Magnetite Structure Research Articles

Upconverting/magnetic Janus-like nanoparticles integrated into spiropyran micelle-like nanocarriers for NIR light- and pH- responsive drug delivery, photothermal therapy and biomedical imaging.

The integration of multiple functionalities into single theranostic platforms offers new opportunities for personalized and minimally invasive clinical interventions, positioning these materials as highly promising tools in modern medicine. Thereby, magneto-luminescent Janus-like nanoparticles (JNPs) were developed herein, and encapsulated into near-infrared (NIR) light- and pH- responsive micelle-like aggregates (Mic) for simultaneous magnetic targeting, biomedical imaging, photothermal therapy, and pH- NIR-light activated drug delivery. The JNPs consisted of NaYF4:Yb,Tm upconverting nanoparticles (UCNPs) on which a well-differentiated magnetite structure (MNPs) grew epitaxially. JNPs were encapsulated together with doxorubicin (Dox) into micelle-like aggregates formed with the stimuli-responsive Poly(NIPAM-co-Spiropyran) copolymer, which responds to UV light, temperature changes, and pH variations, so as to form the JNP-Dox@Mic nanocarrier. Based on physicochemical characterizations, the mechanism for the NIR-activated release of Dox from the JNP-Dox@Mic aggregates is suggested: i) activation of the upconverting emissions with 975 nm light, ii) energy transfer to the material's lattice via nonradiative relaxation, inducing a local temperature increase, iii) resonance energy transfer (RET) from the UV-emission bands to the micelle-like aggregates, and iv) reversible isomerization of the hydrophobic Spiropyran (SP) moiety to a hydrophilic zwitterionic merocyanine (MC) form, leading to Dox delivery. Furthermore, the strong light-to-heat conversion ability of the JNPs was demonstrated through thermal imaging analysis, reaching temperatures up to 108 °C upon irradiation for 60 seconds. The efficacy of these nanocomposites for pH- and NIR-light-induced controlled release was demonstrated using electrophoretic separations and tested against MCF-7 breast cancer cells. While non-irradiated samples of JNP-Dox@Mic were innocuous up to 200 μg.mL-1, irradiation with 975 nm light for 5 minutes reduced cell viability to 26 %. These findings highlight the effective synergy between JNPs and micelle-like aggregates, resulting in versatile heterostructures that could be evaluated for multimodal therapy and imaging strategies.

Magnetochrome-catalyzed oxidation of ferrous iron by MamP enables magnetite crystal growth in the magnetotactic bacterium AMB-1

Magnetotactic bacteria have evolved the remarkable capacity to biomineralize chains of magnetite [Fe(II)Fe(III)2O4] nanoparticles that align along the geomagnetic field and optimize their navigation in the environment. Mechanisms enabling magnetite formation require the complex action of numerous proteins for iron acquisition, sequestration in dedicated magnetosome organelles, and precipitation into magnetite. The MamP protein contains c-type cytochromes called magnetochrome domains that are found exclusively in magnetotactic bacteria. Ablation of magnetochromes in MamP prevents bacteria from aligning with external magnetic fields, showing their importance to maintain this biological function. MamP has been proposed, mostly from in vitro experimentations, to regulate iron redox state and maintain an Fe(II)/Fe(III) balance compatible with magnetite formation via the iron oxidase activity of magnetochromes. To test the proposed function for MamP in vivo in the magnetotactic strain Magnetospirillum magneticum (AMB)-1, we characterized the iron species in chemical MamP-mediated magnetite syntheses as well as in bacteria unable to produce MamP using a combination of physicochemical methodologies. We show that MamP has no apparent control on the speciation and oxidation state of intracellular iron or on the Fe(II)/Fe(III) balance in magnetite. We propose that MamP promotes magnetite growth by incorporating Fe(III) into preexisting magnetite seeds and that magnetite structure and stoichiometry is maintained by further equilibration with dissolved Fe(II) in magnetosome organelles.

