Stoichiometric Magnetite Research Articles

Peak-ring magnetism: Rock and mineral magnetic properties of the Chicxulub impact crater

The Chicxulub impact event at ca. 66 Ma left in its wake the only complex crater on Earth with a preserved peak ring, characterized by a well-developed magnetic anomaly low. To date, little is known about its magnetic properties. The joint Integrated Ocean Drilling Program (IODP) and International Continental Scientific Drilling Program (ICDP) Expedition 364 drill core M0077A revealed that the peak ring consists of uplifted and strongly deformed granitoid basement rocks overlain by a 130-m-thick impact melt and suevite layer. Pre- and postimpact hydrothermal systems affected this basement with maximum temperatures up to 450 °C. We used microscopy, mineral chemistry, temperature-dependent magnetic susceptibility, and hysteresis properties to characterize the magnetic mineralogy of pre-, syn-, and postimpact rocks. Compared to its amount of pure, stoichiometric shocked magnetite, the granitoid basement shows low magnetic susceptibility, which is in line with earlier experimental studies indicating that shock reduces magnetic susceptibility. Cation-substituted magnetite with varying compositions in the melt rocks carries a higher induced and remanent magnetization compared to the basement. In the granitoid basement, magnetite was partially oxidized to hematite by a pre-impact hydrothermal event, but at lithological contacts with high-temperature impact melt rock, this hematite was locally retransformed back to magnetite. Elsewhere in the granitoid basement, the temperature reached in the hydrothermal system was too low for hematite retransformation. It was also too low to anneal all the lattice defects in the shocked magnetite, which likely occurs above 540 °C. The presence of shocked magnetite in the granitoid basement well explains the magnetic anomaly low due to its unusually low induced magnetization.

The Holy Cross Mountains (Poland) terranes palaeoposition and depositional environment in Silurian—new insights from rock magnetic studies

SUMMARY The Holy Cross Mountains (HCM) in Poland, is an isolated natural outcrop of Palaeozoic rocks located within the Trans-European Suture Zone, a tectonic collage of continental terranes adjacent to the Tornquist margin of the Baltica. This uniqueness made the HCM a target for palaeogeographic research. Based on the facies differences, the HCM had been divided into two major units, the southern (the Kielce Unit) and northern (the Łysogóry Unit) part (SHCM and NHCM, respectively). Their position in relation to each other and the Baltica continent during Silurian times is still a matter of discussion, whether both parts of the HCM were separated terranes located along the Baltica margin or they shared in common palaeogeographic history. Here, we present the results of comprehensive rock magnetic measurements applied as a tool to interpret palaeoenvironmental conditions during deposition and burial and therefore allow discussion about the terranes’ relative position. To recognize the magnetic mineral composition and texture of studied Silurian graptolitic shales several rock magnetic measurements were conducted including low-temperature Saturated Isothermal Remanent Magnetization, thermal demagnetization of three-component IRM and hysteresis measurements, as well as anisotropy of magnetic susceptibility (AMS). The sampled rocks come from both units of the HCM. In all analysed samples we found single domain (SD) stoichiometric magnetite of mostly diagenetic (i.e. post-depositional) origin and goethite resulting likely from weathering. In turn, detrital magnetite, even if observed in previously investigated Silurian rocks from the Baltica margin, was not identified in this study, what we attribute to dissolution during diagenesis in the deep-water environment. Solely in the NHCM, SD hematite and maghemite grains were observed, which we interpret as detrital in origin. These grains have been preserved in the suboxic environment of the NHCM sub-basin bottom waters due to their resistance to dissolution in marine waters. Considering the deposition conditions (oxygenation of the near-bottom zone) rather similar for both HCM parts, we associate the presence of aeolian hematite grains solely in the NHCM rocks with a more proximal position of the NHCM than the SHCM in relation to the Baltica continent during late Llandovery (Silurian). This conclusion agrees with some existing palaeogeographic models. In addition to petromagnetic studies focused on the analysis of ferromagnets, AMS measurements were also carried out. The results indicate that the magnetic susceptibility is mainly governed by paramagnetic minerals, mostly phyllosilicates with small ferromagnetic contributions. Oblate AMS ellipsoid and distinct bedding parallel foliation indicate prevailing sedimentary-compactional alignment. Observed magnetic lineation of tectonic origin resulting from weak strain is related presumably to Variscian deformations.

