Magnetic anisotropy of hematite natural crystals: high field experiments

Hematite is one of the most important carriers of remanent magnetization in natural samples. Its strong magnetocrystalline anisotropy makes it difficult to determine one single value for the magnetic anisotropy constant and other magnetic properties. In particular, the anisotropy of hematite within its basal plane is controversial because an assumed triaxial anisotropy compatible with the crystallographic structure has not always been detected. This study presents a comparative analysis of rock magnetic properties, compositional analysis and determination of the magnetic anisotropy constant. Different models with anisotropy constant within the basal plane ranging from 0 to 13 (J m⁻³) are considered in the evaluation of the factors that control the presence or absence of a triaxial anisotropy. A linear relationship between saturation magnetization (M _s ) and coercitivity (B _c ) in measurements at increasing temperatures is observed in samples where anisotropy is either uniaxial or biaxial while those with significant triaxial anisotropies have a power–law relationship between M _s and B _c .     

Glide systems of hematite single crystals in deformation experiments

The critical resolved shear stresses (CRSSs) of hematite crystals were determined in compression tests for r-twinning, c-twinning and {a}<m>-slip in the temperature range 25 °C to 400 °C, at 400 MPa confining pressure, and a strain rate of 10^− 5 s^− 1 by Hennig-Michaeli, Ch., Siemes, H., 1982. Experimental deformation of hematile crstals betwen 25 °C and 400 °C at 400 MPa confining pressure. In: Schreyer, W. (Ed.) High Pressure Research in Geoscience, Schweizerbart'sche Verlagsbuchhandlung, Stuttgart, p. 133–150. In the present contribution newly performed experiments on hematite single crystals at temperatures up to 800 °C at strain rates of 10^− 5 s^− 1 and 300 MPa confining pressure extends the knowledge about the CRSS of twin and slip modes. Optical observations, neutron diffraction goniometry, SEM forescatter electron images and electron backscatter diffraction are applied in order to identify the glide modes. Both twinning systems and {a}<m>-slip were confirmed by these methods. Besides the known glide systems the existence of the (c)<a>-slip system could be stated. Mechanical data establish that the CRSS of r-twinning decreases from 140 MPa at 25 °C to  5 MPa at 800 °C and for {a}<m>-slip from > 560 MPa at 25 °C to  40 MPa at 700 °C. At room temperature the CRSS for c-twinning is around 90 MPa and at 600 °C  60 MPa. The data indicate that the CRSSs above 200 °C seem to be between the values for r-twinning and {a}<m>-slip. For (c)<a>-slip only the CRSS at 600 °C could be evaluated to  60 MPa. Exact values are difficult to determine because other glide systems are always simultaneously activated.     

Bioreduction of natural specular hematite under flow conditions

Dissimilatory reduction of Fe(III) by Shewanella oneidensis MR-1 was evaluated using natural specular hematite as sole electron acceptor in an open system under dynamic flow conditions to obtain a better understanding of biologic Fe(III) reduction in the natural environment. During initial exposure to hematite under advective flow conditions, cells exhibited a transient association with the mineral characterized by a rapid rate of attachment followed by a comparable rate of detachment before entering a phase of surface colonization that was slower but steadier than that observed initially. Accumulation of cells on the hematite surface was accompanied by the release of soluble Fe(II) into the aqueous phase when no precautions were taken to remove amorphous Fe(III) from the mineral surface before colonization. During the period of surface colonization following the detachment phase, cell yield was estimated at 1.5-4 × 10⁷ cells/μmol Fe(II) produced, which is similar to that reported in studies conducted in closed systems. This yield does not take into account those cells that detached during this phase or the Fe(II) that remained associated with the hematite surface. Hematite reduction by the bacterium led to localized surface pitting and localized discrete areas where Fe (II) precipitation occurred. The cleavage plane of hematite left behind after bacterial reduction, as revealed by our results, strongly suggests, that heterogeneous energetics of the mineral surface play a strong role in this bioprocess. AQDS, an electron shuttle shown to stimulate bioreduction of Fe(III) in other studies, inhibited reduction of hematite by this bacterium under the dynamic flow conditions employed in the current study.     

