Bioproduction of cerium-bearing magnetite and application to improve carbon-black supported platinum catalysts.

BACKGROUND: Biogeochemical processing of metals including the fabrication of novel nanomaterials from metal contaminated waste streams by microbial cells is an area of intense interest in the environmental sciences. RESULTS: Here we focus on the fate of Ce during the microbial reduction of a suite of Ce-bearing ferrihydrites with between 0.2 and 4.2 mol% Ce. Cerium K-edge X-ray absorption near edge structure (XANES) analyses showed that trivalent and tetravalent cerium co-existed, with a higher proportion of tetravalent cerium observed with increasing Ce-bearing of the ferrihydrite. The subsurface metal-reducing bacterium Geobacter sulfurreducens was used to bioreduce Ce-bearing ferrihydrite, and with 0.2 mol% and 0.5 mol% Ce, an Fe(II)-bearing mineral, magnetite (Fe(II)(III)2O4), formed alongside a small amount of goethite (FeOOH). At higher Ce-doping (1.4 mol% and 4.2 mol%) Fe(III) bioreduction was inhibited and goethite dominated the final products. During microbial Fe(III) reduction Ce was not released to solution, suggesting Ce remained associated with the Fe minerals during redox cycling, even at high Ce loadings. In addition, Fe L2,3 X-ray magnetic circular dichroism (XMCD) analyses suggested that Ce partially incorporated into the Fe(III) crystallographic sites in the magnetite. The use of Ce-bearing biomagnetite prepared in this study was tested for hydrogen fuel cell catalyst applications. Platinum/carbon black electrodes were fabricated, containing 10% biomagnetite with 0.2 mol% Ce in the catalyst. The addition of bioreduced Ce-magnetite improved the electrode durability when compared to a normal Pt/CB catalyst. CONCLUSION: Different concentrations of Ce can inhibit the bioreduction of Fe(III) minerals, resulting in the formation of different bioreduction products. Bioprocessing of Fe-minerals to form Ce-containing magnetite (potentially from waste sources) offers a sustainable route to the production of fuel cell catalysts with improved performance.

Multilayered Fe3O4@(ZIF-8)3 combined with a computer-vision-enhanced immunosensor for chloramphenicol enrichment and detection.

The misuse and overuse of chloramphenicol poses severe threats to food safety and human health. In this work, we developed a magnetic solid-phase extraction (MSPE) pretreatment material coated with a multilayered metal-organic framework (MOF), Fe3O4 @ (ZIF-8)3, for the separation and enrichment of chloramphenicol from fish. Furthermore, we designed an artificial-intelligence-enhanced single microsphere immunosensor. The inherent ultra-high porosity of the MOF and the multilayer assembly strategy allowed for efficient chloramphenicol enrichment (4.51 mg/g within 20 min). Notably, Fe3O4 @ (ZIF-8)3 exhibits a 39.20% increase in adsorption capacity compared to Fe3O4 @ZIF-8. Leveraging the remarkable decoding abilities of artificial intelligence, we achieved the highly sensitive detection of chloramphenicol using a straightforward procedure without the need for specialized equipment, obtaining a notably low detection limit of 46.42 pM. Furthermore, the assay was successfully employed to detect chloramphenicol in fish samples with high accuracy. The developed immunosensor offers a robust point-of-care testing tool for safeguarding food safety and public health.

Structural Fe(II)-induced generation of reactive oxygen species on magnetite surface for aqueous As(III) oxidation during oxygen activation.

Magnetite is a reductive Fe(II)-bearing mineral, and its reduction property is considered important for degradation of contaminants in groundwater and anaerobic subsurface environments. However, the redox condition of subsurface environments frequently changes from anaerobic to aerobic owing to natural and anthropogenic disturbances, generating reactive oxygen species (ROS) from the interaction between Fe(II)-bearing minerals and O2. Despite this, the mechanism of ROS generation induced by magnetite under aerobic conditions is poorly understood, which may play a crucial role in As(III) oxidation. Herein, we found that magnetite could activate O2 and induce the oxidative transformation of As(III) under aerobic conditions. As(III) oxidation was attributed to the ROS generated via structural Fe(II) within the magnetite octahedra oxygenation. The electron paramagnetic resonance and quenching tests confirmed that O2•-, H2O2, and •OH were produced by magnetite. Moreover, density function theory calculations combined with experiments demonstrated that O2•- was initially formed via single electron transfer from the structural Fe(II) to the adsorbed O2; O2•- was then converted to •OH and H2O2 via a series of free radical reactions. Among them, O2•-and H2O2 were the primary ROS responsible for As(III) oxidation, accounting for approximately 52 % and 19 % of As(III) oxidation. Notably, As(III) oxidation mainly occurred on the magnetite surface, and As was immobilized further within the magnetite structure. This study provides solid evidence regarding the role of magnetite in determining the fate and transformation of As in redox-fluctuating subsurface environments.