Effect of Stoichiometry on Nanomagnetite Sulfidation.

Magnetite (Mt) has long been regarded as a stable phase with a low reactivity toward dissolved sulfide, but natural Mt with varying stoichiometries (the structural Fe(II)/Fe(III) ratio, xstru) might exhibit distinct reactivities in sulfidation. How Mt stoichiometry affects its sulfidation processes and products remains unknown. Here, we demonstrate that xstru is a master variable controlling the rates and extents of sulfide oxidation by magnetite nanoparticles (11 ± 2 nm). At pH = 7.0-8.0 and the initial Fe/S molar ratio of 10-50, the partially oxidized magnetite (xstru = 0.19-0.43) can oxidize dissolved sulfide to elemental sulfur (S0), but only surface adsorption of sulfide, without interfacial electron transfer (IET), occurs on the nearly stoichiometric magnetite (xstru = 0.47). The higher initial rate and extent of sulfide oxidation and S0 production are observed with the more oxidized magnetite that has the higher electron-accepting capability from surface-complexed sulfide (S(-II)(s)). The FeS clusters formed from magnetite sulfidation can be oxidized by the most oxidized magnetite with xstru = 0.19 but not by other magnetite particles. A linear relationship between the Gibbs free energy of reaction and the surface area-normalized initial rate of sulfide oxidation is observed in all experiments under the different conditions, suggesting the S(-II)(s)-magnetite IET dominates magnetite sulfidation at high Fe/S molar ratios and near-neutral pH.

Investigation of magnetite–Co interactions: from environmentally relevant trace Co levels to core–shell Fe3O4@Co(OH)2 nanoparticles with magnetic applications

Three different Co(ii) species are identified at the surface of stoichiometric magnetite (Fe(ii)/Fe(iii) = 0.5) by experiments, modeling, X-ray absorption spectroscopy, and X-ray magnetic circular dichroism. This affects the fate of Co, and the magnetic properties of the nanoparticles.

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.

Paleomagnetic study of impactites from the Karla impact structure suggests protracted postimpact hydrothermalism

AbstractWe present a paleomagnetic study of the ~10 km diameter Karla impact structure in Russia. We sampled the target carbonate rocks, and a yet undocumented fragmental melt‐bearing lithic breccia layer. This impact breccia, which contains carbonate melt, is enriched in stoichiometric magnetite by a factor of ~15 compared to the target lithologies, and carries a stable natural remanent magnetization. The weak remanent magnetization and the presence of both normal and reverse polarities down to the centimeter scale indicate that the breccia does not carry a thermoremanent magnetization (TRM), but rather a chemical remanent magnetization (CRM). The presence of stoichiometric magnetite and the absence of TRM suggest that the magnetite was formed during relatively low‐temperature postimpact hydrothermalism that affected the porous impact breccia layer. During this process, the breccia acquired a CRM. The paleomagnetic direction is compatible with a Cenozoic age for the impact event, but cannot bring more precise constraint on the age because of the stable position of the Eurasian plate over the last 60 Myr. However, the presence of both polarities indicates that mild hydrothermalism took place over a period of time long enough to span at least one reversal of the geomagnetic field, that is, over a time scale of the order of 100 kyr. This confirms that protracted hydrothermal systems associated with impact craters are long lived, even in relatively small craters such as Karla, and are key features of the geologic and environmental effects of impacts on Earth.

Amino-Functionalized Fe3O4@SiO2 Core-Shell Magnetic Nanoparticles for Dye Adsorption.

Fe3O4@SiO2 core-shell nanoparticles (NPs) were synthesized with the co-precipitation method and functionalized with NH2 amino-groups. The nanoparticles were characterized by X-ray, FT-IR spectroscopy, transmission electron microscopy, selected area electron diffraction, and vibrating sample magnetometry. The magnetic core of all the nanoparticles was shown to be nanocrystalline with the crystal parameters corresponding only to the Fe3O4 phase covered with a homogeneous amorphous silica (SiO2) shell of about 6 nm in thickness. The FT-IR spectra confirmed the appearance of chemical bonds at amino functionalization. The magnetic measurements revealed unusually high saturation magnetization of the initial Fe3O4 nanoparticles, which was presumably associated with the deviations in the Fe ion distribution between the tetrahedral and octahedral positions in the nanocrystals as compared to the bulk stoichiometric magnetite. The fluorescent spectrum of eosin Y-doped NPs dispersed in water solution was obtained and a red shift and line broadening (in comparison with the dye molecules being free in water) were revealed and explained. Most attention was paid to the adsorption properties of the nanoparticles with respect to three dyes: methylene blue, Congo red, and eosin Y. The kinetic data showed that the adsorption processes were associated with the pseudo-second order mechanism for all three dyes. The equilibrium data were more compatible with the Langmuir isotherm and the maximum adsorption capacity was reached for Congo red.

