Cd2+ Sorption Alterations in Ultisol Soils Triggered by Different Engineered Nanoparticles and Incubation Times.

The progressive influx of engineered nanoparticles (ENPs) into the soil matrix catalyses a fundamental transformation in the equilibrium dynamics between the soil and the edaphic solution. This all-encompassing investigation is geared towards unravelling the implications of an array of ENP types, diverse dosages and varying incubation durations on the kinetics governing Cd2+ sorption within Ultisol soils. These soils have been subjected to detailed characterizations probing their textural and physicochemical attributes in conjunction with an exhaustive exploration of ENP composition, structure and morphology. To decipher the intricate nuances of kinetics, discrete segments of Ultisol soils were subjected to isolated systems involving ENP dosages of 20 and 500 mg ENPs·kg-1 (AgNPs, CuNPs and FeNPs) across intervals of 1, 3 and 6 months. The comprehensive kinetic parameters were unveiled by applying the pseudo-first-order and pseudo-second-order models. At the same time, the underlying sorption mechanisms were studied via the intra-particle diffusion model. This study underscores the substantial impact of this substrate on the kinetic behaviours of contaminants such as Cd, emphasizing the need for its consideration in soil-linked economic activities and regulatory frameworks to optimize resource management.

Enhanced removal of mercury and lead by a novel and efficient surface-functionalized imogolite with nanoscale zero-valent iron material.

A novel hybrid nanomaterial, nanoscale zero-valent iron (nZVI)-grafted imogolite nanotubes (Imo), was synthesized via a fast and straightforward chemical procedure. The as-obtained nanomaterial (Imo-nZVI) was characterized using transmission electron microscopy (TEM), electrophoretic mobility (EM), and vibrating sample magnetometry (VSM). The prepared Imo-nZVI was superparamagnetic at room temperature and could be easily separated by an external magnetic field. Sorption batch experiments were performed for single- and multicomponent systems and demonstrated that Hg2+ and Pb2+ could be quantitatively adsorbed at pH 3.0. For multicomponent systems, maximum adsorption capacities of 61.6 mg·g-1 and 76.9 mg·g-1 were obtained for Hg2+ and Pb2+ respectively. It was observed that the functional groups in Imo-nZVI interact preferentially with analytes according to the Misono softness parameter. The higher performance of Imo-nZVI compared with Imo and nZVI is related to the increased number of adsorption sites in the functionalized nanomaterial. The sorption equilibrium data obeyed the Langmuir model, while kinetic studies demonstrated that the sorption processes of Hg2+ and Pb2+ followed the pseudo-second-order model. This study suggests that the Imo-nZVI composite can be used as a promising sorbent to provide a simple and fast separation method to remove Hg and Pb ions from contaminated water.

Efficient and selective removal of SeVI and AsV mixed contaminants from aqueous media by montmorillonite-nanoscale zero valent iron nanocomposite.

Nanoscale zero-valent iron (NZVI) and NZVI supported onto montmorillonite (NZVI-Mt) were synthetized and used in this study to remove SeVI and AsV from water in mono- and binary-adsorbate systems. The adsorption kinetics and isotherm data for SeVI and AsV were adequately described by the pseudo-second-order (PSO) (r2>0.94) and Freundlich (r2>0.93) equations. Results from scanning electron microscopy showed that the dimension of the NZVI immobilized on the Mt was smaller than pure NZVI. Using 0.05 g of adsorbent and an initial 200 mg L-1 AsV and SeVI concentration, the maximum adsorption capacity (qmax) and partition coefficient (PC) for AsV on NZVI-Mt in monocomponent system were 54.75 mg g-1 and 0.065 mg g-1·µM-1, which dropped respectively to 49.91 mg g-1 and 0.055 mg g-1·µM-1 under competitive system. For SeVI adsorption on NZVI-Mt in monocomponent system, qmax and PC were 28.63 mg g-1 and 0.024 mg g-1·µM-1, respectively. Values of qmax and PC were higher for NZVI-Mt than NZVI and montmorillonite, indicating that the nanocomposite contained greater adsorption sites for removing both oxyanions, but with a marked preference for AsV. Future research should evaluate the effect of different operational variables on the removal efficiency of both oxyanions by NZVI-Mt.