Multifunctional molecularly imprinted nanozymes with improved enrichment and specificity for organic and inorganic trace compounds.

Although nanozymes exhibit properties superior to those of natural enzymes and conventional engineered enzymes, the development of highly specific nanozymes remains a challenge. New yolk-shell Fe3O4 molecularly imprinted (MIP@void@Fe3O4) nanozymes with peroxidase-like activity were developed by modelling the substrate channels of natural enzymes through molecular imprinting techniques and interfacial affinity modifications in this study. To establish a platform technology for the adsorption and determination of inorganic and organic contaminants, lead ion (Pb2+) and diazinon (DIZ), respectively, were selected as imprinting templates, and a hollow mesoporous shell was synthesized. The as-prepared MIP@void@Fe3O4 nanozymes, characterized using TEM, HRTEM, SEM, FT-IR, TGA, VSM and XPS, not only affirmed the successful fabrication of a magnetic nanoparticle with a unique hollow core-shell structure but also facilitated an exploration of the interfacial bonding mechanisms between Fe3O4 and other shell layers. The enrichment of the MIP@void@Fe3O4 nanozymes due to imprinting was approximately 5 times higher than the local substrate concentration and contributed to the increased activity. Based on selective and competitive recognition experiments, the synthesized nanozymes could selectively recognize organic and inorganic targets with the lowest detection limits (LOD) of 6.6 × 10-9 ppm for Pb2+ and 5.13 × 10-11 M for DIZ. Therefore, the proposed biosensor is expected to be a potent tool for trace pollutant detection, which provides a rational design for more advanced and subtle methods to bridge the activity gap between natural enzymes and nanozymes.

Stability and Speciation of Hydrated Magnetite {111} Surfaces from Ab Initio Simulations with Relevance for Geochemical Redox Processes.

Magnetite is a common mixed Fe(II,III) iron oxide in mineral deposits and the product of (anaerobic) iron corrosion. In various Earth systems, magnetite surfaces participate in surface-mediated redox reactions. The reactivity and redox properties of the magnetite surface depend on the surface speciation, which varies with environmental conditions. In this study, Kohn-Sham density functional theory (DFT + U method) was used to examine the stability and speciation of the prevalent magnetite crystal face {111} in a wide range of pH and Eh conditions. The simulations reveal that the oxidation state and speciation of the surface depend strongly on imposed redox conditions and, in general, may differ from those of the bulk state. Corresponding predominant phase diagrams for the surface speciation and structure were calculated from first principles. Furthermore, classical molecular dynamics simulations were conducted investigating the mobility of water near the magnetite surface. The obtained knowledge of the surface structure and oxidation state of iron is essential for modeling retention of redox-sensitive nuclides.

Design of Magnetic Fe3O4/CeO2 "Core/Shell"-Like Nanocomposites with Pronounced Antiamyloidogenic and Antioxidant Bioactivity.