Clay Minerals and Continental‐Scale Remagnetization: A Case Study of South American Neoproterozoic Carbonates

AbstractThe Neoproterozoic carbonate rocks of the Araras Group (Amazon Craton) and the Sete‐Lagoas and Salitre Formations (São Francisco Craton) share a statistically indistinguishable single‐polarity (reversed) characteristic direction. This direction is associated with paleomagnetic poles that do not align with the expected directions for primary detrital remanence. We employ a combination of classical rock magnetic properties and micro imaging/chemical analysis (in thin sections) using synchrotron radiation to examine these remagnetized carbonate rocks. Magnetic data indicate that most samples lack the anomalous hysteresis properties typically associated with carbonate remagnetization (except for distorted loops). Through a combination of Scanning Electron Microscopy with Energy Dispersive X‐ray Spectroscopy (SEM‐EDS), X‐ray Fluorescence (XRF), and X‐ray Absorption Spectroscopy (XAS), we identified subhedral/anhedral magnetite, or spherical grains with a core‐shell structure of magnetite surrounded by maghemite. These grains are within the pseudo‐single domain size range, as do most of the iron sulfides, and are spatially associated with potassium‐bearing aluminosilicates. While fluid percolation and organic matter maturation play a role, smectite‐illitization appears to be crucial for the growth of these phases. X‐ray diffraction analysis, in addition, identifies these silicates as predominantly highly crystalline illite, suggesting exposure to epizone temperatures. These temperatures were likely reached during the final stages of the Gondwana assembly (Cambrian), but remanence was only locked in afterward, in successive cooling events during the Early Middle Ordovician. This is supported by the carbonates' paleomagnetic pole positions compared to Gondwana's apparent polar wander path, and the absence of reversals, contrasting with the high reversal frequency of the Late Ediacaran/Cambrian.

Influence of the iron-oxide mass fractions of magnetic powdered activated carbon on its hexavalent chromium adsorption performance in water

Magnetic powdered activated carbon (Mag-PAC) is an effective adsorbent to remove hexavalent chromium (Cr(VI)) from water and can be recovered for reuse. However, the tradeoff between the adsorption performance of Cr(VI) and magnetic properties of Mag-PAC remains unclear. Herein, we prepared a series of Mag-PAC adsorbents containing various iron-oxide mass fractions with FeSO4·7H2O as the precursor, using a facile wet-chemical precipitation route and conducted batch experiments to evaluate the Cr(VI) adsorption performance. Results revealed that Mag-PAC was functionalized by magnetic iron oxide comprising crystalline goethite and magnetite structures. Furthermore, its adsorption performance was highly dependent on pH and was most effective at an initial solution pH of 2. Both the sorption rate constant and Cr(VI) adsorption capacity were greatly influenced by magnetization, and they gradually decreased as the iron-oxide mass fraction increased. Among the prepared adsorbents, Mag-PAC-75 (∼32% wt iron) exhibited not only an excellent Cr(VI) adsorption performance (Langmuir adsorption capacity: 75.76 mg/g) but also effective magnetic properties (saturation magnetization: 9.66 emu/g). Coexisting anions had a negligible competitive effect on Cr(VI) removal by Mag-PAC-75 at an initial pH of 2, whereas the presence of tannic acid markedly improved the Cr(VI) elimination. The presence of trivalent chromium on the surface of Mag-PAC-75 confirmed via X-ray photoelectron spectroscopy indicated that some synergistic redox reactions may occur during the sorption process. After five regeneration cycles using NaOH, Mag-PAC-75 continued to exhibit a high Cr(VI) removal efficiency and magnetic stability. These findings indicate that optimizing the adsorption performance and magnetic properties is a key factor for realizing the practical application of Mag-PAC for Cr(VI) removal. Overall, Mag-PAC may have been a promising application prospect for Cr(VI) removal from water due to its high adsorption capacity and magnetic properties, coupled with its good reusability and magnetic stability after regeneration cycles.

