Typical groundwater contamination in the vicinity of industrial brownfields and basic methods of their treatment.

The article deals with simple methods of decontamination of groundwater from the vicinity of brownfields contaminated with organic and inorganic substances. In the literature, thousands of articles on this issue at various sophisticated levels of knowledge can be found. The articles are mostly suitable as an extension of scientific knowledge; however, regarding potential costs and respectively scale-up problems, the applications are limited. It turns out that the vast majority of contaminated water can be effectively decontaminated by simple methods, in a coagulation-sedimentation sequence → simple oxidation and reduction methods for separated water (Fenton reaction, photocatalysis, ozonation, reductive dehalogenation with zero metals) → adsorption of remaining pollutants on simple sorbents, eg on biochar → (possibly bioremediation or advanced physical methods such as membrane filtration) → final purification on activated carbon. Due to the usually limited volume loads of soils with pollutants in the vicinity of brownfields, it is not economically advantageous to build demanding decontamination units for water purification. Usually, the simplest solution is the system to pump-and-treat around the source of contamination, with the main emphasis on highly effective removal of pollutants from water that returns underground. Groundwater was taken from boreholes leading to the saturated zone in the vicinity of several selected industrial brownfields. The solutions are shown on individual typical cases.

Impacts of dietary supplementation with nano-iron and methionine on growth, blood chemistry, liver biomarkers, and tissue histology of heat-stressed broiler chickens.

A 28-day study was done to explore the impact of nano-iron alone or combined with methionine on growth, blood chemistry, liver biomarkers, and tissue histology of heat-stressed chicken. One-day-old Ross 308 chicks were randomly allocated to three groups. Each group was divided into three replicates (13 chicks/replicate). The first group was the control one that was fed a basal diet without supplementation (T0). The second group was fed a basal diet with nano-iron 4 mg kg-1 diet (T1). The third group was fed a basal diet with nano-iron 4 mg kg-1 diet plus methionine 4 g kg-1 diet (T2). The results showed that the birds in the control group had significantly (p < 0.05) higher final weights. Also, a partial relief of heat stress adverse effects was observed on growth by T1 compared to T2. The T2 showed a significantly increased (p < 0.05) free iron (Fe) level and transferrin saturation index. Likewise, T2 significantly (p < 0.05) reduced total iron-binding capacity (TIBC) and transferrin level in comparison with T0 and T1. Also, hepatic impairment and inflammatory response were observed in the T2 group when compared to T0 and T1, besides a bad lipid profile. Further, T2 showed raised levels of Fe and ferritin in their hepatic tissues compared to those T1 and T0. A significant increment of thiobarbituric acid reactive and decrement of reduced glutathione levels in the hepatic tissues of T2 and T1 versus T0 levels were recorded. It is concluded that nano-iron at the level of 4 mg kg-1 in this study is highly absorbed, leading to harmful effects. Further investigations are needed to detect the proper supplemental level.

Chromium Removal Using Soil Loaded with Green Iron Nanoparticles.

Chromate is considered as a serious environmental problem due its toxicity. Iron nanoparticles produced by green tea polyphenols (GT-nZVI) is a powerful reductant, which can effectively reduce Cr(VI) to Cr(III). Nano ZVI suspension was initially conceived ideal for direct injection in the contaminated aquifers. However GT-nZVI presents limited mobility in calcareous aquifers. For this reason the incorporation of nanoiron in a permeable reactive barrier was investigated as an alternative mode of GT-nZVI application. Namely an amount of soil was loaded with nZVI (0.40 mmol/g of soil) and was evaluated for Cr(VI) removal by conducting batch and column tests. Batch tests were carried out by mixing soil samples, loaded with different levels of nZVI from 0.04 to 0.40 mmol per gram, with contaminated groundwater (GW) containing 1300 ppb Cr(VI). Cr(VI) concentration dropped below detection limit within 1 day using the highest nZVI dose. Soil pre-loaded with nZVI (S-nZVI) presented also high efficiency for chromates remediation, when tested under flow conditions by conducting column tests.

Ferroportin mediates the intestinal absorption of iron from a nanoparticulate ferritin core mimetic in mice.