"Core/shell" nanocomposites based on magnetic magnetite (Fe3O4) and redox-active cerium dioxide (CeO2) nanoparticles (NPs) are promising in the field of biomedical interests because they can combine the ability of magnetic NPs to heat up in an alternating magnetic field (AMF) with the pronounced antioxidant activity of CeO2 NPs. Thus, this report is devoted to Fe3O4/CeO2 nanocomposites (NCPs) synthesized by precipitation of the computed amount of "CeO2-shell" on the surface of prefabricated Fe3O4 NPs. The X-ray diffraction, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy data validated the formation of Fe3O4/CeO2 "core/shell"-like NCPs, in which ultrafine CeO2 NPs with an average size of approximately 3-3.5 nm neatly surround Fe3O4 NPs. The presence of a CeO2 "shell" significantly increased the stability of Fe3O4/CeO2 NCPs in aqueous suspensions: Fe3O4/CeO2 NCPs with "shell thicknesses" of 5 and 7 nm formed highly stable magnetic fluids with ζ-potential values of >+30 mV. The magnetization values of Fe3O4/CeO2 NCPs decreased with a growing CeO2 "shell" around the magnetic NPs; however, the resulting composites retained the ability to heat efficiently in an AMF. The presence of a CeO2 "shell" generates a possibility to precisely regulate tuning of the maximum heating temperature of magnetic NCPs in the 42-50 °C range and stabilize it after a certain time of exposure to an AMF by changing the thickness of the "CeO2-shell". A great improvement was observed in both antioxidant and antiamyloidogenic activities. It was found that inhibition of insulin amyloid formation, expressed in IC50 concentration, using NCPs with a "shell thickness" of 7 nm was approximately 10 times lower compared to that of pure CeO2. For these NCPs, more than 2 times higher superoxide dismutase-like activity was observed. The coupling of both Fe3O4 and CeO2 results in higher bioactivity than either of them individually, probably due to a synergistic catalytic mechanism.

Magnetite graphene oxide-albumin conjugate: carrier for the imatinib anticancer drug.

Carbon nanomaterials are widely used in biomedical applications due to their versatile properties. These are the attractive candidates for the carrying of anticancer drugs, genes, and proteins for chemotherapy. Imatinib is an effective chemotherapy drug whose toxicity has created a significant limitation in treatment. In this research, a new biocompatible nanocarrier based on albumin-magnetite graphene oxide conjugates was reported for the loading and release of imatinib. The magnetite graphene oxide nanocomposite was investigated by ultra violet-visible spectroscopy (UV-Vis), field emission scanning electron microscope (FE-SEM), X-ray diffraction spectroscopy (XRD) and energy diepersive X-ray spectroscopy (EDX) methods. The crystallite size of Fe3O4 nanoparticles on graphene oxide obtained from XRD is about 14 nm which is in agreement well with the SEM results. We show that magnetite graphene oxide conjugated with albumin is an extremely efficient carrier. An efficient loading of IM, 81% at pH 7.0, time 2 h and initial concentration of 1 mg/mL was seen onto magnetite graphene oxide-albumin in comparison to graphene oxide and magnetite graphene oxide due to the presence of oxygen and nitrogen functional groups of albumin. Upon the pH 9.0 and 7.0, 7% and 16% imatinib could be released from the magnetite graphene oxide-albumin in a time span of 5 h but when exposed pH 4.0 the corresponding 31% was released in 5 h. After 20 h, 21, 42 and 68% of imatinib was released at pH 9.0, 7.0 and 4.0, respectively. This illustrates the major benefits of the developed approach for biomedical applications.

Improving water treatment using a novel antibacterial kappa-carrageenan-coated magnetite decorated with silver nanoparticles.

In this study, we aimed to fabricate an enhanced antibacterial agent to act against pathogenic bacteria in aqueous environments. To achieve this, silver nanoparticles (AgNPs) were inlaid on a kappa-carrageenan (KC) base and coated on Fe3O4 magnetic cores (Fe3O4@KC@Ag). Superparamagnetic Fe3O4 nanoparticles were designed at the center of the composite nanostructure, allowing magnetic recovery from aqueous media in the presence of a magnet. The synthesized nanoconjugate was characterized in each step using XRD, FT-IR, EDX, FE-SEM, TEM, DLS, VSM, and disk-diffusion antibacterial method. Results show that the nanocomposite system is formed, while the magnetic properties remain practically stable. The agglomeration of the AgNPs was decreased by the trap-like function of KC coating, which resulted in an improved antibacterial activity for the Fe3O4@KC@Ag formulation. These findings suggest that Fe3O4@KC@Ag nanocomposites could be promising agents for combating bacterial infections in aqueous environments.

Lipid membrane modulated control of magnetic nanoparticles within bacterial systems.

