EPR evidence for maghemitization of magnetite in a tropical soil

Electron paramagnetic spectroscopy (EPR) was used in combination with standard rock magnetic methods to study magnetic minerals in a tropical soil. The susceptibility and hysteresis measurements showed magnetite grains with a Curie temperature near 850 K as the dominant magnetic remanence carriers in the soil. A minor Ti content in the magnetite was found by energy dispersive X-ray analysis. In order to get insight into the weathering status of the magnetite, different chemical treatments, including oxalate and citrate–bicarbonate–dithionite (CBD) extraction, were applied to the soil samples. The hysteretic properties exhibited no significant differences between the untreated and the CBD or oxalate treated samples. By contrast, the comparison of the EPR spectra revealed a significant broadening of the linewidth (δB) and a shift of the g -values ( g _eff) to lower fields after the CBD treatment. Furthermore, the spectral parameters g _eff and δB exhibited an angular dependence. At low temperature, the CBD treated samples showed a jump in δB between 120 and 100 K, the temperature range characteristic for the Verwey transition in magnetite. The changes in the spectral properties after the CBD treatment, which dissolves ferric oxides, were attributed to the removal of maghemite formed by the oxidation of magnetite, that is, during the maghemitization of the magnetite grains.     

On the superparamagnetic—stable single domain transition for magnetite, and frequency dependence of susceptibility

Sediments and soils often contain superparamagnetic (SP) magnetite or maghemite grains that cause a frequency dependence of low-field susceptibility X _fd which does not exceed 15 per cent/decade of frequency. Present models predict very different volume distributions for samples with the largest observed frequency dependence of susceptibility. While Stephensons' (1971) power-law model predicts most grains to be smaller than the stable single domain (SSD) threshold, the phenomenological model of >Dearing et al . (1996) suggests that most grains are between 10 and 25 nm in diameter. Finally, the recent calculations of Eyre (1997) indicate very broad volume distributions. This study reviews the nature of the superparamagnetic–stable single domain (SP–SSD) transition. The change of AC susceptibilities with grain size (or temperature) at the SP–SSD boundary is more gradual than commonly assumed. When distributions of particle coercivities and volumes are also considered, X _fd values are much smaller than those calculated by Eyre (1997). Nonetheless, X _fd can be larger than 15 per cent, and a larger frequency dependence has indeed been measured for some samples. The question whether the observed limited X _fd of soils and sediments is a result of a broad distribution or of a bimodal distribution, where SP and SSD grains are restricted to a certain relative abundance, can potentially be answered by susceptibility determinations at more than two frequencies and by measurements of the temperature dependence of susceptibility.     

Effects of weathering on single-domain magnetite in Early Pliocene marine marls

Rock magnetic parameters are often used to recognize variations in the original magnetic mineralogy and for normalizing purposes in palaeointensity studies. Incipient weathering, however, is shown to have a profound but partly reversible influence on the rock magnetic properties of the marls of the Early Pliocene Trubi formation in southern Sicily (Italy). The remanence in the marls resides in single-domain (SD) magnetite grains, but the remanent coercive force (H_cr) shows a strong variation and most values observed are anomalously high ( H_cr) range 36–188 mT).
The enhanced coercivities are attributed to stress in the magnetite grains induced by surface oxidation at low temperature. Upon heating to 150 °C a reduction of coercivities occurs that can be explained by a stress reduction as a result of a reduction of Fe^2- gradient due to a higher diffusion rate at elevated temperature. After heating to 150 °C, coercivities are quite uniform throughout the outcrop and the values are characteristic of SD magnetite (H_cr range 30–38 mT). The bulk susceptibility increases by 4–24 per cent, and the isothermal remanent magnetization (IRM) decreases by 5–11 per cent. The increase in anhysteretic remanent magnetization (ARM) is large: 20–242 per cent. The magnitude of the changes is related to the degree of weathering.
Another effect of heating the marl samples to 150 °C is a substantial reduction of the coercivities of the secondary overprint in the natural remanent magnetization. After heating. separation of the secondary and primary components by alternating-field demagnetization is more efficient. The usual difficulties of thermal demagnetization above 300 °C may thus be avoided by a combination of moderate heating to 150 °C and subsequent alternating-field demagnetization.     