The ferritin core is composed of fine nanoparticulate Fe(3+) oxohydroxide, and we have developed a synthetic mimetic, nanoparticulate Fe(3+) polyoxohydroxide (nanoFe(3+)). The aim of this study was to determine how dietary iron derived in this fashion is absorbed in the duodenum. Following a 4 wk run-in on an Fe-deficient diet, mice with intestinal-specific disruption of the Fpn-1 gene (Fpn-KO), or littermate wild-type (WT) controls, were supplemented with Fe(2+) sulfate (FeSO4), nanoFe(3+), or no added Fe for a further 4 wk. A control group was Fe sufficient throughout. Direct intestinal absorption of nanoFe(3+) was investigated using isolated duodenal loops. Our data show that FeSO4 and nanoFe(3+) are equally bioavailable in WT mice, and at wk 8 the mean ± SEM hemoglobin increase was 18 ± 7 g/L in the FeSO4 group and 30 ± 5 g/L in the nanoFe(3+) group. Oral iron failed to be utilized by Fpn-KO mice and was retained in enterocytes, irrespective of the iron source. In summary, although nanoFe(3+) is taken up directly by the duodenum its homeostasis is under the normal regulatory control of dietary iron absorption, namely via ferroportin-dependent efflux from enterocytes, and thus offers potential as a novel oral iron supplement.

Removal of arsenic from simulation wastewater using nano-iron/oyster shell composites.

In this paper, a nano-iron/oyster shell composite (NI/OS) was firstly prepared by an in-situ synthesis method to explore an efficient treatment technology for arsenic (As) contaminated wastewater. The micromorphologies and composition of the composite were characterized using field emission scanning electron microscopy and Fourier transform infrared spectroscopy. The effects of the preparation parameters, as well as the treatment conditions, on the removal of As(Ⅲ) were also investigated. The characterization results showed that iron nanoparticles with a diameter of 60 nm were introduced into the composite by an in-situ reduction method. The physicochemical properties of the iron nanoparticles, such as diameter and aggregation, were influenced by the iron source more than the choice of reductant and temperature in the synthesis process, and these properties were closely related to the treatment performance of the composite. Under the suitable reaction conditions of a pH value of 6.8, a temperature of 20 °C, and an initial concentration of As(Ⅲ) of 1.8 mg/L, As(Ⅲ) was almost completely removed from the simulation wastewater.

Sodium alginate-encapsulated nano-iron oxide coupled with copper-based MOFs (Cu-BTC@Alg/Fe3O4): Versatile composites for eco-friendly and effective elimination of Rhodamine B dye in wastewater purification.

This study explores the effectiveness of Alginate-coated nano­iron oxide combined with copper-based MOFs (Cu-BTC@Alg/Fe3O4) composites for the sustainable and efficient removal of Rhodamine B (RhB) dye from wastewater through adsorption and photocatalysis. Utilizing various characterization techniques such as FTIR, XRD, SEM, and TEM, we confirmed the optimal synthesis of this composite. The composites exhibit a significant surface area of approximately 160 m2 g-1, as revealed by BET analysis, resulting in an impressive adsorption capacity of 200 mg g-1 and a removal efficiency of 97 %. Moreover, their photocatalytic activity is highly effective, producing environmentally friendly degradation byproducts, thus underlining the sustainability of Cu-BTC@Alg/Fe3O4 composites in dye removal applications. Our investigation delves into kinetics and thermodynamics, revealing a complex adsorption mechanism influenced by both chemisorption and physisorption. Notably, the adsorption kinetics indicate equilibrium attainment within 100 min across all initial concentrations, with the pseudo-second-order kinetic model fitting the data best (R2 ≈ 0.999). Furthermore, adsorption isotherm models, including Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich, elucidate the adsorption behavior, with the Temkin and Dubinin-Radushkevich models showing superior accuracy compared to the Langmuir model (R2 ≈ 0.98 and R2 ≈ 0.96, respectively). Additionally, thermodynamic analysis reveals a negative Gibbs free energy value (-6.40 kJ mol-1), indicating the spontaneity of the adsorption process, along with positive enthalpy (+24.3 kJ mol-1) and entropy (+82.06 kJ mol-1 K) values, suggesting an endothermic and disorderly process at the interface. Our comprehensive investigation provides insights into the optimal conditions for RhB adsorption onto Cu-BTC@Alg/Fe3O4 composites, highlighting their potential in wastewater treatment applications.