Bacterial magnetosomes synthesized by the magnetotactic bacterium Magnetospirillum magneticum are suitable for biomedical and biotechnological applications because of their high level of chemical purity of mineral with well-defined morphological features and a biocompatible lipid bilayer coating. However, utilizations of native magnetosomes are not sufficient for maximum effectiveness in many applications as the appropriate particle size differs. In this study, a method to control magnetosome particle size is developed for integration into targeted technological applications. The size and morphology of magnetosome crystals are highly regulated by the complex interactions of magnetosome synthesis-related genes; however, these interactions have not been fully elucidated. In contrast, previous studies have shown a positive correlation between vesicle and crystal sizes. Therefore, control of the magnetosome vesicle size is tuned by modifying the membrane lipid composition. Exogenous phospholipid synthesis pathways have been genetically introduced into M. magneticum. The experimental results show that these phospholipids altered the properties of the magnetosome membrane vesicles, which yielded larger magnetite crystal sizes. The genetic engineering approach presented in this study is shown to be useful for controlling magnetite crystal size without involving complex interactions of magnetosome synthesis-related genes.

Retention of Iodide by Chloride Green Rust and Magnetite.

Green rust (GR), a layered double hydroxide (LDH) containing Fe, and magnetite can be found in natural and engineered environments. The ability of chloride GR (GR-Cl) and magnetite to retain iodide as a function of various parameters was investigated. Sorption equilibrium is achieved within 1 day of contact time between iodide and preformed GR-Cl in suspension. pHm variations (7.5-8.5) have no significant influence, but the iodide sorption decreases with increasing ionic strength set by NaCl. Sorption isotherms of iodide suggest that the uptake operates via ionic exchange (IC), which is supported by geochemical modeling. The short-range binding environment of iodide associated with GR is comparable to that of hydrated aqueous iodide ions in solution and is not affected by pHm or ionic strength. This finding hints at an electrostatic interaction with the Fe octahedral sheet, consistent with weak binding of charge balancing anions within an LDH interlayer. The presence of sulfate anions in significant amounts inhibits the iodide uptake due to recrystallization to a different crystal structure. Finally, the transformation of iodide-bearing GR-Cl into magnetite and ferrous hydroxide resulted in a quantitative release of iodide into the aqueous phase, suggesting that neither transformation product has an affinity for this anionic species.

Magnetite/ß-cyclodextrin/fly ash composite as an effective and recyclable adsorbent for uranium(VI) capture from wastewater.

As a novel adsorbent for the separation of uranium(VI) from wastewater, Magnetite/ß-cyclodextrin/fly ash composite (Fe3O4/ß-CD/FA) was first prepared via a chemical coprecipitation technology. The characterization results indicated that Fe3O4 and ß-CD had been successfully loaded on FA, which had brought abundant oxygen-containing functional groups, providing numerous adsorptive sites for the removal of uranium(VI). At pH = 5.0 and T = 25 °C, the maximum uranium(VI) removal efficiency and capacity of Fe3O4/ß-CD/FA were higher to 97.8% and 444.4 mg g-1, respectively. Pseudo-second-order and Langmuir models fitted better with the experimental data, illustrating that chemical adsorption dominated the uranium(VI) removal process. In addition, Fe3O4/ß-CD/FA showed good anti-interference ability and recoverability. After five cycles, the removal rate of uranium(VI) on Fe3O4/ß-CD/FA was still higher to 90.4%. The immobilization of uranium(VI) on Fe3O4/ß-CD/FA was mainly ascribed to the synergism of redox reaction, complex reaction, chemical reaction and electrostatic interaction. Given the above, Fe3O4/ß-CD/FA would be regarded as an efficacious, green and promising adsorbent for uranium(VI) separation from wastewater.

Recent advances in studies on magnetosome-associated proteins composing the bacterial geomagnetic sensor organelle.

Magnetotactic bacteria (MTB) generate a membrane-enclosed subcellular compartment called magnetosome, which contains a biomineralized magnetite or greigite crystal, an inner membrane-derived lipid bilayer membrane, and a set of specifically targeted associated proteins. Magnetosomes are formed by a group of magnetosome-associated proteins encoded in a genomic region called magnetosome island. Magnetosomes are then arranged in a linear chain-like positioning, and the resulting magnetic dipole of the chain functions as a geomagnetic sensor for magneto-aerotaxis motility. Recent metagenomic analyses of environmental specimens shed light on the sizable phylogenetical diversity of uncultured MTB at the phylum level. These findings have led to a better understanding of the diversity and conservation of magnetosome-associated proteins. This review provides an overview of magnetosomes and magnetosome-associated proteins and introduces recent topics about this fascinating magnetic bacterial organelle.