Technogenic magnetic particles from steel metallurgy and iron mining in topsoil: Indicative characteristic by magnetic parameters and Mössbauer spectra

Technogenic magnetic particles (TMPs), produced during various industrial processes, are released into the atmosphere as dust and get deposited on the surrounding topsoil. The mineralogical and structural differences of TMPs produced in different technological processes should be reflected in their magnetic properties and therefore should be indicative for industrial pollution sources. The goal of this study was to characterize the TMPs by novel methodological approach, based on combination of magnetic methods and Mössbauer spectroscopy to indicate parameters that are discriminative enough to be used as environmental indicators for iron metallurgy, steel production, and iron mining. We collected the topsoil samples in the vicinity of 4 European iron- and steelworks, located in three different countries (Poland, Norway, and Czech Republic) and operating for minimum 40 years. We sampled also topsoil close to the opencast iron mine, iron ore dressing plant, and over strongly magnetic natural background. Analysis of the hyperfine parameters of the Mössbauer spectra revealed that TMPs are “magnetite-like” minerals with low stoichiometry. It is indicated by ratio of iron ions contributions in B sites (octahedral) and A sites (tetrahedral) in magnetite spinel structure, which is much lower than 2.0 (theoretical value for stoichiometric magnetite). The characteristic feature of TMPs collected from the vicinity of old metallurgical plants (>180 years) was the high contribution of surface components probably related to the surface oxidation/maghemitization. We found that, TMPs can be easily differentiated from geogenic magnetite based on their magnetic parameters. The TMP produced by the iron and steel metallurgy had relatively narrow ranges of magnetic parameters (saturation ratio Mrs/Ms, <0.15, coercivity ratio Bcr/Bc 2.5–6.0 and saturation to susceptibility ratio Mrs/χ 3.5–15). These magnetic parameters may be indicative for TMPs emitted by these pollution sources and helpful in the study of historical pollution sources in topsoil in urban and post-industrial areas.

Study on magnetite oxidation using synchrotron X–ray diffraction and X–ray absorption spectroscopy: Vacancy ordering transition in maghemite (γ–Fe&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;3&lt;/sub&gt;)

The oxidation process from magnetite to hematite through maghemite was investigated by X–ray diffraction (XRD) and X–ray absorption spectroscopic techniques. The XRD pattern of magnetite heated at 100 °C for 3 h showed small reflections of maghemite with partially ordered distribution of vacancy (space group P4132 or P4332). Thereafter, the XRD pattern of magnetite heated at 250 °C for 3 h exhibited extra reflections corresponding to the tetragonal maghemite with fully ordered distribution of vacancy (space group P41212 or P43212). Diffraction peaks of hematite occurred from the magnetite heated at 250 °C, in which maghemite and hematite coexisted with magnetite. Diffraction peaks of magnetite subsequently disappeared at 300 °C. Instead, maghemite and hematite dominated the XRD pattern, but the amount of maghemite reduced from 300 °C. The maghemite completely disappeared at 500 °C, and hematite finally dominated the XRD pattern. Rietveld fitting results clearly showed that the a lattice parameter and site occupancy factor of Fe at the octahedral site continuously decreased at the temperatures from 25 to 300 °C. The X–ray absorption near edge structure (XANES) result showed that the Fe3+/ΣFe increased up to 300 °C and remained constant until 500 °C, indicating that Fe2+ in oxidized magnetite was completely oxidized to Fe3+ at 300 °C. Furthermore, the intensities of radial structure function (RSF) peaks at 1.7 and 3.1 Å corresponding to the Fe–O bonds in octahedral site and the Fe–Fe interaction between the octahedral sites reduced continuously from 25 to 300 °C. The fitting results of the first shells indicated that the coordination number and site occupancy factor at the octahedral site continuously decreased at the temperature range from 25 to 300 °C, which were approximately consistent with those of Rietveld fitting analysis. The a lattice parameter of the oxidized magnetite displayed a linear trend between stoichiometric magnetite and stoichiometric maghemite with a relationship of a = 0.0985x + 8.3397 (x = Fe2+/Fe3+). It was clearly confirmed that during the magnetite oxidation, Fe was continuously removed from the octahedral sites, which resulted in the formation of maghemite with partially ordered distribution of vacancy. Just after magnetite oxidation was completed, the vacancy ordering further progressed by the diffusion of Fe3+ within the structure, leading to the formation of maghemite with fully ordered distribution of vacancy.