Sustained oral intake of nano-iron oxide perturbs the gut-liver axis.

Nanomaterial have shown excellent properties in the food industry. Although iron oxides are often considered safe and widely used as food additives, the toxicity of nano­iron oxide remains unclear. Here we established a subchronic exposure mouse model by gavage, tested the biodistribution of nano­iron oxide, and explored the mechanism of liver injury caused by it through disturbance of the gut-liver axis. Oral intake of nano­iron oxide will likely disrupt the small intestinal epithelial barrier, induce hepatic lipid metabolism disorders through the gut-liver axis, and cause hepatic damage accompanied with hepatic iron deposition. Nano­iron oxide mainly caused hepatic lipid metabolism disorder by perturbing glycerophospholipid metabolism and the sphingolipid metabolism pathways, with the total abundance of phosphatidylcholine (PC) and phosphatidylethanolamine (PE) tending to decrease while that of triglyceride tended to increase, in a time- and dose-dependent manner. The imbalanced lipid homeostasis could cause damage via membrane disruption, lipid accumulation, and lipotoxicity. This data provides information about the subchronic toxicity of nano­iron oxide, highlights the importance of gut-liver axis in the hepatotoxicity.

Nano-size plastics inhibited Cr(VI) species transformation during facilitated transport of green synthesized nano-iron in the presence of oxyanions.

Remediating hexavalent chromium (Cr(VI))-contaminated soils using green synthesized nano-iron (g-nZVI), which merits high reactivity, low cost, and environmental friendliness, has attracted significant attention. However, the broad existence of nano plastics (NPs) could adsorb Cr(VI) and subsequently influence in situ remediation of Cr(VI)-contaminated soil by g-nZVI. To clarify this issue and improve the remediation efficiency, we investigated the co-transport between Cr(VI) and g-nZVI coexisting with sulfonyl-amino-modified nano plastics (SANPs) in water-saturated sand media in the presence of oxyanions (i.e., phosphate and sulfate) at environmentally relevant conditions. This study found that SANPs inhibited the Cr(VI) reduction to Cr(III) (i.e., Cr2O3) by g-nZVI, attributed to nZVI-SANPs hetero-aggregates and Cr(VI) adsorption on SANPs. Notably, "nZVI-[SANPs•••Cr(III)]" agglomerate happened via complexation of [-NH3•••Cr(III)] between Cr(III) from Cr(VI) reduced by g-nZVI and amino group on SANPs. Further, the co-presence of phosphate (stronger adsorption on SANPs than g-nZVI) remarkably suppressed Cr(VI) reduction. Then, it promoted the co-transport of Cr(VI) with nZVI-SANPs hetero-aggregates, which could potentially threaten underground water. Fundamentally, sulfate would instead concentrate on SANPs, hardly impacting the reactions between Cr(VI) and g-nZVI. Overall, our findings provide crucial insights into understanding the Cr(VI) species transformation during co-transport with g-nZVI in ubiquitous complexed soil environments (i.e., containing oxyanions) contaminated by SANPs.

Effective removal of hydrogen sulfide from landfill gases using a modified iron pentacarbonyl desulfurization agent and the desulfurization mechanism.

High-efficiency desulfurization is key to the recovery and use of landfill gases. In this study, a nano­iron oxide desulfurization agent modified from iron pentacarbonyl was prepared in n-decane (DE) and hexadecane (HE) by ultrasonic disruption without any supporting materials and its hydrogen sulfide removal ability and desulfurization mechanism were studied. The yield of the desulfurization agent was higher when HE was used as the solvent; however, the products generated by both solvents had the same crystal type and similar properties. The efficiency of the desulfurization agent was significantly improved at 150-200 °C, exceeding 90% at 150 °C with single sulfur production. The maximum sulfur adsorption capacity of the desulfurization agent produced after 3 h of DE ultrasonic treatment at 200 °C (DE3) was 492 mg/g (desulfurization efficiency = 97.33%), while that of the agent produced after 3 h of HE ultrasonic treatment at 250 °C (HE3) was 522 mg/g (desulfurization efficiency = 99.30%). The desulfurization reaction involved both chemical adsorption and catalytic decomposition and the catalytic decomposition reaction rate was lower than that of chemical adsorption. Therefore, the more FexSy produced in the chemical adsorption process, the better catalytic performance was.