Study of phenobarbital removal from the aqueous solutions employing magnetite-functionalized chitosan.

Due to its wide use in anticonvulsant pharmacotherapy, phenobarbital (PHEN) is an aquatic contaminant with a high prevalence in the environment. In this adsorption study, chitosan and chitosan-based magnetic adsorbents containing different amounts of incorporated magnetite (CS, CS·Fe3O4 1:1, CS·Fe3O4 1:5, and CS·Fe3O4 1:10) were used for phenobarbital removal. The magnetic adsorbents were synthesized by co-precipitation method and characterized through FTIR, XRD, MEV, and VSM analysis. In PHEN adsorption, the equilibrium and adsorption kinetic were better adjusted by the Sips and pseudo-second-order model, respectively. Among the four nanoadsorbents used, the maximum phenobarbital adsorption capacity was 94.60 mg g-1 using 25 mg of CS·Fe3O4 1:5, with a concentration of PHEN (50 mg L-1), pH 7.0 at room temperature. The parameters of pH, adsorbent dosage, ionic strength, and thermodynamic study were tested for the adsorbent with the highest performance (CS·Fe3O4 1:5). The nanoadsorbent demonstrates efficiency in the removal of the contaminant for diverse adsorption cycles. Finally, the protocol employing magnetic adsorbents dispenses the subsequent steps of filtration and centrifugation.

Stimulation the immune response through ξ potential on core-shell 'calcium oxide/magnetite iron oxides' nanoparticles.

This study investigated the role of ξ Potential on Monometallic (MM) and Bimetallic (BM) Calcium Oxide/Magnetite Iron Oxides nanoparticles to stimulate the immune response. Metallic nanoparticles (MNPs) were biosynthesis using Pseudomonas fluorescens S48. MNPs characterization was carried out by UV-Vis spectra, XRD analysis, Zeta potential and Particles size, SEM-EDS, and TEM, and the concentrations were calculated by ICP-AES. The immune system activity was measured by estimation of lymphocytes transformation, phagocytic activity. The end point was in evaluating the toxicity of Metallic NPs by comet assay. SEM-EDS and TEM micrographs showed that MM CaO and Fe3O4 represent a perfect example of zero-dimensional (0-D) NPs with cubic and spherical particles in shape, while BM CaO/Fe3O4 NPs appeared in the form of Core-shell structure. The variations effect of novelty MM, BM CaO/Fe3O4 NPs in enhancing immune activity were based on the ξ Potential whereas negatively and positively charged. These findings demonstrate that the cationic CaO/Fe3O4 NPs are inefficient in stimulating the immune system which causes a high cytotoxic effect. But the anionic CaO/Fe3O4 NPs have advantages in targeting the immune system because of enhanced delivery to the cells through adsorptive endocytosis as well as the half-life clearance from the blood.

Synthesis and characterization of hydrogel-based magnetite nanocomposite adsorbents for the potential removal of Acid Orange 10 dye and Cr(VI) ions from aqueous solution.

Magnetic responsive hydrogels (CMX-cl-P4VP/M-NPs) were successfully synthesized through in situ co-precipitation procedure and investigated using various techniques. The surface morphology analysis revealed that the M-NPs were uniformly distributed within the hydrogel matrix and had average sizes ranging from 4.98 to 15.02 nm. The graft copolymer containing nanoparticles exhibited a sensitive magnetic response, and their recovery could be facilitated by applying a magnetic field. The purpose of this research is to study the ability of the prepared magnetic hydrogel to remove AO-10 dye and hexavalent chromium ions (Cr(VI)) from the aqueous solution under various factors, namely contact time, pH, amount of adsorbent, coexisting ions and AO-10 and Cr(VI) concentrations. The outcomes of the batch adsorption demonstrated that the adsorbent hydrogel incorporated with a low percentage (10 %) of M-NPs had a strong affinity for the removal of AO-10 dye and Cr(VI) ions at an optimum pH = 3, and the removal percentage reached 99.3 and 97.4 % for 500 mg L-1 and 300 mg L-1 of AO-10 dye and Cr(VI) ions within 90, 50 min, respectively. The data were well-fitted by pseudo-first-order kinetics. The maximum adsorption capacities of AO-10 dye and Cr(VI) ions onto adsorbent were 2448 and 574.7 mg g-1 at 298 K, calculated from the Langmuir model.