Synthesis, structure and magnetic properties of Mn-substituted magnetite for magnetorheological materials

Iron(II)-manganese(II) ferrite with the composition Mn0.3Fe2.7O4 was synthesized using the coprecipitation method (with various options for subsequent thermal and mechanical treatment of the precipitate). The material was studied by X-ray phase analysis, infrared spectroscopy, scanning electron microscopy and magnetometry. The powder, which was fired in argon at 740°C (8.0 h) and high-energy grinding (1.0 h) at the final stage of synthesis, is a promising functional filler for magnetorheological materials. An oil suspension based on this powder shows a high shear stress value (3500 Pa at 625 mT). In addition, this powder has a high oil absorption capacity, which ensures sedimentation stability of the suspension.

Using the High-Entropy Approach to Obtain Multimetal Oxide Nanozymes: Library Synthesis, In Silico Structure-Activity, and Immunoassay Performance.

High-entropy nanomaterials exhibit exceptional mechanical, physical, and chemical properties, finding applications in many industries. Peroxidases are metalloenzymes that accelerate the decomposition of hydrogen peroxide. This study uses the high-entropy approach to generate multimetal oxide-based nanozymes with peroxidase-like activity and explores their application as sensors in ex vivo bioassays. A library of 81 materials was produced using a coprecipitation method for rapid synthesis of up to 100 variants in a single plate. The A and B sites of the magnetite structure, (AA')(BB'B'')2O4, were substituted with up to six different cations (Cu/Fe/Zn/Mg/Mn/Cr). Increasing the compositional complexity improved the catalytic performance; however, substitutions of single elements also caused drastic reductions in the peroxidase-like activity. A generalized linear model was developed describing the relationship between material composition and catalytic activity. Binary interactions between elements that acted synergistically or antagonistically were identified, and a single parameter, the mean interaction effect, was observed to correlate highly with catalytic activity, providing a valuable tool for the design of high-entropy-inspired nanozymes.

Ultrafast generation of hidden phases via energy-tuned electronic photoexcitation in magnetite

Phase transitions occurring in nonequilibrium conditions can evolve through high-energy intermediate states inaccessible via equilibrium adiabatic conditions. Because of the subtle nature of such hidden phases, their direct observation is extremely challenging and requires simultaneous visualization of matter at subpicoseconds and subpicometer scales. Here, we show that a magnetite crystal in the vicinity of its metal-to-insulator transition evolves through different hidden states when controlled via energy-tuned ultrashort laser pulses. By directly monitoring magnetite's crystal structure with ultrafast electron diffraction, we found that upon near-infrared (800 nm) excitation, the trimeron charge/orbital ordering pattern is destroyed in favor of a phase-separated state made of cubic-metallic and monoclinic-insulating regions. On the contrary, visible light (400 nm) activates a photodoping charge transfer process that further promotes the long-range order of the trimerons by stabilizing the charge density wave fluctuations, leading to the reinforcement of the monoclinic insulating phase. Our results demonstrate that magnetite's structure can evolve through completely different metastable hidden phases that can be reached long after the initial excitation has relaxed, breaking ground for a protocol to control emergent properties of matter.

Synthesis of novel iron Oxide/Carbon dots green nanocomposites for bacteria detection and antibacterial agent applications

