Magneto-chemical characterisation of Saharan dust deposited on snow in Poland.

Recent research has convincingly shown the advantages of combining environmental magnetism and geochemical analyses for the proxy estimation of anthropogenic pollution due to their atmospheric deposition in local environments. Few studies have also focused on anthropogenic particles deposited on snow. However, papers reporting on Sahara dust particles deposited on snow in central Europe and which involve magnetic methods are missing. To the best of our knowledge, this is the first study investigating the magnetic features of the SDE recorded in snowfall in this part of Europe (i.e. Poland). Our aim was to provide the magnetic characteristics and chemical elemental compositions of a snow horizon containing Saharan dust deposited near the Polish Jakuszyce meteorological station during a snowfall event that occurred from the 1st to the February 7, 2021. Samples of snow with and without Saharan dust were analysed with respect to iron oxide contents (magnetic susceptibility, hysteresis loop, magnetic remanence acquisition) and compared with chemical compositions. Our results revealed the presence of both ferrimagnetic magnetite and antiferromagnetic hematite in the dust-enriched horizon, and the diamagnetic behaviour of the reference layer consisting of 'pure' snow. The samples recorded the presence of geogenic elements such as Al, Fe, Mn, and Ti, anthropogenic elements such as As, Co, Cr, Cu, Ni, Pb, and Zn, and nutrients including Ca and K. The total concentrations of geogenic elements, nutrients, and anthropogenic elements in the snow samples with deposited Saharan dust were, respectively, >3700, >320, and >110 times greater than in the samples without Saharan dust. These findings may serve as reference data for a variety of environmental magnetic studies.

Cationic Polymer-Coated Magnetic Nanoparticles with Antibacterial Properties: Synthesis and In Vitro Characterization.

Uniformly sized magnetite nanoparticles (Dn = 16 nm) were prepared by a thermal decomposition of Fe(III) oleate in octadec-1-ene and stabilized by oleic acid. The particles were coated with Sipomer PAM-200 containing both phosphate and methacrylic groups available for the attachment to the iron oxide and at the same time enabling (co)polymerization of 2-(dimethylamino)ethyl methacrylate and/or 2-tert-butylaminoethyl methacrylate at two molar ratios. The poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) and poly[2-(dimethylamino)ethyl methacrylate-co-2-tert-butylaminoethyl methacrylate] [P(DMAEMA-TBAEMA)] polymers and the particles were characterized by 1H NMR spectroscopy, size-exclusion chromatography, transmission electron microscopy, dynamic light scattering, thermogravimetric analysis, magnetometry, and ATR FTIR and atomic absorption spectroscopy. The antimicrobial effect of cationic polymer-coated magnetite nanoparticles tested on both Escherichia coli and Staphylococcus aureus bacteria was found to be time- and dose-responsive. The P(DMAEMA-TBAEMA)-coated magnetite particles possessed superior biocidal properties compared to those of P(DMAEMA)-coated one.

Quantification of pedogenic particles masked by geogenic magnetic fraction.

Pedogenic magnetic fraction in soils is attributed to fine-grained particles, i.e. superparamagnetic grains. In the case of a strongly magnetic geogenic fraction, pedogenic magnetic contribution is hard to detect. To the best of our knowledge, detailed research into the masking of pedogenic superparamagnetic grains and quantification of this effect has not yet been carried out. The principal aim of our research is to quantify the influence of coarse-grained ferrimagnetic fraction on the detection of the superparamagnetic grains. In order to describe the masking phenomenon, volume and frequency-dependent magnetic susceptibility were determined on a set of laboratory prepared samples composed of natural substances: a diamagnetic quartz matrix, detrital coarse-grained ferrimagnetic crystals from alkaline and ultra-alkaline igneous rocks, and superparamagnetic soil concretions formed in the Haplic Cambisol. Mineralogy, concentration, type and grain size of the tested material were described by parameters of environmental magnetism. The magnetic parameters distinguish both geogenic multidomain and pedogenic superparamagnetic grains. The magnetic signal of the superparamagnetic grains is gradually masked by the increasing proportion of multidomain grains of magnetite/maghemite. The experiment clearly describes the masking effect and brings new insight to studies dealing with strongly magnetic soils of natural and/or highly contaminated origin as a tool for estimation of superparamagnetic pedogenic contribution.