Effect of inherent anisotropy on the strength of natural granite residual soil under generalized stress paths

It is universally known that residual soils behave very differently from sedimentary soils. While the latter is widely known as cross-anisotropic, little is known regarding the strength anisotropy of residual soils. This study presents how the inherent anisotropy affects the strength of natural granite residual soils under generalized conditions, where intact specimens were carefully prepared and sheared under triaxial compression, extension, simple shear, and hollow cylinder torsional shear tests. The strength of natural residual soil, in terms of ultimate stress ratio M and undrained shear strength S_u, is found to be significantly anisotropic in a different way from normally consolidated clays with the maximum strength obtained under triaxial compression and the minimum under simple shear or at intermediate principal stress direction. As a result, the existing method failed to measure the anisotropy degree of the studied soil. Two parameters were proposed accordingly to quantify the anisotropic strength under general conditions, taking the special strength anisotropy pattern and cohesive-frictional nature of GRS into account. The proposed parameters enable the direct comparison of strength anisotropy among soils. This study serves as a data set to better understand residual soils regarding their anisotropic behaviors under generalized conditions. Although specific to granite residual soils in China, this study is expected to be more widely applicable to other weathered geomaterials.

     

Elastic shear stiffness anisotropy and fabric anisotropy of natural clays

Natural clays usually show anisotropic stiffness due to their deposition process and anisotropic in situ stress state. The stiffness anisotropy depends on both of the stress anisotropy and fabric anisotropy, while the latter can be quantified by the stiffness anisotropy at isotropic stress states. This paper measures the K₀ value (i.e., stress anisotropy) and elastic shear stiffness anisotropy of natural Shanghai clay in a triaxial apparatus with horizontal and vertical bender elements. The results show that the K₀ value of Shanghai clay lies in the range of 0.40–0.66, and an empirical equation is proposed to estimate the K₀ value based on the plasticity index and initial void ratio. The fabric anisotropy of natural Shanghai clay lies in the range of 1.2–1.4 with a stronger fabric in the horizontal plane. Moreover, the experimental data of the stiffness anisotropy and fabric anisotropy of different clays in the literature are reviewed and analyzed. It reveals that the stiffness anisotropy generally increases, while the fabric anisotropy remains nearly the same during K₀ consolidation. For normally consolidated clay, the fabric anisotropy generally lies in the range of 1.1–1.7. For overconsolidated clays, the fabric anisotropy generally increases as the overconsolidation ratio increases. Empirical equations are proposed to approximately estimate the fabric anisotropy of clays based on its stress normalized elastic shear stiffness.

     

Magnetic anisotropy of calcite at room-temperature

The intrinsic room temperature magnetic properties of pure calcite were determined from a series of natural crystals, and they were found to be highly dependent on the chemical composition. In general, dia-, para-, and ferromagnetic components contribute to the magnetic susceptibility and the anisotropy of magnetic susceptibility (AMS). With a combination of magnetic measurements and chemical analysis these three contributions were determined and related to their mineralogical sources. The intrinsic diamagnetic susceptibility of pure calcite is − 4.46 ± 0.16 × 10^− 9 m³/kg (− 12.09 ± 0.5 × 10^− 6 SI) and the susceptibility difference is 4.06 ± 0.03 × 10^− 10 m³/kg (1.10 ± 0.01 × 10^− 6 SI). These diamagnetic properties are easily dominated by other components. The paramagnetic contribution is due to paramagnetic ions in the crystal lattice that substitute for calcium; these are mainly iron and manganese. The measured paramagnetic susceptibility agrees with the values calculated from the known concentration of paramagnetic ions in the crystals according to the Curie law of paramagnetic susceptibility. Substituted iron leads to an increase in the AMS. The paramagnetic susceptibility difference was found to correlate linearly with the iron content for concentrations between 500 and 10,000 ppm. An empirical relation was determined: (k₁ − k₃)^para (kg/m³) = Fe-content (ppm) × (1 ± 0.1) × 10^− 12 (kg/m³/ppm). The maximum susceptibility difference (Δk = k₁ − k₃) was found to be unaffected by iron contents below 100 ppm. Ferromagnetic contributions due to inclusions of ferromagnetic minerals can dominate the susceptibility. They were detected by acquisition of isothermal remanent magnetization (IRM) and their contribution to the AMS was separated by high-field measurements.     

