (FBC) made from pure Fe₂O₃ and peanut shell. Moreover, a high leaching of reactive silica from RBC was observed which affected the formation of corrosion products of ZVI and competed with arsenic for active adsorption sites. Despite this, RBC still exhibited a maximum adsorption capacity of 17.44 and 57.56 mg/g towards As(III) and As(V) respectively at pH 3.0. Overall, this study provides an interesting insight into upcycling ISSA into useful media for sorptive removal of arsenic from aqueous solutions.

Nanoscale zero-valent iron (nZVI) might generate positive and negative effects on plant growth, since it acts as either hazardous or growth-promotion role. It is still unclear whether such dual roles can be mediated by arbuscular mycorrhizal fungi (AMF) in plant-AMF symbiosis. We first identified that in 1.5 g kg⁻¹ nZVI (≤1.5 g kg⁻¹ positively), maize biomass was increased by 15.83%; yet in 2.0 g kg⁻¹ nZVI, it turned to be declined by 6.83%, relative to non-nZVI condition (CK, p < 0.05), showing a negative effect. Interestingly, the inoculation of AMF massively improved biomass by 45.18% in 1.5 g kg⁻¹ nZVI, and relieved the growth inhibition by 2.0 g kg⁻¹ nZVI. The event of water use efficiency followed similar trend as that of biomass. We found that proper concentration of nZVI can positively interact with rhizosphere AMF carrier, enabling more plant photosynthetic carbon to be remobilized to mycorrhiza. The scanning of transmission electron microscopy showed that excessive nZVI can infiltrate into root cortical cells and disrupt cellular homeostasis mechanism, significantly increasing iron content in roots by 76.01% (p < 0.05). Simultaneously, the images of scanning electron microscopy showed that nZVI were attached on root surface to form an insoluble iron ion (Fe³⁺) layer, hindering water absorption. However, they were efficiently immobilized and in situ intercepted by extraradical hyphae in mycorrhizal-nZVI symbiosis, lowering iron translocation efficiency by 6.07% (p < 0.05). Herein, the optimized structure remarkably diminished aperture blockage at root surface and improved root activities by 30.06% (p < 0.05). Particularly, next-generation sequencing demonstrated that appropriate amount of nZVI promoted the colonization and development of Funneliformis mosseae as dominant species in rhizosphere, confirming the positive interaction between AMF and nZVI, and its regulatory mechanism. Therefore, dual effects of nZVI can be actively mediated by AMF via rhizosphere interactions. The findings provided new insights into the safe and efficient application of nanomaterials in agriculture.

Since lead, cadmium and arsenic have completely opposite chemical behaviors, it is very difficult to stabilize all these three heavy metals simultaneously. Herein, a novel iron-doped hydroxyapatite composite (Fe-HAP) was developed via an ultrasonic-assisted microwave hydrothermal method for the simultaneous remediation of lead-, cadmium-, and arsenic-co-contaminated soil in Hunan Province, South China. Using DTPA/sodium bicarbonate extractant to extract bioavailable Pb, Cd and As in soil after Fe-HAP remediation for 60 days, the immobilization efficiencies were 79.77%, 51.3% and 37.5% for Pb, Cd and As, respectively. The soil extractable and exchangeable fractions of Pb, Cd and As decreased significantly. In batch experiments, the adsorption kinetics of Pb, Cd and As on Fe-HAP were well described by pseudo-second-order models, indicating that the adsorption is controlled by chemisorption. In the Langmuir adsorption isotherm, the maximum adsorption capacities of Cd²⁺ and As(V) were 476.2 mg g⁻¹ and 195.69 mg g⁻¹, respectively, while Pb²⁺ fit the Freundlich model better. The XRD, SEM and XPS analyses indicated that Fe-HAP formed stable minerals of Pb₅(PO₄)₃OH, Cd₃(PO₄)₂·4H₂O, Cd(OH)₂ and Fe₃(AsO₄)₂·6H₂O with Pb, Cd and As. Overall, its facile and efficient immobilization performance indicate that Fe-HAP has potential for practical applications in integrative remediation of Pb-, Cd-, and As- co-contaminated soil.

Soil contamination by potentially toxic elements (PTEs) is one of the greatest threats to environmental degradation. Knowing where PTEs accumulated in soil can mitigate their adverse effects on plants, animals, and human health. We evaluated the potential of using long-term remote sensing images that reveal the bare soils, to detect and map PTEs in agricultural fields. In this study, 360 soil samples were collected at the superficial layer (0–20 cm) in a 2574 km² agricultural area located in São Paulo State, Brazil. We tested the Soil Synthetic Image (SYSI) using Landsat TM/ETM/ETM+, Landsat OLI, and Sentinel 2 images. The three products have different spectral, temporal, and spatial resolutions. The time series multispectral images were used to reveal areas with bare soil and their spectra were used as predictors of soil chromium, iron, nickel, and zinc contents. We observed a strong linear relationship (−0.26 > r > −0.62) between the selected PTEs and the near infrared (NIR) and shortwave infrared (SWIR) bands of Sentinel (ensemble of 4 years of data), Landsat TM (35 years data), and Landsat OLI (4 years data). The clearest discrimination of soil PTEs was obtained from SYSI using a long term Landsat 5 collection over 35 years. Satellite data could efficiently detect the contents of PTEs in soils due to their relation with soil attributes and parent materials. Therefore, distinct satellite sensors could map the PTEs on tropics and assist in understanding their spatial dynamics and environmental effects.