Magnetic Superporous Poly(2-hydroxyethyl methacrylate) Hydrogel Scaffolds for Bone Tissue Engineering.

Magnetic maghemite (γ-Fe2O3) nanoparticles obtained by a coprecipitation of iron chlorides were dispersed in superporous poly(2-hydroxyethyl methacrylate) scaffolds containing continuous pores prepared by the polymerization of 2-hydroxyethyl methacrylate (HEMA) and ethylene dimethacrylate (EDMA) in the presence of ammonium oxalate porogen. The scaffolds were thoroughly characterized by scanning electron microscopy (SEM), vibrating sample magnetometry, FTIR spectroscopy, and mechanical testing in terms of chemical composition, magnetization, and mechanical properties. While the SEM microscopy confirmed that the hydrogels contained communicating pores with a length of ≤2 mm and thickness of ≤400 µm, the SEM/EDX microanalysis documented the presence of γ-Fe2O3 nanoparticles in the polymer matrix. The saturation magnetization of the magnetic hydrogel reached 2.04 Am2/kg, which corresponded to 3.7 wt.% of maghemite in the scaffold; the shape of the hysteresis loop and coercivity parameters suggested the superparamagnetic nature of the hydrogel. The highest toughness and compressive modulus were observed with γ-Fe2O3-loaded PHEMA hydrogels. Finally, the cell seeding experiments with the human SAOS-2 cell line showed a rather mediocre cell colonization on the PHEMA-based hydrogel scaffolds; however, the incorporation of γ-Fe2O3 nanoparticles into the hydrogel improved the cell adhesion significantly. This could make this composite a promising material for bone tissue engineering.

Cerium Oxide-Decorated γ-Fe2O3 Nanoparticles: Design, Synthesis and in vivo Effects on Parameters of Oxidative Stress.

Magnetic γ-Fe2O3/CeOx nanoparticles were obtained by basic coprecipitation/oxidation of iron chlorides with hydrogen peroxide, followed by precipitation of Ce(NO3)3 with ammonia. The appearance of CeOx on the magnetic particle surface was confirmed by X-ray photoelectron spectroscopy (XPS), powder X-ray diffraction (XRD), and elemental analysis; a magnetometer was used to measure the magnetic properties of γ-Fe2O3/CeOx. The relatively high saturation magnetization of the particles (41.1 A·m2/kg) enabled magnetic separation. The surface of γ-Fe2O3/CeOx particles was functionalized with PEG-neridronate of two different molecular weights to ensure colloidal stability and biocompatibility. The ability of the particles to affect oxidative stress in hereditary hypertriglyceridemic (HHTg) rats was tested by biological assay of the liver, kidney cortex, and brain tissues. An improvement was observed in both enzymatic [superoxide dismutase (SOD), catalase (CAT), and glutathione peroxidase (GPx)] and non-enzymatic (reduced (GSH) and oxidized (GSSG) glutathione) levels of antioxidant defense and lipid peroxidation parameters [4-hydroxynonenal (4-HNE) and malondialdehyde (MDA)]. The results corresponded with chemical determination of antioxidant activity based on 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay, proving that in the animal model γ-Fe2O3/CeOx@PEG2,000 nanoparticles effectively scavenged radicals due to the presence of cerium oxide, in turn decreasing oxidative stress. These particles may therefore have the potential to reduce disorders associated with oxidative stress and inflammation.

Antibacterial Silver-Conjugated Magnetic Nanoparticles: Design, Synthesis and Bactericidal Effect.