Due to the widespread of pathogens and infectious diseases, rapid detection and antibacterial agents are needed. Antibacterial nanomaterials have attracted attention due to their advantageous properties and unique mechanisms. Besides, the green route approach to synthesizing nanoparticles has attracted interest due to being environmentally friendly, biocompatible, and non-toxic. In this study, carbon dots (Cdots), a promising antibacterial material, have been combined with the Fe3O4 nanoparticles as the carrier and produce Fe3O4/Cdots nanocomposite via green synthesis for bacteria detection and antibacterial agents. Green synthesis was achieved with Moringa oleifera leaves extract as reducing agent on Fe3O4 and watermelon peel as carbon source on Cdots. X-ray diffraction shows a cubic inverse spinel structure of magnetite. The phase composition of the nanocomposites consists of magnetite and carbon. The particle size of nanocomposites is 13.4 nm with semi-spherical morphology and high surface area. The bonding analysis and element composition are consistent with phase composition estimation that confirms the existence of Fe3O4 and Cdots on the nanocomposites and lacks other impurities. The vibrating sample magnetometer shows the superparamagnetic behavior of the samples. Nanocomposites were used to detect Escherichia coli (E. coli) bacteria. The quenching of photoluminescence of the nanocomposite shows an increase in the amount of E. coli bacteria. Furthermore, nanocomposites produce high inhibition zones against E. coli bacteria within 48 h, offering excellent antibacterial properties. Hence, nanocomposites provide a promising agent for bacteria detection and antibacterial treatment.

Innovative Agrowaste Banana Peel Extract-Based Magnetic Iron Oxide Nanoparticles for Eco-Friendly Oxidative Shield and Freshness Fortification

This study presents the synthesis of agro-waste banana peel extract-based magnetic iron oxide nanoparticles (BPEx-MIONPs), emphasizing antioxidant capacity and food preservation. Using iron (III) chloride hexahydrate (FeCl3 · 6 H2O) as a precursor and a reducing agent from agro-waste peel extract, a precisely controlled process yielded BPEx-MIONPs. Characterization involved X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and Fourier-transform infrared spectroscopy (FTIR). XRD revealed tetragonal Fe2O3, cubic magnetite structure, and monoclinic FexOy-NPs with an average size of 14.8 nm. TEM and SEM revealed diverse morphologies. TEM displayed both spherical and elongated nanoparticles, with some appearing as thin fibrils. In contrast, SEM images depicted an array primarily consisting of spherical nanoparticles, resembling coral reef formations. FTIR confirmed Fe–O bonds (1000 –400 cm-1). The antioxidant assessment showed robust DPPH free radical scavenging; BPEx achieved 100% inhibition at 18 min, and BPEx-MIONPs had an IC50 of ~ 136 µg/mL. BPEx-MIONPs, stabilized with banana-based bioplastic, effectively preserved grapes, reducing weight loss to 6.2% on day 3, compared to the control (19.0%). This pioneering study combines banana peel antioxidants with magnetic iron oxide nanoparticles, providing sustainable solutions for food preservation and nano-packaging. Ongoing research aims to refine conditions and explore broader applications of BPEx-MIONPs.Graphical

Copper-substituted magnetite as a Fenton-like catalyst boosted with electromagnetic heating

Copper-substituted magnetite samples Fe3-xCuxO4 (x = 0.0; 0.02; 0.05; 0.1) were synthesized using the co-precipitation method. XRD data revealed that the synthesized samples retain the cubic spinel structure of magnetite. The obtained materials were tested as heterogeneous Fenton catalysts to destroy organic pollutants and inactivate bacteria. The model organic pollutants were oxytetracycline, Congo Red dye, and Methylene Blue dye having neutral, anionic, and cationic nature, respectively. These organic pollutants differ in their adsorption on magnetite surface: oxytetracycline < Congo Red < Methylene Blue. The same order stays for their decomposition rates. The copper-substituted magnetite catalysts also ensure effective inactivation of E.coli bacteria. A contact time of 60 min is sufficient to reduce the number of bacteria by 6-log. In all tests, the catalytic activity of magnetite increases with the increase in Cu content. The maximum catalytic activity was recorded for the Fe2.9Cu0.1O4 sample. Since the copper-substituted magnetite samples are ferromagnetic, they absorb a high-frequency electromagnetic field. Electromagnetic heating results in a significant increase in catalytic activity: the rate constants of the studied catalytic reactions are increased by 1.5–5 times. Thus, copper-doped magnetite is a hetero-Fenton catalyst capable of increasing activity by electromagnetic heating. The adjustable catalytic activity may be useful in water disinfection, where bacterial load varies greatly.