Harnessing chlorin e6 loaded by functionalized iron oxide nanoparticles linked with glucose for target photodynamic therapy and improving of the immunogenicity of lung cancer.

BACKGROUND: Non-small-cell lung cancer (NSCLC) is the most common malignant lung tumor and is difficult to be eradicated due to its immunosuppressive microenvironment. Chlorin e6 (Ce6)-mediated photodynamic therapy (PDT) could improve immunogenicity while destroying malignant tumor cells. However, the clinic application of Ce6-mediated PDT is limited by Ce6's poor water solubility and insufficient accumulation in lung cancer. To address this issue, Ce6 was loaded onto functionalized iron oxide nanoparticles linked with glucose to improve the distribution of Ce6 in lung cancer. MATERIALS AND RESULTS: The results of transmission electron microscopy (TEM), UV-Vis spectrophotometry, dynamic light scattering and near-infrared (NIR) spectroscopy confirmed the successful preparation of the composites. Confocal and flow cytometry showed IO-PG-GLU-Ce6 significantly enhanced the uptake of Ce6 by lung cancer cells and produced more reactive oxygen species (ROS) under NIR light irradiation. In addition, the detection of cell viability, proliferation and apoptosis indicated IO-PG-GLU-Ce6 achieved stronger photo-toxicity to lung cancer cells. Moreover, IO-PG-GLU-Ce6 treatment effectively damaged the DNA of lung cancer cells and thereby activated STING, up-regulated the expression of IFN-ß, HMGB1 and HSP90, indicating augmented immunogenicity of lung cancer cells. Further results of in vivo, organ imaging and tissue fluorescence sections demonstrated IO-PG-GLU-Ce6 significantly improved the distribution of Ce6 in tumor tissues of lung cancer-bearing mice as well. Finally, the findings of in vivo study and immunohistochemistry confirmed the better efficacy of IO-PG-GLU-Ce6. HE staining results of vital organs suggested that the composites were less toxic. CONCLUSION: In conclusion, Ce6 loaded by functionalized iron oxide nanoparticles linked with glucose exhibited both target photodynamic efficacy and the ability to enhance its immunogenicity in lung cancer. This study provides a promising strategy for augment of the targeting delivery of Ce6 and its mediated photodynamic and immunotherapy.

Mechanical Characterization of Hybrid Nano-Filled Glass/Epoxy Composites.

Fiber-reinforced polymer (FRP) composite materials are very versatile in use because of their high specific stiffness and high specific strength characteristics. The main limitation of this material is its brittle nature (mainly due to the low stiffness and low fracture toughness of resin) that leads to reduced properties that are matrix dominated, including impact strength, compressive strength, in-plane shear, fracture toughness, and interlaminar strength. One method of overcoming these limitations is using nanoparticles as fillers in an FRP composite. Thereby, this present paper is focused on studying the effect of nanofillers added to glass/epoxy composite materials on mechanical behavior. Multiwall carbon nanotubes (MWCNTs), nano-silica (NS), and nano-iron oxide (NFe) are the nanofillers selected, as they can react with the resin system in the present-case epoxy to contribute a significant improvement to the polymer cross-linking web. Glass/epoxy composites are made with four layers of unidirectional E-glass fiber modified by nanoparticles with four different weight percentages (0.1%, 0.2%, 0.5%, and 1.0%). For reference, a sample without nanoparticles was made. The mechanical characterizations of these samples were completed under tensile, compressive, flexural, and impact loading. To understand the failure mechanism, an SEM analysis was also completed on the fractured surface.

Enhanced aggregation and sedimentation of nanoscale zero-valent iron (nZVI) with polyacrylamide modification.