Removal of arsenic from aqueous solution by natural siderite and hematite

Batch and column experiments were conducted to examine the capability of naturally formed hematite and siderite to remove As from drinking water. Results show that both minerals were able to remove As from aqueous solutions, but with different efficiencies. In general, each material removed arsenate much more efficiently than As–DMA (dimethylarsinic acid), with the lowest adsorption efficiency for arsenite. The best removal efficiency for As species was obtained using a hematite, with a grain size range between 0.25 and 0.50 mm. The adsorption capacity for inorganic As(V) reached 202 μg/g. The pH generally had a great impact on the arsenate removal by the Fe minerals studied, while arsenite removal was slightly dependent on the initial pH of between 3 and 10. The presence of phosphate always had a negative effect on arsenate adsorption, due to competitive adsorption between them. A column packed with hematite in the upper half and siderite in the lower half with a grain size range of 0.25–0.5 mm proved to be an efficient reactive filter for the removal of all As species, causing a decrease in As concentration from 500 μg/L (including 200 μg/L As(V) as arsenate, 200 μg/L As(III) as arsenite and 100 μg/L As(V) as DMA) to less than 10 μg/L after 1055 pore volumes of water were filtered at a flow rate of 0.51 mL/min. After 2340 pore volumes passed through the column filter, the total inorganic As in the effluent was less than 5 μg/L. The total As load in the column filter was estimated to be 0.164 mg/g. Results of μ-synchrotron X-ray fluorescence analysis (μ-XRFA) suggest that coatings of fresh Fe(III) oxides, formed on the surface of the siderite grains after two weeks of operation, greatly increased the adsorption capacity of the filling material towards As.     

Magnetic susceptibility of natural diamonds

Doklady Earth Sciences -     

考虑各向异性的软黏土扰动状态本构模型

以大量试验结果为依据,运用物理意义明确、获取简便快捷、经济实用的土电阻率结构指标进行软黏土扰动变量的表征和测定。以三轴试验与电阻率测试结果为基础,进行了扰动函数的构建。在软黏土扰动状态描述中,引入旋转硬化因子,用以考虑应力诱发各向异性,进而构建了考虑各向异性的软黏土扰动状态概念本构模型。模型从一定程度上克服了传统扰动变量获取方法的弊端,克服了传统借用数学演绎手段建立扰动函数的不足,提高了模型应用的适用性。在模型构建中,融入初始应力各向异性的影响,从而使模型能更好地反映软土实际工程情况。三轴排水剪切试验验证结果表明,该模型可较好反映软黏土受荷下的结构变化情况和受力特性。     

Nanotopography of synthetic and natural dolomite crystals

Examination with scanning electron microscopy (SEM) and scanning force microscopy (SFM) revealed etch pits, layers and islands on dolomite crystal faces synthesized from calcite in Ca‐Mg‐Cl solutions at 200 °C and a wide variety of natural dolomites. Layers are broad, flat structures bounded by steps less than 100 nm high and greater than 1 μm wide. Islands are rounded topographic highs <20 nm high and <200 nm wide. The nanotopography of synthetic dolomite changed from islands throughout most of the reaction to layers at 100% dolomite. Island nanotopography formed on both Ca‐rich and near‐stoichiometric dolomite. Analyses of reaction products from dolomite synthesis indicates that there are no SFM‐detectable products formed in <10 h. SEM‐detectable products formed in 15 h. X‐ray diffraction (XRD)‐detectable products formed in ≈18 h, and the reaction went to completion in ≈40 h. Based on SFM analyses, the induction period for dolomitization in these experiments accounts for ≈20% of the total reaction time necessary to dolomitize CaCO₃ completely under the experimental conditions used here. Island nano‐ topography is inferred to occur at higher degrees of supersaturation than layer nanotopography for three reasons. First, island nanotopography on synthetic calcite and gypsum forms at higher supersaturations than layer nanotopography. Secondly, island nanotopography formed in solutions with higher degrees of supersaturation with respect to dolomite. Thirdly, the greater surface roughness of a crystal face composed of islands compared with layers indicates that island surfaces have higher surface energy than layer surfaces. Therefore, the stability of island surfaces requires a higher degree of supersaturation. Because islands and layers form under a wide range of conditions, their presence provides broadly applicable criteria for evaluating relative degrees of supersaturation under which ancient dolomite formed. Comparison of synthetic dolomites with natural dolomites demonstrates (1) similar nanotopography on natural and synthetic dolomites and (2) both natural planar and non‐planar dolomite may have island nanotopography.     