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.

Methotrexate anti-cancer drug removal using Gd-doped Fe3O4: Adsorption mechanism, thermal desorption and reusability

One of the means of removing anthropogenic contaminants such as anti-cancer drugs from widely understood water environments is through adsorption. However, it is imperative to ensure that adsorbed contaminants do not find their way back into the environment, hence the quest for this study. Gadolinium (Gd)-doped Fe3O4 was synthesized, characterized, and applied for the removal of methotrexate (MEX), an anti-cancer drug. The incorporation of Gd did not alter the crystal structure of magnetite, having crystallite size and the d-spacing of 10 nm and 2.516 Å respectively. The magnetic saturation slightly reduced from 71 before doping to 67 emu g −1 after adding 5% atomic weight of Gd. The BET-specific surface area increased from 87 to 102 m2 g−1 when the content of Gd was 15%. The particle size is within the range of 10–20 nm. The dopant shifted the isoelectric point of the adsorbent nanoparticles to a more positive value which favored the adsorption of methotrexate at pH 7. The adsorption capacity increased from 28 mg g−1 (0%_Gd) to 64 mg g−1 (5%_Gd). The addition of CaCl2, due to the hydrophobic effect increased the amount of MEX that was removed. To ensure that the adsorbed MEX did not escape to the environment, Gd-doped Fe3O4 was thermally decomposed from the surface of the doped magnetite and reused for up to 4 cycles. The proposed mechanisms of adsorption were due to electrostatic and hydrogen bond interaction.

Antioxidant action of L-cysteine anchored on the surface of magnetite nanoparticles

This study addresses the synthesis, characterization, and evaluation of L-Cysteine (L-Cys) molecules anchored on superparamagnetic iron oxide nanoparticles (SPIONs), mainly magnetite (Fe3O4), for potential drug delivery applications. Fe3O4 nanoparticles are obtained via co-precipitation and functionalized with L-Cys to improve biocompatibility and antioxidant activity. To optimize the functionalization process, the dimerization of cysteine to cystine is investigated by varying the reaction time and mass proportions. The samples are characterized by powder X-ray diffraction (PXRD), Fourier transform infrared (FTIR) and Raman spectroscopies, transmission electron microscopy (TEM), and magnetic curves. These results confirm that L-Cys molecules are anchored on the nanoparticle surface through their carboxylate groups, with free SH groups present in the dispersed nanoparticles. However, in the solid state, L-Cys dimerization leads to a cystine crystal structure, resulting in no free SH groups. The nanoparticles have a magnetite structure with an average crystallite size of (8.7±0.8) nm and superparamagnetic behavior. In vitro biological assays show the antioxidant effect of L-Cysteine on the surface of the nanoparticles.

Kinetics of spontaneous phase transitions from wüstite to magnetite in superparamagnetic core-shell nanocubes of iron oxides.

Iron oxide nanoparticles with a wüstite structure have been prepared by thermal decomposition. In air, they undergo a spontaneous transition into a thermodynamically more stable magnetite structure that grows from the surface. The thickness of this magnetite shell increases with time, thereby producing a series of core-shell nanoparticles. We investigated the kinetics of this phase transition in 23 nm nanocubes using time-resolved XRD, from which the fractions of individual phases were determined by the Rietveld refinement. This kinetics is described theoretically using three coupled reaction-diffusion master equations for the concentrations of oxygen, wüstite, and magnetite, in which both the diffusion of oxygen and its reaction with wüstite are thermally activated. The coefficients of these terms were adjusted so that the predictions of the model reproduce the XRD data at 298 K and 353 K, whereas the predictive capability of the model was assessed by comparing its predictions with measurements at 403 K.