Mechanistic insights into simultaneous removal of copper, cadmium and arsenic from water by iron oxide-functionalized magnetic imogolite nanocomposites.

Imogolite and magnetic imogolite-Fe oxide nanocomposites (Imo-Fe50 and Imo-Fe25, at 50 and 25 % Fe loading (w/w), respectively) were synthesized and tested for the removal of aqueous copper (Cu), cadmium (Cd), and arsenic (As) pollutants. The materials were characterized by transmission electron microscopy, and specific surface area and isoelectric point measurements. The Fe-containing samples were additionally characterized by Mössbauer spectroscopy and vibrating-sample magnetometry. Significant differences were found in the morphological, electrophoretic, and magnetic characteristics between imogolite and the nanocomposites. The in-situ Fe-oxide precipitation process modified the active surface sites of the imogolite. The Fe-oxide, mainly magnetite, favored the contaminants' adsorption over the pristine imogolite. The adsorption kinetics of these pollutants were adequately described by the pseudo-second order and intraparticle diffusion models. The kinetic models showed that surface adsorption was more important than intraparticle diffusion in the removal of the pollutants by all the adsorbents. The Langmuir-Freundlich model described the experimental adsorption data, and both nanocomposites showed greater adsorption capacity than the imogolite. The adsorption of Cu and Cd was sensitive to cationic competition, showing a decrease of the adsorption capacity when the two cations coexisted, while their adsorption increased in the presence of arsenate.

Imogolite Synthetized in Presence of As(III) Induces Low Cell Toxicity and Hemolysis, in Vitro, Potential Stabilization of Arsenite Present in Aqueous Systems.

Imogolite is a nanotubular aluminosilicate that has low toxicity in biological systems and due to its morphological and surface properties has a growing interest in environmental applications and biomedical areas. Its synthesis is highly sensitive to the presence of other ions, being able to inhibit or retard the process of imogolite formation, which could change the cytotoxic response of this substrate, something scarcely reported in the literature. In this context, the presence of arsenite during the synthesis of imogolite caused significant changes in the dimensions and surface behavior of these nanotubes. Cell viability was evaluated on EA.hy926 and HepG2 cells by (3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide) assay at 24 h. Meanwhile, the potential effects on human red blood cells, namely, hemolysis and morphological changes, were determined at 0 and 24 h. The range of % As tested of the nanotube showed cell toxicity similar to the control condition. Similarly, the As-based nanotubes induced hemolysis similar to controls and slight morphological changes of red blood cells at 0 and 24 h of exposition. These results indicate that As-based imogolite-like nanotubes are not toxic nor hemolytic and can be potentially used in processes like water purification.

Synthesis and characterization of zeolite-based composites functionalized with nanoscale zero-valent iron for removing arsenic in the presence of selenium from water.

We studied the sorption of As(V) in single and multi-component (As(V)-Se(VI)) aqueous systems using nanoscale zero-valent iron (nZVI) and nZVI-functionalized zeolite (Z-nZVI) adsorbents. Morphological and physico-chemical characterization of the adsorbents was conducted using X-ray diffraction (XRD), scanning electron microscopy (SEM), surface area and electrophoretic mobility measurements. SEM and XRD analyses showed that Fe-nanoparticle size and crystallinity were better preserved in Z-nZVI than nZVI after As(V) sorption. Highly efficient As(V) removal was achieved for all tested adsorbents with a minimal competition effect of Se(VI). In the single-component system, the equilibrium As(V) sorption time on nZVI and Z-nZVI was 40 and 60 min, respectively, while in the multi-component system, this time was 90 min for both the adsorbents. The Freundlich and pseudo-second-order models provided good fittings for the experimental sorption data (r2>0.96). The As(V) removal capacity was higher using Z-nZVI than nZVI both in the single and multi-component systems, suffering minimal differences in removal in both cases. The results suggested that Z-nZVI had more specific surface sites for As(V) than nZVI and zeolite, which makes Z-nZVI a more effective adsorbent than nZVI for the removal of As(V) from aqueous solutions in the presence of other oxyanions.