The causes of low-temperature demagnetization of remanence in multidomain magnetite

In this paper, the mechanisms of low-temperature demagnetization of remanence in multidomain magnetite are considered. New experimental observations of the behaviour of the saturation isothermal remanence, thermoremanence and partial thermoremanence at low temperatures are presented. The results show that there are two main contributions to this low-temperature demagnetization. The first and predominant contribution (type-1 demagnetization) is due to 'kinematic' domain state reorganization and occurs throughout cooling from room temperature to the Verwey transition, T _v , at 120–124  K. The second contribution arises from the change in anisotropy from cubic to monoclinic at T _v , which changes the overall domain structure of the grain. On warming in zero field, some domain walls will not return to their original positions but will take up a position that leads to a lower net remanence (type-2 demagnetization). In stoichiometric magnetite, demagnetization does not occur at 130  K at the isotropic point, T _k , contrary to some previous predictions. In non-stoichiometric magnetite, the influence of the Verwey transition is greatly reduced, and anomalous behaviour is observed at T _k .     

Review of the low-temperature magnetic properties of magnetite from a rock magnetic perspective

The low-temperature magnetic properties of magnetite are reviewed, and implications for rock magnetism considered. The behaviour of fundamental properties of magnetite at low temperatures near the Verwey transition ( T _v ) are documented, and attention is given to various Verwey transition theories. The low-temperature behaviour of the magnetic energies that control domain structure is reviewed in detail. For the first time in rock magnetic literature, the low-temperature anomaly in spontaneous magnetization ( M _s ) is documented and the differences between the saturation magnetization and M _s near the Verwey transition are discussed. It is argued that the low-temperature behaviour of the magnetocrystalline anisotropy, and in particular the anomaly at T _v , is most likely to affect multidomain remanence during low-temperature cycling. For multidomain crystals it is calculated that the large increase in magnetocrystalline anisotropy intensity and reduction in symmetry on cooling through T _v is likely to reduce the stability of closure domains.     

Coercive force of single crystals of magnetite at low temperatures

The temperature dependence of coercive force H _c was studied on well-characterized and stoichiometric millimetre-sized single crystals of magnetite at a series of 16 temperatures from 300 to 10 K using a SQUID magnetometer. H _c decreases gradually with cooling to the isotropic temperature, T _i = 130 K, where the first magnetocrystalline anisotropy constant K ₁ becomes zero. H _c exhibits a sharp increase at the Verwey transition, T _v = 120 K, where the structure changes from cubic to monoclinic. In crossing the Verwey transition, H _c increases by more than two orders of magnitude, from 20 μT to 2.4 mT, and the shape of the hysteresis loops becomes wasp-waisted.
Observed coercivity between 300 K and 170 K varies with temperature as λ _s / M _s , where λ _s is the magnetostriction constant and M _s is the saturation magnetization, indicating that the coercivity in MD magnetite is controlled mainly by internal stress associated with dislocations or other crystal defects. It seems likely that the stable single-domain-like magnetic memory observed in large MD magnetite crystals is due to magnetoelastically pinned domain walls. The discontinuous change in H _c at the Verwey transition is controlled by abrupt changes in magnetocrystalline and magnetostriction constants due to crystal deformation from cubic to monoclinic structure.     

Comparison of methods to model the gravitational gradients from topographic data bases

A number of methods have been developed over the last few decades to model the gravitational gradients using digital elevation data. All methods are based on second-order derivatives of the Newtonian mass integral for the gravitational potential. Foremost are algorithms that divide the topographic masses into prisms or more general polyhedra and sum the corresponding gradient contributions. Other methods are designed for computational speed and make use of the fast Fourier transform (FFT), require a regular rectangular grid of data, and yield gradients on the entire grid, but only at constant altitude. We add to these the ordinary numerical integration (in horizontal coordinates) of the gradient integrals. In total we compare two prism, two FFT and two ordinary numerical integration methods using 1" elevation data in two topographic regimes (rough and moderate terrain). Prism methods depend on the type of finite elements that are generated with the elevation data; in particular, alternative triangulations can yield significant differences in the gradients (up to tens of Eötvös). The FFT methods depend on a series development of the topographic heights, requiring terms up to 14th order in rough terrain; and, one popular method has significant bias errors (e.g. 13 Eötvös in the vertical–vertical gradient) embedded in its practical realization. The straightforward numerical integrations, whether on a rectangular or triangulated grid, yield sub-Eötvös differences in the gradients when compared to the other methods (except near the edges of the integration area) and they are as efficient computationally as the finite element methods.     

Contribution of domain rotation to the magnetic susceptibility of spherical two-domain particles of magnetite

Summary. Starting with a simplified picture of the presumed magnetization configuration in a two-domain sphere of magnetite, the initial susceptibility due to rotation of the magnetization in the domains has been calculated. In particles between 100 and 300 nm in diameter the calculated susceptibility for randomly oriented particles drops rapidly from about 6 to a little over 3, which is the value to be expected for large multidomain particles. The results agree well with the available experimental results and imply that in magnetite particles in this size range the low field susceptibility is dominated by the domain rotation and that wall motion is effectively inhibited.