Nanoscale zero-valent iron (nZVI) settled slowly and incompletely in a nano-iron reactor (NIR) in wastewater treatment, and the effluent quality and processing capacity of nZVI were degenerated. Herein, three types of polyacrylamide (PAM), anionic-APAM (nZVIAPAM), cationic-CPAM (nZVICPAM), and nonionic-NPAM (nZVINPAM)) were applied to modify the nZVI (nZVIPAM), which were proved to enhance aggregation and sedimentation in the gravity settling clarifier of NIR. PAM modification lead to aggregate by forming large agglomerates. The median sizes of aggregates were 32, 194, 168 and 133 µm respectively for nZVI, nZVICPAM, nZVINPAM, and nZVIAPAM. Under quiescent conditions, bare nZVI needed 5 min to reach sedimentation equilibrium, while nZVIPAM just within 1 min nZVICPAM settled more quickly and completely than nZVINPAM and nZVIAPAM. The Fe concentration in the dynamic flow NIR effluent could keep a low level for 8 h for nZVIPAM, while bare nZVI for 6 h. Iron concentration was 3.11, 0.037, 0.93, and 1.20 mg·L-1 for nZVI, nZVICPAM, nZVINPAM, and nZVIAPAM after 8-h-reaction. Meanwhile, the reactivity of nZVIPAM was kept much longer for lead removal in the NIR. Results demonstrated PAM modifications (especially CPAM) provided a reliable solution for nZVI aggregation and sedimentation in wastewater treatment.

Bactericidal and Fungistatic Properties of LDPE Modified with a Biocide Containing Metal Nanoparticles.

The aim of this study was to ascertain whether the combined action of metal nanoparticles (silver, copper, zinc oxide, iron oxide) would ensure the appropriate biocidal properties oflow-density polyethylene (LDPE) against pathogenic microorganisms. According to the research hypothesis, appropriately selected concentrations of the applied metal nanoparticles allow for a high level of biocidal activity of polymeric materials against both model and pathogenic bacterial strains (Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, Legionella pneumophila, Salmonella enterica subsp. enterica) and fungi (Aspergillus brasiliensis, Saccharomyces cerevisiae, Candida albicans, Penicilium expansum), whilst ensuring the safety of use due to the lack of migration of particles to the surrounding environment. Studies have shown that adding 4% of a biocide containing Ag, Cu, ZnO, and Fe2O3 nanoparticles is the most optimal solution to reduce the number of S. aureus, S. enterica and P. aeruginosa by over 99%. The lowest effectiveness was observed against L. pneumophila bacteria. As for E. coli, a higher biocide content did not significantly increase the antibacterial activity. The results showed a high efficiency of the applied biocide at a concentration of 2% against fungal strains. The high efficiency of the obtained biocidal results was influenced by the uniform dispersion of nanoparticles in the material and their low degree of agglomeration. Furthermore, a slight migration of components to the environment is the basis for further research in the field of the application of the developed materials in industry.

Development of Dioctyl Phthalate@Fe3O4 Nanocomposite Reinforced Hollow Fiber Solid/ Liquid Phase Microextraction Followed by HPLC-DAD for the Determination of Atorvastatin and Gemfibrozil in Human Urine.

BACKGROUND: The desirable levels of lipids, especially in patients with coronary artery disease, might not be achievable with a single lipid-lowering drug; thus, combination therapy using atorvastatin and gemfibrozil seems to be a promising approach. However, the potential for drugdrug interaction needs to be taken into consideration, and the combination (atorvastatin and gemfibrozil) is recommended only when other options for reducing lipids have been exhausted. OBJECTIVES: Many studies are conducted for the determination of atorvastatin or gemfibrozil in biological fluids and tablets; however, the simultaneous determination of the two drugs in complex biological matrices is limited. Consequently, the development of a sensitive method for simultaneous determination of atorvastatin and gemfibrozil in urine samples is urgently needed to make sure that the doses of both medications are given to patients correctly to prevent the risk of side effects outcomes associated with the adverse drug-drug interaction. METHODS: A synthesized nanocomposite sorbent, dioctyl phthalate coated on the surface of magnetite (DOP@Fe3O4), was reinforced and immobilized into the pores of 2.5 cm segment hollow fiber microtube via ultrasonication, and the lumen of the microtube was filled with 1-octanol as an organic solvent with two ends heat-sealed. The prepared (DOP@Fe3O4-HF-SLPME) device was directly immersed into 10 mL of a sample solution containing atorvastatin and gemfibrozil with agitation. Subsequently, the microextraction device was transferred to HPLC-micro-vial containing an appropriate solvent, and the selected analytes were desorbed under ultrasonication prior to HPLCDAD analysis. The main factors influencing the adsorption and desorption process of the selected drugs have been optimized. RESULTS: The DOP@Fe3O4-HF-SLPME combined with the HPLC-DAD method was analytically evaluated for the simultaneous determination of atorvastatin and gemfibrozil in human urine samples using the optimized conditions. In spiked urine samples, the method showed a good linearity R2˃ 0.998, RSD from 1.41- 5.33%, and the limits of detection/ quantification (LOD/ LOQ) were 0.11/ 0.36 and 0.73/ 2.42 µg L-1 for atorvastatin and gemfibrozil, respectively. The enrichment factors of atorvastatin and gemfibrozil were 83.4 and 101.2, with extraction recoveries of 80.9% and 99.0%, respectively. The developed method demonstrated comparable results against referenced methods and a satisfactory result for determining the selected drugs in the patient's urine samples. CONCLUSION: The DOP@Fe3O4-HF-SLPME followed by HPLC-DAD was proved to be an efficient, sensitive, and cost-effective biopharmaceutical analysis method for trace levels of atorvastatin and gemfibrozil in the biological fluid matrix.