High-coercivity magnetic minerals in archaeological baked clay and bricks

SUMMARYThe thorough understanding of magnetic mineralogy is a prerequisite of any successful palaeomagnetic or archaeomagnetic study. Magnetic minerals in archaeological ceramics and baked clay may be inherited from the parent material or, more frequently, formed during the firing process. The resulting magnetic mineralogy may be complex, including ferrimagnetic phases not commonly encountered in rocks. Towards this end, we carried out a detailed rock magnetic study on a representative collection of archaeological ceramics (baked clay from combustion structures and bricks) from Bulgaria and Russia. Experiments included measurement of isothermal remanence acquisition and demagnetization as a function of temperature between 20 and &amp;gt;600 °C. For selected samples, low-temperature measurements of saturation remanence and initial magnetic susceptibility between 1.8 and 300 K have been carried out. All studied samples contain a magnetically soft mineral identified as maghemite probably substituted by Ti, Mn and/or Al. Stoichiometric magnetite has never been observed, as evidenced by the absence of the Verwey phase transition. In addition, one or two magnetically hard mineral phases have been detected, differing sharply in their respective unblocking temperatures. One of these unblocking between 540 and 620 °C is believed to be substituted hematite. Another phase unblocks at much lower temperatures, between 140 and 240 °C, and its magnetic properties correspond to an enigmatic high coercivity, stable, low-unblocking temperature (HCSLT) phase reported earlier. In a few samples, high- and low unblocking temperature, magnetically hard phases appear to coexist; in the others, the HCSLT phase is the only magnetically hard mineral present.

К ВОПРОСУ О ВЛИЯНИИ ДИСПЕРСНЫХ ОКСИДОВ ЖЕЛЕЗА НА ТЕРМОДИНАМИЧЕСКОЕ СОСТОЯНИЕ ТЖМТ В НЕИЗОТЕРМИЧЕСКИХ УСЛОВИЯХ

In the initial period of HLMT development, it was shown that ensuring the corrosion resistance of structural steels is associated with ensuring a certain oxygen regime of the coolant. To control it, oxygen TDA sensors were created later. It was assumed that the oxygen activity in HLMC in different temperature zones of the circulation loop obeys the so-called "isoconcentration" distribution, which, when formally recalculated the measured oxygen TDA values, gives a constant concentration value at different temperatures. However, later it turned out that such a distribution of TDA is not always realized. The observed character of deviations could be explained by the influence of iron impurity. At the same time, quantitative estimates of this effect were carried out under the assumption of the formation of stoichiometric magnetite under conditions of its thermodynamic stability in the entire range of temperatures and concentrations of the initial components. The limitation of this approach lies, first of all, in the fact that it does not take into account the processes of dissociation of solid-phase iron oxides, which can occur in the hot zone when appropriate conditions are created, which can be realized with a decrease in the content of dispersed iron oxides. The importance of taking this factor into account is due to the fact that, during corrosion testing of steels in HLMC, the processes of dissociation of magnetite are actually observed in practice. Within the framework of this work, a computational method for assessing the effect of filtration processes on the thermodynamic state of HLMC has been developed. Quantitative estimates of the effect of the content of dispersed oxides in HLMC on the thermodynamic state of the coolant under non-isothermal conditions in iso-concentration and non-iso-concentration modes have been obtained and which can be used in calculation codes and comparison of experimental results with calculations.

