Cadmium (Cd) availability can be significantly affected by soil properties. The effect of pH value on Cd availability has been confirmed. Paddy soils in South China generally contain high contents of iron (Fe). Thus, it is hypothesized that Fe fractions, in addition to pH value, may play an important role in the Cd bioavailability in paddy soil and this requires further investigation. In this study, 73 paired soil and rice plant samples were collected from paddy fields those were contaminated by acid mine drainage containing Cd. The contents of Fe in the amorphous and DCB-extractable Fe oxides were significantly and negatively correlated with the Cd content in rice grain or straw (excluding DCB-extractable Fe vs Cd in straw). In addition, the concentration of HCl-extractable Fe(II) derived from Fe(III) reduction was positively correlated with the Cd content in rice grain or straw. These results suggest that soil Fe redox could affect the availability of Cd in rice plant. Contribution assessment of soil properties to Cd accumulation in rice grain based on random forest (RF) and stochastic gradient boosting (SGB) showed that pH value should be the most important factor and the content of Fe in the amorphous Fe oxides should be the second most important factor in affecting Cd content in rice grain. Overall, compared with the studies from temperate regions, such as Europe and northern China, Fe oxide exhibited its unique role in the bioavailability of Cd in the reddish paddy soil from our study area. The exploration of practical remediation strategies for Cd from the perspective of Fe oxide may be promising.

In this current work, the magnetic composite microsphere containing glutamine modified chitosan and silica coated Fe3O4 nanoparticles (CS-Gln-MCM) has been successfully prepared and extensively characterized, which is a kind of biodegradable materials. CS-Gln-MCM shows enhanced removal efficiency for both acid green 25 (AG25), an amphoteric dye, and mercury ions (Hg²⁺) from water in the respective while measured pH range compared with chitosan magnetic composite microsphere (CS-MCM) without modification. It is due to the fact that the grafted amino acid provides a variety of additional adsorption active sites and diverse adsorption mechanisms are involved. In AG25 and Hg²⁺ aqueous mixture, the modified adsorbents bear preferential adsorption for AG25 over Hg²⁺ in strong acidic solutions ascribed to multiple interactions between AG25 and CS-Gln-MCM, such as hydrogen bonding and electrostatic interactions. While, in weak acidic conditions, an efficient simultaneous removal is observed for different adsorption effects involved in aforementioned two pollutants. Besides, CS-Gln-MCM illuminates not only short equilibrium time for adsorption of each pollutant less than 20.0 min but also rapid magnetic separation from water and efficient regeneration after saturated adsorption. Therefore, CS-Gln-MCM bears great application potentials in water treatment.

This study aimed at determining the fate of trace elements (TE) following soil organic waste (OW) application. We used a unique combination of X-ray absorption spectroscopy analyses, to determine TE speciation, with incubation experiments for in situ monitoring of TE availability patterns over a time course with the technique of the diffusive gradients in thin films (DGT). We showed that copper (Cu) and zinc (Zn) availability were both increased in OW-amended soil, but their release was controlled by distinct mechanisms. Zn speciation in OW was found to be dominated by an inorganic species, i.e. Zn sorbed on Fe oxides. Zn desorption from Fe oxides could explain the increase in Zn availability in OW-amended soil. Cu speciation in OW was dominated by organic species. Cu release through the mineralization of organic carbon from OW was responsible for the increase in Cu availability.

Magnetic and geochemical parameters of soils are determined with respect to geology, pedogenesis and anthropopression. Depending on local conditions these factors affect magnetic and geochemical signals simultaneously or in various configurations. We examined four type of soils (Entic Podzol, Eutric Cambisol, Humic Cambisol and Dystric Cambisol) developed on various bedrock (the Tumlin Sandstone, basaltoid, amphibolite and serpentinite, respectively). Our primary aim was to characterize the origin and diversification of the magnetic and geochemical signal in soils in order to distinguish the most reliable methods for correct interpretation of measured parameters. Presented data include selected parameters, both magnetic (mass magnetic susceptibility – χ, frequency-dependent magnetic susceptibility – χfd and thermomagnetic susceptibility measurement – TSM), and geochemical (selected heavy metal contents: Co, Cr, Cu, Fe, Mn, Ni, Pb, Zn). Additionally, the enrichment factor (EF) and index of geoaccumulation (Igeo) were calculated. Our results suggest the following: (1) the χ/Fe ratio may be a reliable indicator for determining changes of magnetic signal origin in soil profiles; (2) magnetic and geochemical signals are simultaneously higher (the increment of χ and lead and zinc was noted) in topsoil horizons because of the deposition of technogenic magnetic particles (TMPs); (3) EF and Igeo evaluated for lead and zinc unambiguously showed anthropogenic influence in terms of increasing heavy metal contents in topsoil regardless of bedrock or soil type; (4) magnetic susceptibility measurements supported by TSM curves for soil samples of different genetic horizons are a helpful tool for interpreting the origin and nature of the mineral phases responsible for the changes of magnetic susceptibility values.