Graphene-magnetite functionalized diatomite for efficient removal of organochlorine pesticides from aquatic environment.

A unique composite based on graphene oxide, magnetite, and diatomite was synthetized by eco-friendly dry coating technique for the removal of four toxic organochlorine pesticides from agricultural drainage. The prepared composite was fully characterized using X-ray fluorescence (XRF), X-ray diffraction (XRD), particle size analyzer, Vibrating-sample magnetometer (VSM), magnetic susceptibility meter, zeta potential, scanning electron microscopy-energy dispersive X-ray spectrometer (SEM-EDS), and Brunauer-Emmett-Teller analysis (BET) techniques. The characterization results confirmed the fabrication of a discrete core/shell structured composite possess both adsorptive and magnetic nature. The surface area, pore volume and pore diameter were 23.4 m2/g, 0.0026 cm3/g, and 4.5 nm, respectively. The amenability to use the fabricated composite as an adsorbent for some organochlorine pesticides was investigated under different conditions of concentration, time, pH, and temperature. Batch adsorption experiment showed that 97% removal efficiency was observed for all the studied pesticides with adsorption capacities of 7.78 mg/g after 2 h contact time and at any pH region. The adsorption was exothermic (ΔH < 0), spontaneous (ΔG° < 0), followed pseudo 2nd order kinetics (R2 > 0.998), and fitted well to Langmuir's isotherm pattern for all pesticides (R2 > 0.98). It is assumed that organochlorine pesticides were initially physisorbed by the graphene nanoplatelets via hydrophobic and π-π interactions along with chemisorption for forming monolayer. Moreover, the pesticides molecules could diffuse in the DMG composite micropores and be trapped in the structural defects. The regeneration of the composite exhibited over 90% removal efficiency even after seven cycles. The fabricated composite was examined to remove organochlorine from a real water sample, the obtained results suggest the possibility to use this composite as an economical, effective and sustainable adsorbent for the treatment of pesticides contaminating water.

Effective removal of Cr(VI) and methyl orange by nano magnetite loaded starch/muscovite biocomposite: Characterization, experiments, advanced modeling, and physicochemical parameters interpretation.

Magnetite nanoparticles (MNPs) synthesized from heated basalt were used to support a biocomposite prepared from muscovite (Mus) and carbohydrate polymer starch (St). The developed Mus/St/MNPs composite was characterized by XRD, FTIR, FESEM, TGA, DSC, and Zeta potential techniques. This multifunctional composite showed outstanding adsorption properties for hexavalent chromium (Cr(VI)) and methyl orange (MO) removal at 25-55 °C and pH 3.0. The adsorption isotherms were fitted to Langmuir model for Cr(VI) and Freundlich equation for MO. To understand microscopically these systems and to analyze their adsorption geometry and interactions mechanism, three statistical physics models were utilized. Theoretical calculations indicated that Cr(VI) ions were adsorbed on composite surface presenting a combination of horizontal and vertical positions, while the aggregated MO molecules displayed a non-parallel adsorption orientation and multi-interactions mechanism. The saturation adsorption capacity increased from 243.37 to 371.59 mg/g for Cr(VI) and 409.29 to 457.62 mg/g for MO at 25 and 55 °C (i.e., endothermic interactions). Cr(VI) and MO adsorption on Mus/St/MNPs was controlled by van der Waals forces, hydrogen bonding, and electrostatic interactions where the calculated adsorption energies were 12.5-30.62 kJ/mol. The utilized adsorbent was easily reactivated and reused several times where regenerated Mus/St/MNPs composite showed nearly 79 % of Cr(VI) and 85 % of MO adsorption capacities even after the fourth adsorption-desorption cycle. This study contributes to understand the physicochemical factors of Cr(VI) and MO adsorption on multifunctional adsorbents like MNPs/carbohydrate polymers/aluminosilicates interface.

Synthesis and characterization of magnetic organic montmorillonite: efficient adsorption of hexavalent chromium.