Experimental investigation of shear strength of sands with inherent fabric anisotropy

Loading direction-dependent strength of sand has been traditionally characterized in the principal stress space as a direct extension of the Mohr–Coulomb criterion. A recent study found that it is more appropriate to define anisotropic strength of sand on failure/shear planes, but this proposition has only been demonstrated with discrete element method (DEM) simulations. The present study experimentally investigates anisotropic shear strength of sands in this new framework. Three granular materials with distinct grain characteristics ranging from smooth and rounded particles to flaky and angular particles are tested with the bedding plane inclination angle ψ _b varying over the full range of 0°–180°. The main objective is to study how the peak friction angle ? _p of sand is affected by the ψ _b angle and how the ψ _b–? _p relationship evolves with the change of characteristics of constituent sand particles. We find that the general trend of ψ _b–? _p curves for real sands resembles what was predicted by DEM in a previous study, whereas rich anisotropic strength behavior is revealed by the laboratory data. The effects of normal stress and initial density, as well as shear dilation behavior at different shear directions, are also studied.     

Investigation of the anisotropy of black shale in dynamic tensile strength

Shale usually exhibits strong anisotropy due to depositional environment and pre-existed microcracks caused by geological loading for a long time. Characterizing mechanical anisotropy properties of shale, especially the tensile strength anisotropy, plays an important role in the successful exploitation of shale gas. In this work, static and dynamic tests with semi-circular bending (SCB) specimen are conducted using hydraulic servo-control machine and modified split Hopkinson pressure bar (SHPB) system, respectively. To survey the tensile strength anisotropy of shale induced by stratification, samples are cored and cut into half by diametrical cutting along different angles relative to the stratification (0°, 30°, 45°, 60°, 90°, C0°). For dynamic tests, the utilization of pulse shaping technique ensures that the samples obtain dynamic equilibrium. The tensile strength values exhibit clear anisotropy under both static and dynamic loading conditions and show typical loading rate dependence at a given angle. An anisotropic index named α_k is defined to describe the tensile strength anisotropy at a certain loading rate. The outcomes illustrate that the anisotropic index decreases as the loading rate increases. In addition, failure pattern owns different characteristic under different loading angles with respect to the stratification. These phenomena may be explained by the pre-existing microcracks, and cracks interaction during dynamic loading conditions.     

Constitutive modeling of the destructuration and anisotropy of natural soft clay

The mechanical behavior of natural clays is affected by their inherent anisotropy and metastable soil structure. A simple hierarchical model that considers initial anisotropy and destructuration was formulated within the framework of critical state soil mechanics. In the proposed model, stress sensitivity and a destructuration index were introduced to account for the degree of bonding and the rate of destructuration, respectively. An inclined yield surface was used to incorporate the effect of the initial anisotropy. The proposed model can be degenerated to the Modified Cam Clay model by setting the initial stress sensitivity equal to unity and using a horizontal yield surface. Reasonable agreement between the model simulations and the experimental results on a variety of stress paths demonstrated that the proposed model can capture well the deformation behavior of natural clay and reconstituted soil. The model was implemented into the finite element program for the numerical analysis of an embankment on soft clay improved with prefabricated vertical drains. The numerical predictions were compared with the field-measured data in terms of embankment settlement. Additionally, the numerical simulations were analyzed in terms of horizontal displacements, excess pore water pressure, mean effective stress and volumetric strain. All of the simulations and comparisons indicate the importance of considering the effects of plastic anisotropy, interparticle bonding and destructuration caused by loading beyond yield stress and field disturbance in analyzing the behavior of an embankment on natural soft clay.     