Adsorption of arsenic onto films based on chitosan and chitosan/nano-iron oxide.

Films made from neat chitosan and chitosan with magnetic nanoparticles (MNPs) were tested as adsorbents of arsenate ions. Sorption equilibrium and sorption kinetics studies are reported, including different models applied to enlighten experimental observations and predict results. The sorption of As (V) was reasonably explained using Freundlich isotherm for neat chitosan film although it was better represented by Langmuir equation for the composite sample. The experimental kinetics results showed that the adsorption of arsenate ions is very fast during the first minutes and then the composite seems to reach saturation, while a slow desorption in the chitosan film was observed and acceptably fitted with a pseudo first order reversible model. The adsorbent containing MNPs presented higher adsorption capacity, which was associated to the additional adsorbent capacity provided by the MNPs and its much more irregular surface area that leads to an enhanced adsorption surface. For instance, at 10 mg/L equilibrium concentration, which corresponds to an initial concentration of As (V) much higher than the normal concentration of arsenate in natural water, chitosan-MNP sample exhibits a removal capacity of 10.4 mg/g that is more than six times higher than the 1.6 mg/g shown by the chitosan film.

Nano iron materials enhance food waste fermentation.

Anaerobic fermentation can produce valuable chemicals from food waste, such as butyric acid, lactic acid, and ethanol. Three nano iron materials, i.e. zero-valence iron (nZVI), ferric oxide (nFO), and magnetite (nM), were tested to improve food waste fermentation with mixed inoculation. nZVI and nFO enhanced the dissolution and conversion of carbohydrate to lactate, dependent on different mechanisms, while nM had almost no effects due to its aggregation at high doses. nZVI alleviated the drop of pH, kept the ORP at an anaerobic level, increased functional enzymes, and resulted in a high hydrolysis rate of 45% and lactic acid yield of 0.16 g/g VSfed at the dose of 500 mg/(Lfed·d). nFO increased the ORP to 100 mV, stimulated the enrichment of Pseudomonas, and increased the abundance of Lactobacillus_panis, leading to hydrolysis rate of 47% and lactic acid yield of 0.19 g/gVSfed at the dose of 200 mg/(Lfed·d).

Synthesis and Application of Zero-Valent Iron Nanoparticles in Water Treatment, Environmental Remediation, Catalysis, and Their Biological Effects.

Present and past anthropogenic pollution of the hydrosphere and lithosphere is a growing concern around the world for sustainable development and human health. Current industrial activity, abandoned contaminated plants and mining sites, and even everyday life is a pollution source for our environment. There is therefore a crucial need to clean industrial and municipal effluents and remediate contaminated soil and groundwater. Nanosized zero-valent iron (nZVI) is an emerging material in these fields due to its high reactivity and expected low impact on the environment due to iron's high abundance in the earth crust. Currently, there is an intensive research to test the effectiveness of nZVI in contaminant removal processes from water and soil and to modify properties of this material in order to fulfill specific application requirements. The number of laboratory tests, field applications, and investigations for the environmental impact are strongly increasing. The aim of the present review is to provide an overview of the current knowledge about the catalytic activity, reactivity and efficiency of nZVI in removing toxic organic and inorganic materials from water, wastewater, and soil and groundwater, as well as its toxic effect for microorganisms and plants.