The thermal maturity of sedimentary basins as revealed by magnetic mineralogy

AbstractThe thermal evolution of sedimentary basins is usually constrained by maturity data, which is interpreted from Rock‐Eval pyrolysis and vitrinite reflectance analytical results on field or boreholes samples. However, some thermal evolution models may be inaccurate due to the use of elevated maturities measured in samples collected within an undetected metamorphic contact aureole surrounding a magmatic intrusion. In this context, we investigate the maturity and magnetic mineralogy of 16 claystone samples from Disko‐Svartenhuk Basin, part of the SE Baffin Bay volcanic margin. Samples were collected within thermal contact metamorphic aureoles near magma intrusions, as well as equivalent reference samples not affected by intrusions. Rock‐Eval pyrolysis (Tmax), and vitrinite reflectance (Ro) analysis were performed to assess the thermal maturity, which lies in the oil window when 435°C ≤ Tmax ≤ 470°C and 0.6%–0.7% ≤ Ro ≤ 1.3%. In addition, we performed low‐ (&lt;300K) and high‐temperature (&gt;300K) investigations of isothermal remanent magnetization to assess the magnetic mineralogy of the selected samples. The maturity results (0.37% ≤ Ro ≤ 2%, 22°C ≤ Tmax ≤ 604°C) show a predominance of immature to early mature Type III organic matter, but do not reliably identify the contact aureole when compared to the reference samples. The magnetic assemblage of the immature samples consists of iron sulphide (greigite), goethite and oxidized or non‐stoichiometric magnetite. The magnetic assemblage of the early mature to mature samples consists of stoichiometric magnetite and fine‐grained pyrrhotite (&lt;1 μm). These results document the disappearance of the iron sulphide (greigite) and increase in content of magnetite during normal burial. On the other hand, magnetite is interpreted to be the dominant magnetic mineral inside the contact aureole surrounding dyke/sill intrusions where palaeotemperatures indicate mature to over‐mature state. Interestingly, the iron sulphide (greigite) is still detected in the contact aureole where palaeotemperatures exceeded 130°C. Therefore, the magnetic mineralogy is a sensitive method that can characterize normal burial history, as well as identify hidden metamorphic contact aureoles where the iron sulphide greigite is present at temperatures beyond its stability field.

Crystallographic Changes Accompanying the Verwey Transition in a Magnetite from Steatite

The crystallographic structural analysis of the magnetite of a steatite rock at 298 K, (saturation magnetization, σ = 95.0 J T-1 kg-1) showed two cubic networks and, below Verwey temperature (TV ca.120 K) a monoclinic structure, basing on their cell dimensions and different transitional behaviors when reducing the temperature. A monoclinic structure was identified from their cell dimensions and different transition behaviors when reducing the temperature. The average chemical formula of this almost stoichiometric magnetite was deduced from the chemical analysis, 298 K-Mossbauer and the structural refinement. The Rietveld fitting of the 298 K X-ray pattern is Fe3+Fe0.953+Fe0.882+Cr0.043+Al0.043+Mg0.052+Ni0.022+⊗0.02O4, where [ ] and { } stand for cations in tetrahedral and octahedral coordination symmetries, respectively. The crystallographic structure below TV in this magnetite was observed from synchrotron X-ray diffraction data (XRD), collected at 15 K. It was identified three structures: two cubic (space group, Fd3m), with significantly different lattice parameters, and one monoclinic (P2/c).

Shell-mediated control of surface chemistry of highly stoichiometric magnetite nanoparticles.

Magnetite (Fe3O4) nanoparticles are one of the most studied nanomaterials for different nanotechnological and biomedical applications. However, Fe3O4 nanomaterials gradually oxidize to maghemite (γ-Fe2O3) under conventional environmental conditions leading to changes in their functional properties that determine their performance in many applications. Here we propose a novel strategy to control the surface chemistry of monodisperse 12 nm magnetite nanoparticles by means of a 3 nm-thick Zn-ferrite epitaxial coating in core/shell nanostructures. We have carried out a combined Mössbauer spectroscopy, dc magnetometry, X-ray photoelectron spectroscopy and spatially resolved electron energy loss spectroscopy study on iron oxide and Fe3O4/Zn0.6Fe2.4O4 core/shell nanoparticles aged under ambient conditions for 6 months. Our results reveal that while the aged iron oxide nanoparticles consist of a mixture of γ-Fe2O3 and Fe3O4, the Zn-ferrite-coating preserves a highly stoichiometric Fe3O4 core. Therefore, the aged core/shell nanoparticles present a sharp Verwey transition, an increased saturation magnetization and the possibility of tuning the effective anisotropy through exchange-coupling at the core/shell interface. The inhibition of the oxidation of the Fe3O4 cores can be accounted for in terms of the chemical nature of the shell layer and an epitaxial crystal symmetry matching between the core and the shell.