The effect of strength anisotropy on the bearing capacity of spudcan foundations

The vertical bearing capacity of spudcan foundations in strength anisotropic soils is investigated numerically using the MIT-S1 model implemented in the AFENA finite element package. The model in AFENA is validated against existing laboratory test data of normally consolidated soil. The bearing capacities of spudcans in soils with isotropic and anisotropic strengths are compared. Soil with isotropic strength is simulated using an elasto-plastic model. It is found that the bearing capacity of a spudcan in an anisotropic soil is reduced by about 9% for a rough spudcan and 3% for a smooth spudcan on average. There is a combined effect of soil anisotropy and spudcan roughness on the spudcan bearing capacity. Moreover, the effect of the pressuremeter strength of an anisotropic soil on foundation capacity can’t be ignored.     

Effect of microstructure and weathering on the strength anisotropy of porous rhyolite

To study the effect of microstructure and weathering on the strength anisotropy of rock, unconfined compressive strength (UCS) tests were carried out on three porous rhyolites having the same original lithology, but different weathering periods of 2600, 20,000 and 40,000 years. The rock is mainly composed of glassy groundmass, with flow structure. UCS tests were undertaken on a series of samples at 15° intervals, from right angles to the flow structure (β=90°) to parallel (β=0°), where β is the angle between the direction of the applied load and the direction of the flow structure. The test results show that UCS-values are maximum when β=0–30° and minimum when β=60–90°. This differs from previous reports for layered anisotropic rocks such as sandstone, sandy shale, schist etc., for which, UCS-values are maximum at β=0 or 90°. It is also found that UCS-values for β=60–90° reduce rapidly in the initial stage of weathering (the first 20,000 years), while for β=0–30°, the reduction rate increases after 20,000 years. This shows that the effect of weathering on strength anisotropy is not uniform, but depends on the weathering processes of the microstructures of the rock.     

Composite magnetic anisotropy fabrics: experiments, numerical models and implications for the quantification of rock fabrics

Magnetic fabrics from rocks with multiple mineral-preferred orientations may have anisotropy ellipsoids whose shape and orientation arise from the addition of two or more component fabrics. Our numerical models and experiments demonstrate that such composite magnetic fabrics do not directly reflect the shapes and/or orientations of the individual mineral fabrics and we provide criteria for the recognition and interpretation of composite fabrics in natural rocks. These criteria include:

1. (1) the orientation of the maximum susceptibility axis is located at the intersection of two planar fabrics, and

2. (2) the shape of the susceptibility ellipsoid changes from oblate to prolate and the degree of anisotropy decreases, as the relative intensity of two planar component fabrics becomes equal and as the angle between the planar fabrics increases.

Composite magnetic fabrics are observed in the shales and slates of the Martinsburg Formation, Lehigh Gap, Pennsylvania. Modeling of the AMS (anisotropy of magnetic susceptibility) and ARMA (anhysteretic remanent magnetization anisotropy) behavior constrains the relative degree of anisotropy of the bedding-parallel and cleavage-parallel fabrics. In particular, ARMA model results allow a good estimate of magnetite fabric strength.

We conclude that, in the presence of composite magnetic fabrics, quantitative measures of finite strain in deformed rocks are limited by the ability to accurately determine the degree of anisotropy and relative susceptibility of each component fabric. Such determinations require knowledge of the mineral(s) that are responsible for the measured magnetic fabric and their behavior during deformation.     