A Stable Fe3O4-Based Hybrid Anodes for High Performance Li-Ion Batteries

There is an increasing demand for high-performance Li-ion batteries especially due to environmental concerns. To meet the high-performance requirements of the Li-ion batteries, conversion-type anodes stand out with their capacities. The crystal structure of magnetite (Fe3O4) benefits from its empty interstitial sites which hinders volume changes during the insertion and extraction of lithium ions. Combined with its high theoretical lithium storage capacity and abundance, Fe3O4 has great potential as an alternative anode. Yet in its practical use, the material suffers from severe capacity degradation, mainly due to the formation of a passive metallic iron layer on the electrode [1]. Another suggested mechanism responsible for the deterioration of the performance is the formation of electrochemically inactive FeO-based side products upon delithiation process [2].In this study, we utilize reduced graphene oxide (rGO) as a substrate for the ultrafine Fe3O4 nanoparticles to form a two-dimensional hybrid material with improved characteristics. Under a mild hydrothermal condition, nanoparticles were deposited by a simple redox process in an interconnected porous network of graphene. Graphene aids in improving the Fe3O4 performance not only by reducing the charge transfer resistance, buffering the volume change induced stresses and facilitating the ion transport but also by forming an effective interface with the delocalized electrons of Fe3O4 to further result in the increase of battery capacitance by the interfacial conjugation mechanism, as confirmed by in-situ EIS measurements. The Fe3O4 particles have been effectively stabilized on the rGO surface, becoming less prone to agglomeration during cycling. Consequently, the deliverable specific capacity of the hybrid material was gradually improved upon extended cycling, reaching from 1500 mAh/g up to 2200 mAh/g at 0.5 A/g at the end of 100 cycles of operation. The increase of the specific capacity during the extended cycling was attributed to the chemical and structural changes of the electrode material evaluated by TEM and ex-situ EELS measurements. It was confirmed that the particle size is greatly reduced to 1-2 nm scale, improving the lithium-ion diffusion kinetics by the increased surface area and reversibility of the redox reaction upon graphene contribution. Moreover, the aged cells were observed to still deliver around 1100 mAh/g capacity upon more than 250 times cycling at 1 A/g, indicating the great potential of the ultrafine Fe3O4 decorated reduced graphene hybrids as superior performance Li-ion battery anode materials.

Synergistic Antioxidant and Preservative Potential of Tomato Extract–Magnetic Iron Oxide Nanoparticles in Bio-Coating and Food Applications

This study details the synthesis of tomato extract–magnetic iron oxide nanoparticles (TEx-MIONPs), focusing on the antioxidant capacity and food preservation applications. Utilizing key reagents, including 98% iron (III) chloride hexahydrate, a controlled process yielded TEx-MIONPs. The characterization involved X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and Fourier-transform infrared spectroscopy (FTIR). XRD analysis revealed a predominant cubic magnetite structure. TEM and SEM depicted diverse morphologies, such as ultrasmall cubic and quasi-spherical structures. FTIR spectroscopy confirmed Fe–O bonds in a mixed phase of Fe2O3 and Fe3O4. Antioxidant activity assessment showcased the potent scavenging effects of TEx and TEx-MIONPs against DPPH free radicals, with 100% inhibition after 20 min and an IC50 of about 137 µg/mL, respectively. Furthermore, TEx-MIONPs, when stabilized with banana-based bioplastic and utilized as nanocoating preservation materials, demonstrated efficacy in grape preservation by exhibiting a lower weight loss rate compared to the control group over six days. Specifically, the weight loss rate for preserved grapes was 28.6% on day 6, contrasting with 34.6% for the control. This pioneering study amalgamates the natural antioxidant properties of tomatoes with the enhanced characteristics of magnetic iron oxide nanoparticles, offering sustainable solutions for food preservation and nanopackaging. Ongoing research aims to refine the experimental conditions and explore the broader applications of TEx-MIONPs in various contexts.