This research compared two potential adsorbents for the efficient adsorption of toxic hexavalent chromium. The non-magnetic material STAC-Mt and the magnetic material FeSO4-STAC-Mt were synthesized by a simple impregnation method using montmorillonite (Mt), octadearyl dimethyl ammonium chloride (STAC) and ferrous sulfate as raw materials. The structural and morphological characteristics of both adsorbents were investigated by BET, XRD, FTIR, Zeta, VSM, TEM, SEM and XPS techniques. SEM and TEM results clearly revealed that FeSO4-STAC-Mt had a more loosely curled structure than STAC-Mt and the existence of well dispersed diamond-shaped magnetic particles. The saturation magnetization intensity of 17.949 emu/g obtained by VSM further confirmed the presence of magnetite particles in FeSO4-STAC-Mt. Due to the superparamagnetic properties of magnetite, the adsorption performance of FeSO4-STAC-Mt was better than STAC-Mt. FeSO4-STAC-Mt adsorbed up to 43.98 mg/g of Cr(VI), meanwhile it was easily separated from the reaction mixture by an external magnetic field. Intermittent adsorption studies at pH, adsorbent dosage and time revealed a rapid Cr(VI) adsorption process. In combination with response surface optimization analysis, a removal rate of 98.03% of Cr(VI) was obtained at pH 5-6. The adsorption process was properly described by the pseudo-second-order kinetic equation and the Langmuir equation, and the adsorption process was chemisorption and single molecular layer adsorption. In addition, the removal of Cr(VI) reached 72.68% after five cycles, demonstrating the good stability of the FeSO4-STAC-Mt.

Rapid Removal of Organic Pollutants from Aqueous Systems under Solar Irradiation Using ZrO2/Fe3O4 Nanoparticles.

Pure water scarcity is an emerging, all-around problem that globally affects both the life quality and the world's economy. Heterogeneous photocatalysis under solar irradiation is a promising technique for the organic pollutants (e.g., pesticides, drugs) removal from an aqueous environment. Furthermore, the drawbacks of commercially available photocatalysts can be successfully overcome by using innovative nanoparticles, such as ZrO2/Fe3O4. Four ZrO2/Fe3O4 nanopowders with a different mass ratio of ZrO2 and Fe3O4 were synthesized using the chemical co-precipitation method. XRD analysis showed the presence of magnetite and hematite Fe-oxide phases in all samples. The content of the magnetite phase increased with the addition of 19% ZrO2. The efficiency of the newly synthesized ZrO2/Fe3O4 nanoparticles was investigated in the rapid removal of selected pollutants under various experimental conditions. Nevertheless, the influence of the water matrix on photocatalytic degradation was also examined. The obtained data showed that using ZrO2/Fe3O4 nanosystems, an appropriate removal rate of the selected pesticides and pharmaceuticals can be reached after 120 min of solar irradiation. Further, the total organic carbon measurements proved the mineralization of the target emerging pollutants. ZrO2/Fe3O4 nanoparticles are economically feasible, as their removal from the suspension can be easily achieved using affordable, environmentally-friendly magnetic separation.

Redox Potentials of Magnetite Suspensions under Reducing Conditions.

Predicting the redox behavior of magnetite in reducing soils and sediments is challenging because there is neither agreement among measured potentials nor consensus on which Fe(III) | Fe(II) equilibria are most relevant. Here, we measured open-circuit potentials of stoichiometric magnetite equilibrated over a range of solution conditions. Notably, electron transfer mediators were not necessary to reach equilibrium. For conditions where ferrous hydroxide precipitation was limited, Nernstian behavior was observed with an EH vs pH slope of -179 ± 4 mV and an EH vs Fe(II)aq slope of -54 ± 4 mV. Our estimated EHo of 857 ± 8 mV closely matches a maghemite|aqueous Fe(II) EHo of 855 mV, suggesting that it plays a dominant role in poising the solution potential and that it's theoretical Nernst equation of EH[mV] = 855 - 177 pH - 59 log [Fe2+] may be useful in predicting magnetite redox behavior under these conditions. At higher pH values and without added Fe(II), a distinct shift in potentials was observed, indicating that the dominant Fe(III)|Fe(II) couple(s) poising the potential changed. Our findings, coupled with previous Mössbauer spectroscopy and kinetic data, provide compelling evidence that the maghemite/Fe(II)aq couple accurately predicts the redox behavior of stoichiometric magnetite suspensions in the presence of aqueous Fe(II) between pH values of 6.5 and 8.5.