Assessment of biochar and/or nano zero-valent iron for the stabilisation of Zn, Pb and Cd: A temporal study of solid phase geochemistry under changing soil conditions.

The remediation of a soil contaminated with Zn, Pb and Cd was tested by using biochar (BC), nano zero-valent iron (nZVI) and a combination of these two (BC + nZVI). Each amendment was individually applied to the soil at 2 wt%. We tested the influence of (i) the used amendments, (ii) time, and (iii) soil moisture conditions on the metal availability and soil physico-chemical parameters using various extraction methods, as well as soil pore water samplings. We found that metal availability was mainly affected by pH under the influence of time and water content. Among the tested treatments, BC was the most successful, resulting in the lowest amounts of the target metals in the pore water and the smallest temporal changes in metal concentrations and pH in the soil. The use of nZVI efficiently decreased water-extractable Pb in the short- and long-term. The BC + nZVI treatment also yielded promising results regarding the immobilisation of the studied metals. Time provoked a general decrease in pH, which occasionally increased the available metal concentrations. Raising the soil water content increased the pH and subsequently lowered the available metal concentrations in the pore water. The mechanisms of metal stabilisation were further investigated by SEM/EDS. The results indicated that the used soil amendments enhanced the binding of Zn, Pb, and Cd on Fe/Mn/Al oxides/hydroxides, which in turn resulted in the stabilisation of the target metals.

A physical-based interpretation of mechanism and kinetics of Cr(VI) reduction in aqueous solution by zero-valent iron nanoparticles.

The aim of this paper is to show the results obtained by investigating the reduction of hexavalent Chromium [Cr(VI)] by iron nano-particles in aqueous solution, interpreted in light of the particle-grain model. The diffusional and geometric parameters that govern and describe the reacting system were estimated from the evidences deriving from the characterization and the experiments conducted, allowing assumptions based on physical principles. Such procedure rendered the particle-grain model a valid choice for the interpretation of the results obtained. The model, used in its dimensionless form, was tested according to a preliminary procedure aimed at analyzing the sensitivity of the system, by varying within wide ranges the ratio between the reaction rate, the diffusive mass transfer rate, and the particle-grain radius, to show how reliable its potential application may be. Subsequently, a non-linear regression procedure was used to estimate the two main parameters of the model that affect the reduction process: (i) the diffusion coefficient within the solid layer produced along with the reaction, Dpc (6.02 E-13 m2 s-1), and (ii) the kinetic constant of the surface reaction, kc (0.21 m s-1). The values found for the parameters were perfectly in line with theoretical considerations and experimental evidences.

Potential electron donor for nanoiron supported hydrogenotrophic denitrification: H2 gas, Fe0, ferrous oxides, Fe2+(aq), or Fe2+(ad)?

The mechanism of electron transmission in combined nanoiron-bacteria denitrification cannot be explained by the classic model, in which an Fe0H2-nitrate transferring chain is proposed. In this study, we used characteristic techniques and electrochemical analysis to investigate the necessity of molecular hydrogen for the combined denitrifying system using commercial nanoiron with Alcaligenes eutrophus, and to analyze its potential electron donor. Based on our results, nitrate removal and its by-products (NO2- and NH4+) generation was not significantly affected by residual H2 gas, indicating that H2 was not necessary for hydrogenotrophic denitrification. As to the potential electron donor analysis, nanoscale zero-valent iron did not appear to be the electron donor due to its high level of toxicity (83% mortality using nanoiron versus 36% in the control cells). In addition, when iron oxides (Fe3O4, Fe2O3 and FeOOH on the nanoiron surface) and free ferrous ions [Fe2+(aq)] were present alone, they were not utilized by the bacteria to degrade nitrate. According to the results of electrochemical analysis, adsorbed ferrous iron [Fe2+(ad)] on ferric oxides might be the electron donor in this kind of nitrate removal.