The recent rapid expansion of nanotechnologies has increased concern over the impact of engineered nanoparticles (ENPs) on the environment and biota. Although the toxicity of ENPs has received considerable attention in the recent years, there are still gaps in our knowledge of the mechanisms responsible for their effects. In this study, we tested the toxicity of various metal oxide ENPs (Al₂O₃, CuO, Fe₃O₄, MnO, TiO₂, and ZnO), including nanowires together with their bulk counter particles and soluble metal salts, on germinating seeds of Sinapis alba L. Fe₃O₄, TiO₂, MnO₂, and Al₂O₃ ENPs did not negatively affected seed germination at any tested concentrations. However, CuO and ZnO ENPs showed a dose-dependent inhibition of germination. Metal ions were more toxic than metal oxide particles at corresponding concentrations. The highest toxicity was exhibited by Cu, followed by Zn, Fe, Al, and Mn ions. A comparison of ENPs with bulk materials did not reveal significantly higher ENP toxicity. Similarly, nanowires showed effects similar to other nanoparticles and bulk materials. Our results indicate that the nanosize or shape of particles did not play a crucial role, whereas metal ions released into cultivation media and accumulated in seedlings contributed significantly to the phytotoxicity of metal oxides.

Fe₃O₄-CuO@montmorillonite was prepared using coprecipitation method, and its structure was determined by XRD, IR, and transmission electron micrograph (TEM). Montmorillonite in Fe₃O₄-CuO@montmorillonite nanocomposite allowed the silicate layer of montmorillonite to behave as a barrier, which prevented the agglomeration and natural crystallization of Fe₃O₄ and CuO. Furthermore, the chlorine dioxide (ClO₂) oxidative degradation of anthracene-contaminated soil was studied in detail using Fe₃O₄-CuO@montmorillonite as a magnetic heterogeneous catalyst. The operating parameters such as ClO₂ concentration, catalyst dosage, reaction time, and pH were evaluated. Compared with the conventional ClO₂ oxidation process without the catalyst, the ClO₂ catalytic oxidation system could significantly enhance the degradation efficiency. Under the optimal condition (anthracene concentration 89.8 mg/kg, water soil mass ratio 3:1, initial pH 7, ClO₂ concentration 1 mol/kg, catalyst dosage 1 g/kg, reaction time 30 min, and reaction temperature 25 °C), anthracene degradation efficiency achieved 96.2 %. The catalyst could be easily reused by magnetic separation and used at least 8 cycles without obvious loss of activity. The kinetic studies revealed that the ClO₂ catalytic oxidation degradation of anthracene-contaminated soil with Fe₃O₄-CuO@montmorillonite as catalyst followed pseudo-first-order kinetics with respect to ClO₂ concentration. Thus, this study showed potential application of ClO₂ catalytic oxidation process in remediation of organic pollutant-contaminated soil.

Lignite (PK), bituminous (FI) and biomass (SE) fly ashes (FAs) were mineralogically and geochemically characterised, and their element leachability was studied with batch leaching tests. The potential for acid neutralisation (ANP) was quantified by their buffering capacity, reflecting their potential for neutralisation of acid mine drainage. Quartz was the common mineral in FAs detected by XRD with iron oxide, anhydrite, and magnesioferrite in PK, mullite and lime in FI, and calcite and anorthite in SE. All the FAs had high contents of major elements such as Fe, Si, Al and Ca. The Ca content in SE was six and eight times higher compared to PK and FI, respectively. Sulphur content in PK and SE was one magnitude higher than FI. Iron concentrations were higher in PK. The trace element concentrations varied between the FAs. SE had the highest ANP (corresponding to 275 kg CaCO₃ tonne⁻¹) which was 15 and 10 times higher than PK and FI, respectively. The concentrations of Ca²⁺, SO₄²⁻, Na⁺ and Cl⁻ in the leachates were much higher compared to other elements from all FA samples. Iron, Cu and Hg were not detected in any of the FA leachates because of their mild to strong alkaline nature with pH ranging from 9 to 13. Potassium leached in much higher quantity from SE than from the other ashes. Arsenic, Mn and Ni leached from PK only, while Co and Pb from SE only. The concentrations of Zn were higher in the leachates from SE. The FAs used in this study have strong potential for the neutralisation of AMD due to their alkaline nature. However, on the other hand, FAs must be further investigated, with scaled-up experiments before full-scale application, because they might leach pronounced concentrations of elements of concern with decreasing pH while neutralising AMD.