Zn-substituted iron oxide nanoparticles from thermal decomposition and their thermally treated derivatives for magnetic solid-phase extraction

Controlled thermal decomposition of zinc and iron acetylacetonates in the presence of oleic acid and oleylamine provided surfactant-capped magnetic nanoparticles with narrow size distribution and the mean diameter of ≈15 nm. The combined study by XRD, XRF and Mössbauer spectroscopy revealed three important features of the as-prepared nanoparticles. First, the actual ratio of Zn:Fe was considerably lower in the product compared to the initial ratio of metal precursors (0.14 vs. 0.50). Second, a pure stoichiometric Zn-doped magnetite system, specifically of the composition Zn0.37Fe2.63O4, with no signatures of oxidation to maghemite was formed. Third, Zn2+ ions were distributed at both tetrahedral and octahedral sites, and the observed preference for the tetrahedral site was only twice as high as for theoctahedral site. Furthermore, carbon-coated nanoparticles were achieved by pyrolysis of the surfactants at 500 °C, providing a potential sorbent of organic pollutants with room-temperature magnetization as high as 79.1 emu g−1 and very low carbon content of 5 wt%. The thermal treatment, albeit intended only for the carbonization of surfactants, did alter also the non-equilibrium cation distribution toward the equilibrium one by the relocation of a considerable fraction of the octahedrally coordinated Zn2+ to the tetrahedral sites. Preliminary experiments with magnetic solid-phase extraction of β-estradiol from aqueous solutions evidenced applicability and reusability of the carbon-coated product in the separation of steroid pollutants.

Revisiting the Phase Transition of Magnetite under Pressure

Using a highly stoichiometric magnetite, the pressure-induced phase transitions of Fe3O4 have been revisited here by performing Fe K-edge X-ray absorption and magnetic circular dichroism measurements up to P = 65 GPa at room temperature and 71 GPa at 20 K. We have observed a structural transition at around 27 GPa from magnetite to a high-pressure phase h-Fe3O4 with the loss of the net ordered magnetic moments for both temperatures. The orthorhombic CaTi2O4-type (Bbmm) structure of the high-pressure phase h-Fe3O4 has been determined by combining experimental studies and theoretical simulations of the Fe K-edge X-ray absorption near-edge structure spectra. The long-time discussed pressure induced spin crossover, and inverse to normal spinel structure transitions in Fe3O4 can be deterministically excluded from the present study up to ∼65 GPa.

Domain structure of volcanics’ ferromagnetic grains: A case study of the Saatly ultradeep well, Azerbaijan

Various magnetic properties of magnetic minerals show strong grain-size depen-dence. This dependency occurs because these parameters are influenced by the magnetic grain-size (domain state) of the samples. Natural rocks often contain a mixture of different magnetic minerals with different grain-size (domain states). Thus determination of the domain state is important. The Saatly ultradeep well’s volcanics were used as a research material. In the depth intervals of 3540—8126 m the volcanics had been revealed by the borehole. According to data of the petrographic and microprobe analysis the volcanogenics of the ultradeep borehole is conditionally divided into a two parts: 1) the upper part (an interval of depths of 3540—5500 m); 2) the bottom part (an interval of depths of 5500—8126 m). In the upper part of section according to microprobe analysis of volcanogenic rocks ore grains are presented by two generations: 1) large grain of titanomagnetites (Ti-poor), homogeneous or with a decay structures; 2) small-sized usually well faced grain of practically stoichiometric magnetite. So, homogeneous small-sized grains or fragments of decay large grains (which are strongly changed chemically) can have properties of single-domain particles. Here the ferromagnetic grains (especially in the depth interval 3540—5000 m) are often noted as a pseudo-single domain. In the bottom part of the section the presence of multidomain grains of the Ti-poor titano-magnetite is noted. And since depths of 7000 m the oxidized magnetite is also observed. The pseudo-single-domain grains are fixed much less than in the upper section. And, since a depth mark of 7300 m and deeper, they are absent wholly. In the result of rese-arch it turned out that the ferromagnetic is presented by basically multidomain grains. It should be noted that Lauri—Fuller’s Criterion is not applicable at identification of a domain structure of the complex ensemble of the ferromagnetic grains.