New insights into the adsorptive characteristics of trihalomethane precursors from surface water using magnetic powdered activated carbon

Powdered activated carbon (PAC) can effectively eliminate dissolved organic matter (DOM) as a precursor of trihalomethane (THM), but its application has raised concerns regarding its separation and the overelevated formation of brominate THM species in treated water after chlorination. Although magnetic PAC (Mag-PAC) has been proposed as an easily separable adsorbent for water treatment, its removal by Mag-PAC remains unknown. In this study, a novel Mag-PAC adsorbent for removing DOM and controlling THM formation from surface water was fabricated, evaluated using batch experiments, and compared with PAC. Our results found that Mag-PAC blended the advantages of PAC and magnetic particles, having an efficient removal performance toward DOM with an adsorption capacity of 2.84–3.69 mg-C/g and good magnetic separability of 10.15 emu/g. The iron oxide coating on the carbon matrices was predominantly distributed in the presence of crystalline goethite and magnetite structures. Chemisorption was the dominant mechanism of DOM adsorption by Mag-PAC. The sorption rate of DOM was influenced by the impregnation of iron oxide, but such impregnation did not significantly affect the DOM adsorption capacity. Aromatic DOM, humic-acid and fulvic-acid like compounds were efficiently adsorbed by the Mag-PAC. Compared with PAC, Mag-PAC exhibited a higher reduction in lifetime cancer risks from THMs through the ingestion pathway by decreasing the formation potential of trichloromethane and bromodichloromethane, which generated high unit risks among various THM species. These findings highlight the potential of Mag-PAC as an effective sorbent for DOM removal to control the formation of THM in surface water.

Facilely prepared heterogeneous Fenton catalyst Fe(Fe0.69Al0.31)2O4@C for catalytic wet peroxide oxidation of ciprofloxacin in batch and continuous reactor: Reaction intermediates and toxicity evaluation

Herein, by using a simple co-precipitation method Al-doped magnetite spinel nanoparticle encapsulated in the carbon matrix Fe(Fe0.69Al0.31)2O4@C was synthesised and its catalytic activity was examined as a heterogeneous Fenton catalyst towards the catalytic wet peroxide oxidation (CWPO) of antibiotic pollutant 20 ppm ciprofloxacin (CIP) in batch and continuous reactors. Under the optimized conditions, 0.5 g·L-1 Fe(Fe0.69Al0.31)2O4@C in batch reactor mineralized 51 % of CIP was achieved within 180 min at 50 °C and pH 3 by utilizing 1.2 mM or 4S H2O2 (S = stoichiometry; 47 mol H2O2:1 mol CIP) which is significantly less concentration compared to other heterogeneous Fenton catalysts. Impressive long-lasting catalytic activity was demonstrated in the up-flow fixed bed reactor, for 110 h with 44 % TOC removal and less than 1 ppm Fe leaching in the effluent water. Kinetic studies on the rate of decomposition of H2O2 revealed that Fe(Fe0.69Al0.31)2O4@C effectively decomposed the H2O2 like the homogeneous Fenton catalyst. The XPS results confirmed the influence of Al on iron ions in the magnetite structure through a substantial shift in higher binding energy for Fe3+ and introduced a more electropositive character on the Fe3+(δ+) that successively expedites the kinetically slow Fe3+ reduction reaction with H2O2 to produce HOO•. The π electrons of the graphitic carbon facilitate the electron transfer between the carbon matrix and Fe(Fe0.69Al0.31)2O4 nanoparticles to enhance the CIP degradation. The acute toxicity assessment studies validated the non-toxic nature of the effluent water obtained from batch and continuous reactors. A degradation pathway was proposed based on the eleven intermediate products identified using LC-HRMS analysis.