In this study, we focused on the performance of phosphate recovery in the case of magnetic iron oxide (MIO) particles and iron oxide nanotubes (INTs) with synthetic wastewater. MIO particles were prepared by a co-precipitation method, and INTs were prepared with a potentiostatic anodization method of zerovalent iron foil in electrolyte-containing sulfate and fluoride. Although MIO had the fast adsorption rate, INT had a higher adsorption capacity per surface area rather than MIO. The adsorption isotherm of MIO and INT was approximated by a Freundlich type. Phosphate adsorbed on MIO and INT was effectively desorbed with alkaline solutions. For phosphate recovery, MIO needs a magnetic recovery device, whereas, when INT was used for phosphate recovery, another recovery step is not necessary. Both methods showed effective adsorption performance for phosphate recovery in wastewater.

Drainage filters using porous granular material constitute new innovative technologies for remediating phosphorus (P) from agricultural tile drainage water. In drainage filters where convective velocities are often high, we hypothesize that intragranular diffusion may affect solute transport depending on filter characteristics and flow rate. This was investigated for six drainage filter materials (Leca, Filtralite-P®, granulated limestone, crushed seashells, calcined diatomite earth (CDE), and a poorly ordered Fe oxide aggregate (CFH)) conducting a tritium (³H₂O) tracer experiment at low (0.26 cm h⁻¹), medium (23 cm h⁻¹), and high (41 cm h⁻¹) flux densities. The filter materials differed widely with respect to grain-size distribution (D ₅₀ from 1.6 to 3.3 mm), uniformity coefficient (1.7 to 2.2), particle density (1.75 to 2.76 g cm⁻³), bulk density (0.34 to 1.46 g cm⁻³), and water-filled porosity (0.39 to 0.73 cm³ cm⁻³). Measurements of specific surface area (SSA) included both SSABET and SSAEGME to ensure inclusion of the intragranular microporosity, not accounted by N₂-BET. SSA varied widely across methods and allowed the differentiation of filters according to the significance of the intragranular porosity. Tritium transport varied from approximately equilibrium transport at all flow rates in Leca, Filtralite-P®, and limestone, to progressive non-equilibrium transport as flow rate increased in Seashells, CDE, and CFH. In general, the filter materials were highly variable in hydro-physical properties. Filters with (approximately) equilibrium transport were, however, all characterized by low specific surface areas. The non-equilibrium transport was explained by an intragranular diffusion in filters with larger specific surface area (Seashells, CDE, and CFH).

We evaluated the biogeochemical processes occurring in the rhizosphere of different native plants growing spontaneously in a copper-contaminated soil in an abandoned mine site in NE Brazil. We also assessed the effects that these processes have on copper mobility and toxicity and discuss the potential use of the plants as pioneer species in restoration programs. For these purposes, we determined chemical (pH, macronutrients, % TOC, and % TIC) and mineralogical (XRD) properties in both rhizosphere and nonrhizosphere soils (bulk soil), and we used the sequential extraction method (SEM) to extract copper from both soils. The study findings show that the plants have greatly altered the physicochemical characteristics of the soil that is directly influenced by their roots. Different plant species appear to act through different processes, thus altering various soil components and affecting the biogeodynamic cycling of essential nutrients and copper. The changes in the physical-chemical characteristics of the rhizosphere affected copper dynamics, mainly manifested as significantly lower concentrations of potentially bioavailable copper, i.e., exchangeable and carbonate-associated copper, in this soil fraction. The concentration of copper associated with noncrystalline Fe oxides was also higher in the rhizosphere, thus enhancing the immobilization and probably minimizing the risks of copper toxicity and mobility. The biogeochemical processes observed in the rhizosphere of the species under study seem to indicate that the plants promote phytostabilization of copper in their rhizosphere zone, and they thus show desirable characteristics for use in phytoremediation programs.