PURPOSE: The aim was to design and thoroughly characterize monodisperse Fe3O4@SiO2-Ag nanoparticles with strong antibacterial properties, which makes them a candidate for targeting bacterial infections. METHODS: The monodisperse Fe3O4 nanoparticles were prepared by oleic acid-stabilized thermal decomposition of Fe(III) oleate; the particles were coated with silica shell using a water-in-oil reverse microemulsion, involving hydrolysis and condensation of tetramethyl orthosilicate. Resulting Fe3O4@SiO2 particles were modified by (3-mercaptopropyl)trimethoxysilane to introduce 1.1 mmol SH/g. Finally, the Fe3O4@SiO2-SH nanoparticles were decorated with silver nanoclusters formed by reduction of silver nitrate with NaBH4. The particles were analyzed by FTIR, X-ray photoelectron and atomic absorption spectroscopy, dynamic light scattering and vibrating sample magnetometry. The antibacterial activity of the Fe3O4@SiO2 and Fe3O4@SiO2-Ag nanoparticles was tested against Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli bacteria cultivated on Luria agar plates or in Luria broth. RESULTS: The superparamagnetic Fe3O4@SiO2-Ag nanoparticles (21 nm in diameter; saturation magnetization 26 A∙m2/kg) were successfully obtained and characterized. Inhibitory and toxic effects against bacteria were documented by incubation of the Fe3O4@SiO2-Ag nanoparticles with Staphylococcus aureus and Escherichia coli. CONCLUSIONS: The combination of magnetic properties together with bactericidal effects is suitable for the disinfection of medical instruments, water purification, food packaging, etc.

Peroxidase-like activity of magnetic poly(glycidyl methacrylate-co-ethylene dimethacrylate) particles.

Poly(glycidyl methacrylate) (PGMA) is prone to modifications with different functional groups, magnetic fluids or direct coupling with biological molecules. The purpose of this research was to synthesize new magnetically responsive particles with peroxidase-like activity. Poly(glycidyl methacrylate-co-ethylene dimethacrylate) [P(GMA-EDMA)] particles containing carboxyl groups were obtained by emulsifier-free emulsion polymerization and hydrolysis and oxidation of PGMA with KMnO4, resulting in poly(carboxymethyl methacrylate-co-ethylene dimethacrylate) [P(CMMA-EDMA)] particles. Thionine (Th) was also attached to the particles [(P(CMMA-EDMA)-Th] via EDC/NHS chemistry to observe its effect on electron transfer during the oxidation reaction. Finally, the particles were coated with a nitric acid-stabilized ferrofluid in methanol. The resulting magnetic particles were characterized by several methods, including scanning and transmission electron microscopy, X-ray photoelectron spectroscopy, and vibrating sample magnetometry. The effect of EDMA on the P(CMMA-EDMA) particle size and size distribution was investigated; the particle size changed from 300 to 340 nm, and the particles were monodispersed with a saturation magnetization of 11 Am2/kg. Finally, the effects of temperature and pH on the peroxidase-like activity of the magnetic P(CMMA-EDMA) and P(CMMA-EDMA)-Th particles were investigated. The particles, which exhibited a high activity at pH 4-6 and at ∼37 °C, represent a highly sensitive sensor component potentially useful in enzyme-based immunoassays.

Monodisperse magnetic poly(glycidyl methacrylate) microspheres for isolation of autoantibodies with affinity for the 46 kDa form of unconventional Myo1C present in autoimmune patients.

Monodisperse nonmagnetic macroporous poly(glycidyl methacrylate) (PGMA) microspheres were synthesized by multistep swelling polymerization of glycidyl methacrylate, ethylene dimethacrylate and 2-[(methoxycarbonyl)methoxy]ethyl methacrylate (MCMEMA). This was followed (a) by ammonolysis to modify the microspheres with amino groups, and (b) by incorporation of iron oxide (γ-Fe2O3) into the pores to render the particles magnetic. The resulting porous and magnetic microspheres were characterized by scanning and transmission electron microscopy (SEM and TEM), atomic absorption and Fourier transform infrared spectroscopy (AAS and FTIR), elemental analysis, vibrating magnetometry, mercury porosimetry and Brunauer-Emmett-Teller adsorption/desorption isotherms. The microspheres are meso- and macroporous, typically 5 µm in diameter, contain 0.9 mM · g-1 of amino groups and 14 wt.% of iron according to elemental analysis and AAS, respectively. The particles were conjugated to p46/Myo1C protein, a potential biomarker of autoimmune diseases, to isolate specific autoantibodies in the blood of patients suffering from multiple sclerosis (MS). The p46/Myo1C loaded microspheres are shown to enable the preconcentration of minute quantities of specific immunoglobulins prior to their quantification via SDS-PAGE. The immunoglobulin M (IgM) with affinity to Myo1C was detected in MS patients. Graphical abstract Monodisperse magnetic poly(glycidyl methacrylate) microspheres were synthesized, conjugated with 46 kDa form of unconventional Myo1C protein (p46/Myo1C) via carbodiimide (DIC) chemistry, and specific autoantibodies isolated from blood of multiple sclerosis (MS) patients; immunoglobulin M (IgM) level increased in MS patients.