Innovative magnetic catalyst facilitates biodiesel production via transesterification of sunflower and waste cooking oils

ABSTRACT The surging global demand for biofuels, precipitated by concerns regarding fossil fuel limitations and their associated environmental consequences has thrust biodiesel into the spotlight as a promising alternative of energy source. In this research endeavor, a novel magnetic catalyst, denoted as K compounds/Fe3O4, was developed by incorporating potassium into the magnetite structure via sol–gel method. This catalyst was applied in the transesterification reaction to convert sunflower and waste cooking oils to biodiesel. It was found that the most effective catalyst for biodiesel production was synthesized by using potassium nitrate at a concentration of 1 M and calcination temperature of 550°C in the catalyst preparation stage. The K compounds/Fe3O4 catalyst was characterized by XRD, XRF, FTIR, SEM, ASAP, and VSM techniques. SEM images demonstrated the porous structure of the catalyst. The GC-mass analysis confirmed the formation of fatty acid methyl esters. The effects of the operating conditions including reactor temperature (55 to 75°C), catalyst dosage (2.5 to 12.5 wt.%), methanol to oil molar ratio (9:1 to 18:1), time (4 to 14 h) were investigated. The best operating conditions were selected inclusive of temperature 65°C, catalyst dosage 5 wt.%, methanol-to-oil ratio 12:1, and time 8 h, and at these operating conditions, biodiesel production efficiencies of 96.28% and 84.05% were obtained for sunflower and waste cooking oils, respectively. The reusability and regeneration of the K compounds/Fe3O4 were studied for five cycles.

Pb diffusion in magnetite: Dating magnetite crystallization and the timing of remanent magnetization in banded iron formation

The ferrimagnetic mineral magnetite (Fe3O4) is abundant in banded iron formation (BIFs), and has the potential to provide UPb or PbPb age information on these rocks because it incorporates small amounts of U during growth. Combined with age measurements, paleomagnetic studies of BIF magnetites may also yield insight into the history of Earth's magnetic field and its relationship to early evolution of Earth's interior and atmosphere.Reliable magnetite ages utilizing Pb isotopes require knowledge of Pb diffusion in the magnetite structure. For this reason, we undertook an experimental investigation of Pb diffusion in magnetite by diffusing Pb2+ ions into pre-polished slabs of natural magnetite oriented parallel to {001} or {111}. A mixture of PbSO4 and Fe2O3 was used as a surface powder source to supply Pb2+ diffusant at the sample surface and at the same time buffer the oxygen fugacity of the system at magnetite-hematite (MH)—a typical fO2 for banded iron formations (BIFs) due to the common presence of both iron oxides (and where Pb2+ is stable relative to other Pb valence states). Diffusion experiments spanned temperatures of 500–675 °C and durations of 75 to 2035 h. Following each experiment, in-diffused Pb was depth-profiled using Rutherford backscattering spectroscopy (RBS) and Pb diffusivities were calculated from the profiles using an infinite half-space diffusion model. The following diffusion law for Pb2+ in magnetite is based upon 12 independent diffusivity measurements:DPb (m2·s−1) = (9 × 10−17 m2·s−1) exp.(−98,000 J·mol−1)/RT)where the uncertainties in the pre-exponential constant and activation energy are ±6% and ± 15%, respectively.Pb diffusion in magnetite over the temperature range of our study is orders of magnitude slower than projected for other divalent cations based on down-temperature extrapolation of previously measured diffusion laws (e.g., for Mn2+, Fe2+, Co2+, and Ni2+). This finding is encouraging in terms of the potential suitability of magnetite for UPb age determinations of BIFs and other magnetite-bearing rocks. Indeed, classical Dodson closure temperatures well above 500 °C are not unrealistic in cases where magnetite crystals having large diffusion domains (e.g., >100 μm in radius) are cooled relatively rapidly (e.g., at 100 °C/MYr). This is of particular significance for paleomagnetic studies, since the Curie temperature of magnetite is 580 °C and therefore the age of magnetization in magnetite-bearing rocks may be directly dated. However, slow cooling of magnetites having small diffusion domains can lead to Pb loss at temperatures of 200 °C or lower. Pb mobilization is evaluated for various time-temperature scenarios that involve both heating and cooling as well as “closed-loop” time-temperature paths. We conclude that UPb or PbPb age determinations of BIF magnetites are potentially reliable, but isotopic results should be assessed in concert with knowledge of the thermal history of the host rock and the effective grain size of the magnetites.