Distribution of contaminant trace metals inadvertently provided by phosphorus fertilisers: movement, chemical fractions and mass balances in contrasting acidic soils.

The frequent use of phosphorus (P) fertilisers accompanied by nitrogen and potassium sources may lead to a serious long-term environmental issue because of the presence of potentially hazardous trace metals (TM) in P fertilisers and unknown effects on the TM chemical fractions in agricultural soils. A 16-month-long column experiment was conducted to investigate the mobility and chemical forms of Cd, Cu, Cr, Ni, and Zn introduced into a Mollisol and an Andisol through surface incorporation (0-2 cm) of triple superphosphate (TSP) fertiliser. The effects of urea and potassium chloride (KCl) applications were investigated as well. After 15 cycles of 300-mm irrigation, TSP addition increased the 4 M HNO3 extractable TM concentration in the upper (0-5 cm) section of soils. Beyond this depth, metals showed no significant mobility, with minimal leaching losses (< 1.9%, 25-cm depth). The TM chemical forms in the 0-5 cm section were significantly (p < 0.01) affected by the soil type and fertilisers addition. Cadmium, Ni, and Zn were the elements which appeared in a larger proportion (up to 30%) in the most labile fraction (KNO3 extractable) in fertilised soils. The impact of urea depended on the nitrification-related changes in soil pH, while fertilisation with KCl tended to increase the KNO3 fraction of most metals probably due to K+ exchange reactions. Chromium remained minimally affected by the urea and KCl applications since this contaminant is strongly bound to the less labile solid phases. The low mobility of TM was governed mainly by their interaction with the solid phases rather than by their speciation at soil pH. The mass balance showed that the geochemical processes underwent in time by the P fertiliser increased the amount of TM extracted by the chemical fractionation scheme, therefore the reaction period of TSP with soil particles should be taken into account for evaluating TM availability. Long-term soil fertilisation could inadvertently contribute to an increased concentration and availability of these P fertilisers-born contaminants in the cultivated layer of acidic soils.

Preparation of nanoscale iron (oxide, oxyhydroxides and zero-valent) particles derived from blueberries: Reactivity, characterization and removal mechanism of arsenate.

The application of iron nanoparticles (FeNPs) to the removal of various pollutants has received wide attention over the last few decades. A synthesis alternative to obtain these nanoparticles without using harmful chemical reagents, such as NaBH4, is the use of extracts from different natural sources that allow a lesser degree of agglomeration, in a process known as green synthesis. In this study, FeNPs were synthesized by 'green' (hereafter, BB-Fe NPs) and 'chemical' (hereafter, nZVI) methods. Extracts of leaves and blueberry shoots (Vaccinium corymbosum) were used as reducing agents for FeCl3·6H2O solution in the green synthesis method. FeNPs were characterized using transmission electron microscopy (TEM), scanning electron microscopy (SEM), electrophoretic migration, Brunauer-Emmett-Teller (BET) surface area analysis and X-ray diffraction (XRD) and evaluated for the removal of As(V) from aqueous systems. In both synthesis methods, XRD analysis confirmed the presence of the different kinds of iron nanoparticles. SEM analysis showed that the average size of BB-Fe NPs was 52.4nm and that a variety of nanoparticles of different forms and associated structures, such as lepidocrocite, magnetite, and nZVI, were present, while the dimensions of nZVI were 80.2nm. Comparatively significant differences regarding the electrophoretic mobility were found between both materials pre- and post-sorption of As(V). The velocity of As(V) removal by BB-Fe NPs was slower than that by nZVI, reaching equilibrium at 120min compared to 60min for nZVI. The removal kinetics of As(V) were adequately described by the pseudo-second-order kinetic model, and the maximum adsorbed amounts of this analyte are in close accordance with the experimental results. The Langmuir-Freundlich model is in good agreement with our experimental data, where the sorption capacity of nZVI and BB-Fe NPs was found to be 52.23 ± 6.06 and 50.40 ± 5.90 (mg·g-1), respectively. The use of leaves of Vaccinium corymbosum affords an easy-to-synthesize, low-cost, and eco-friendly material with capabilities similar to nZVI. BB-Fe NPs are promising for arsenic remediation, which has emerged as a new alternative for water purification and sanitation.