Magnetic mapping of distribution of wood ash used for fertilization of forest soil.

The effect of wood-ash fertilization on forest soils has been assessed mainly through geochemical methods (e.g., content of soil organic matter or nutrients). However, a simple and fast method of determining the distribution of the ash and the extent of affected soil is missing. In this study we present the use of magnetic susceptibility, which is controlled by Fe-oxides, in comparing the fertilized soil in the forest plantation of pine and oak with intact forest soil. Spatial and vertical distribution of magnetic susceptibility was measured in an oak and pine plantation next to stems of young plants, where wood ash was applied as fertilizer. Pattern of the susceptibility distribution was compared with that in non-fertilized part of the plantation as well as with a spot of intact natural forest soil nearby. Our results show that the wood-ash samples contain significant amount of ferrimagnetic magnetite with susceptibility higher than that of typical forest soil. Clear differences were observed between magnetic susceptibility of furrows and ridges. Moreover, the dispersed ash remains practically on the surface, does not penetrate to deeper layers. Finally, our data suggest significant differences in surface values between the pine and oak plants. Based on this study we may conclude that magnetic susceptibility may represent a simple and approximate method of assessing the extent of soil affected by wood-ash.

Magnetoconductive maghemite core/polyaniline shell nanoparticles: Physico-chemical and biological assessment.

Nanoparticles of various compositions are increasingly being used in many areas of medicine. The aim of this study was to develop nanoparticles, which would possess both magnetic and conductive properties and, thus improve their suitability for a wider range of biomedical applications. Namely, it would enable both the particle manipulation and imaging using their magnetic properties and simultaneous stimulation of electro-sensitive cell types using their magnetic properties, which can be used in tissue therapy, engineering and as biosensors. Maghemite (γ-Fe2O3) particles were prepared by the co-precipitation of Fe(2+) and Fe(3+) salts with ammonium hydroxide, followed by the controlled oxidation with NaOCl. The polyaniline (PANI) shell on the γ-Fe2O3 nanoparticles was obtained by the polymerization of aniline hydrochloride with ammonium peroxydisulfate in an aqueous solution of poly(N-vinylpyrrolidone) at two reaction temperatures (0 and 25 °C). The resulting γ-Fe2O3&PANI particles were characterized by both the light and transmission electron microscopies, dynamic light scattering, magnetic measurements, UV-vis and energy dispersive X-ray (EDAX) spectroscopy. The size of the starting γ-Fe2O3 particles was 11 nm, that increased to 25 nm after the modification with PANI. The incubation of both the γ-Fe2O3 and γ-Fe2O3&PANI nanoparticles with the human neuroblastoma derived SH-SY5Y cells for 8 days showed neither significant decrease in the cell viability, nor detectable changes in the cell morphology. This indicates, that the particles have no detectable cytotoxicity in cell culture and represent a promising tool for further use in biomedical applications.

Identification of magnetic particulates in road dust accumulated on roadside snow using magnetic, geochemical and micro-morphological analyses.

The aim of this study is to test the applicability of snow surveying in the collection and detailed characterization of vehicle-derived magnetic particles. Road dust extracted from snow, collected near a busy urban highway and a low traffic road in a rural environment (southern Finland), was studied using magnetic, geochemical and micro-morphological analyses. Significant differences in horizontal distribution of mass specific magnetic susceptibility (χ) were noticed for both roads. Multi-domain (MD) magnetite was identified as the primary magnetic mineral. Scanning electron microscope (SEM) analyses of road dust from both roads revealed: (1) angular-shaped particles (diameter∼-300 µm) mostly composed of Fe, Cr and Ni, derived from circulation of motor vehicles and (2) iron-rich spherules (d∼2-70 µm). Tungsten-rich particles (d<2 µm), derived from tyre stud abrasion were also identified. Additionally, a decreasing trend in χ and selected trace elements was observed with increasing distance from the road edge.