Magnetic, geochemical and granulometric properties of street dust from Warsaw (Poland)

The study presents variations in the magnetic properties and heavy metal concentrations of five granulometric fractions, i.e. 1000–500 μm, 500–250 μm, 250–100 μm, 100–71 μm and <71 μm, for street dust collected at two locations in Warsaw. Combination of grain-size determination, magnetometry, electron microscope observation, mineral composition and chemical analyses was applied as an effective and multidisciplinary approach for the complete characterization of individual fractions of street dust. The magnetic properties of street dust are influenced by its grain size; concentration-dependent magnetic parameters, e.g. magnetic susceptibility, saturation magnetization, saturation remanence and anhysteretic remament magnetization of the finest fraction (d < 0.071 mm) are about three times higher than that of the coarsest fraction (d > 0.5 mm). For all fractions the main magnetic mineral is near stoichiometric magnetite. The dust fractions with grain size <250 μm additionally contain a phase with a Curie point ~770 °C, ascribable to metallic iron. The smallest contribution to the total mass is from the finest size fractions, which contain the highest concentrations of the traffic-related heavy metals. Traffic intensity are well reflected at the two sites studied by the concentration of anthropogenic magnetic particles which are strongly associated with traffic-related heavy metals. Magnetic extracts of the finest dust fraction contain a mixture of spherical magnetic particles and irregular angular particles of iron-oxides with traces of Mg, Al, Na, Ca, K, and Si. Detailed studies preferentially oriented toward to the finest fractions of street dust are a critical issue in terms of potential effects on population health.

A novel hybrid nanoparticle based on Fe3O4/TMAOH/poly(L-co-D,L lactic acid-co-trimethylene carbonate) prepared through the solvent displacement method

TMAOH-dispersed nanoparticles of magnetite were first prepared through the reduction–precipitation of ferric chloride with Na2SO3 and NH4OH. The TMAOH-dispersed (Fe3O4) magnetic nanoparticles were then surface-coated with poly(L-co-D,L lactic acid-co-trimethylene carbonate) (PLDLA-co-TMC) to obtain the corresponding hybrid system (Fe3O4/TMAOH/PLDLA-co-TMC). Samples of so prepared material were analyzed by Fourier-transform infrared spectroscopy (FTIR), powder X-ray diffraction (XRD), magnetization measurements up to 2.5 T, and Mossbauer spectroscopy. Results indicate that this magnetic iron oxide soon after the synthesis is structurally close enough to a typically pure stoichiometric magnetite. FTIR data support clears evidences confirming the efficiency of the solvent displacement method to assure coating the TMAOH-dispersed (Fe3O4) magnetic nanoparticles with the terpolymer while preserves the main chemical structural characteristic of the nanosized magnetite.

The effects of dislocations on crystallographic twins and domain wall motion in magnetite at the Verwey transition

Pure magnetite experiences a first-order phase transition (the Verwey transition) near 120–125 K wherein the mineral’s symmetry changes from cubic to monoclinic. This transformation results in the formation of fine-scale crystallographic twins and is accompanied by a profound change in magnetic properties. The Verwey transition is critical to a variety of applications in environmental magnetism and paleomagnetism because its expression is diagnostic for the presence of stoichiometric (or nearly stoichiometric) magnetite and cycling through the Verwey transition tends to remove the majority of multidomain magnetic remanence. Internal and external stresses demonstrably affect the onset of the Verwey transition. Dislocations create localized internal stress fields and have been cited as a possible source of an altered Verwey transition in deformed samples. To further investigate this behavior, a laboratory-deformed magnetite sample was examined inside a transmission electron microscope as it was cooled through the Verwey transition. Operating the microscope in the Fresnel mode of Lorentz microscopy enabled imaging of the interactions between dislocations, magnetic domain walls, and low-temperature crystallographic twin formation during the phase transition. To relate the observed changes to more readily measurable bulk sample magnetic behavior, low-temperature magnetic measurements were also taken using SQUID magnetometry. This study allows us, for the first time, to observe the Verwey transition in a defect-rich area. Dislocations, and their associated stress fields, impede the development of monoclinic magnetite twin structures during the phase transition and increase the remanence of a magnetite sample after cooling and warming through the Verwey transition.