Change of magnetic properties due to fluctuations of hydrocarbon contaminated groundwater in unconsolidated sediments.

Sediments affected by fluctuations of hydrocarbon contaminated groundwater were studied at a former military site. Due to remediation, groundwater table fluctuation (GWTF) extends over approximately one meter. Three cores were collected, penetrating through the GWTF zone. Magnetic parameters, sediment properties and hydrocarbon content were measured. We discovered that magnetic concentration parameters increased towards the top of the GWTF zone. Magnetite is responsible for this enhancement; rock magnetic parameters indicate that the newly formed magnetite is in a single domain rather than a superparamagnetic state. The presence of hydrocarbons is apparently essential for magnetite to form, as there is clearly less magnetic enhancement in the core, which is outside of the strongly contaminated area. From our results we conclude that the top of the fluctuation zone has the most intensive geomicrobiological activity probably responsible for magnetite formation. This finding could be relevant for developing methods for simply and quickly detecting oil spills.

Magnetic anomalies of forest soils in the Upper Silesia-Northern Moravia region.

Previous investigations revealed a strong magnetic anomaly due to soil magnetic enhancement in the industrialized cross-border area of Upper Silesia (Poland) and Northern Moravia (Czech Republic). Since industrial and urban dusts contain magnetic particles, this soil magnetic enhancement is assumed to be of anthropogenic origin, caused by a high concentration of atmospherically deposited magnetic particles, accumulated in topsoil layers. This assumption is proved by investigations of vertical profiles of magnetic susceptibility along a transect crossing the border area of the two countries. The results show that the population of magnetic minerals in the organic horizon is different from that in the mineral horizons. The vertical distribution of magnetic susceptibility and thermomagnetic analysis suggests negligible lithogenic contribution. The observed relationship between magnetic susceptibility and some heavy metals, confirmed by micromorphological observations and microchemical analysis of magnetic particles separated from the organic horizons of forest topsoil, has proved the usefulness of soil magnetometry for pollution study.

Magnetic response of soils and vegetation to heavy metal pollution--a case study.

Fast and cost-effective detection of industrial pollution can significantly promote its ecological, economic, and social assessment. A magnetometric method, used for qualitative determination of anthropogenic contamination, meets these requirements but needs further development in more quantitative terms. It could be used successfully in numerous cases when the heavy metals coexist with strongly magnetic iron oxide particles in the source dust. We present an integrated magnetic and geochemical study that examines the utility of magnetometric techniques for rapid, qualitative detection of metallic pollutants in soils and vegetation. The new aspect of our approach, in comparison with previously published articles on this subject, is the combined investigation (magnetic and geochemical) of both soils and vegetation, thus using an additional medium for employing the magnetometry as a pollution proxy at a site. The study area is a small (approximately 3 km2) region in the suburbs of Sofia (Bulgaria), with the main pollution source being a metallurgical factory. Soil samples have been taken from the topmost 20 cm from private gardens, located at different distances from the factory. Vegetation samples were taken from ryegrass (both leaves and roots) and leaves from two kinds of deciduous trees (maple and acacia). The results show that both vegetation and soils are characterized by enhanced magnetic properties, compared to background material, which is due to the presence of magnetite particles of anthropogenic origin accompanying heavy metal emissions. SEM images and microprobe analyses reveal the presence of a significant amount of particles, containing heavy metals (including iron) in vegetation samples taken close to the main pollution source. Correlation analyses show a statistically significant link (correlation coefficients ranging from 0.6 to 0.7) between magnetic susceptibility and the main heavy metals (Cu, Zn, Pb) in soil samples, indicating that the magnetic susceptibility can provide a proxy method for identifying the relative contribution of industrial pollution in soils and vegetation, that is reliable, inexpensive, and less time-consuming than standard chemical analyses.