Tensile strength and its anisotropy measured by point and line-loading of sandstone

Tensile fracture is an ubiquitous feature of rock failure ranging in size from microfracture around Griffith cracks to the large-scale explosive failure accompanying rock bursts in underground cavities. Hence the resistance of rock to failure in tension, the tensile strength, is one of the fundamental parameters of rock strength. The tensile strength of rock is, however, a most elusive parameter which is difficult to measure and to define.

The tensile strength, and its variation with direction, was determined by the pointloading and the line-loading (Brazilian test) methods for nine rocks from five sandstone formations in New Brunswick, Canada. Altogether 319 double point-load and 357 line-load tests were conducted on discs having a diameter of 22.9 mm and thickness of 7.9 mm.

The tensile strength determined by the point-load test and as calculated by the Frocht formula was found to be consistently lower than that obtained by the line-loading technique. To some extent, the difference is due to the fact that most of the sandstones are anisotropic with respect to tensile strength and that the constraints in the point-load test are such that fracture occurs along the plane of minimum tensile strength; the computed tensile strength therefore represents a minimum value. To a greater extent, the lower tensile strength calculated from the point-load test is due to the difference in the states of stress induced by the two techniques. When correction is made for the anisotropy, the tensile strength from the Brazilian test is still 3.76 times larger than the one obtained from the point-load test.

The Brazilian test seems to yield a more accurate definition of both the tensile strength and its variation with direction. The point-load test is more suitable for the determination of the minimum value of tensile strength and the direction of the preferred fracture plane.     

The anisotropy of magnetic susceptibility in biotite, muscovite and chlorite single crystals

The anisotropy of magnetic susceptibility (AMS) of single crystals of biotite, muscovite and chlorite has been measured in order to provide accurate values of the magnetic anisotropy properties for these common rock-forming minerals. The low-field AMS and the high-field paramagnetic susceptibility are defined. For the high-field values, it is necessary to combine the paramagnetic deviatoric tensor obtained from the high-field torque magnetometer with the paramagnetic bulk susceptibility measured from magnetization curves of the crystals. This leads to the full paramagnetic susceptibility ellipsoid due to the anisotropic distribution of iron cations in the silicate lattice. The ellipsoid of paramagnetic susceptibility, which was obtained for the three phyllosilicates, is highly oblate in shape and the minimum susceptibility direction is subparallel to the crystallographic c-axes. The anisotropy of the susceptibility within the basal plane of the biotite has been evaluated and found to be isotropic within the accuracy of the instrumental measurements. The degree of anisotropy of biotite and chlorite is compatible with previously reported values while for muscovite the smaller than previously published values. The shape of the chlorite AMS ellipsoid for all the samples is near-perfect oblate in contrast with a wide distribution of oblate and prolate values reported in earlier studies. Reliable values are important for deriving models of the magnetic anisotropy where it reflects mineral fabrics and deformation of rocks.     

CO clumping in speleothems: Observations from natural caves and precipitation experiments

The oxygen isotope composition of speleothems is an important proxy of continental paleoenvironments, because of its sensitivity to variations in cave temperature and drip water δ¹⁸O. Interpreting speleothem δ¹⁸O records in terms of absolute paleotemperatures and δ¹⁸O values of paleo-precipitation requires quantitative separation of the effects of these two parameters, and correcting for possible kinetic isotope fractionation associated with precipitation of calcite out of thermodynamic equilibrium. Carbonate clumped-isotope thermometry, based on measurements of Δ₄₇ (a geochemical variable reflecting the statistical overabundance of ¹³C¹⁸O bonds in CO₂ evolved from phosphoric acid digestion of carbonate minerals), potentially provides a method for absolute speleothem paleotemperature reconstructions independent of drip water composition. Application of this new technique to karst records is currently limited by the scarcity of published clumped-isotope studies of modern speleothems. The only modern stalagmite reported so far in the literature yielded a lower Δ₄₇ value than expected for equilibrium precipitation, possibly due to kinetic isotope fractionation.Here we report Δ₄₇ values measured in natural speleothems from various cave settings, in carbonate produced by cave precipitation experiments, and in synthetic stalagmite analogs precipitated in controlled laboratory conditions designed to mimic natural cave processes. All samples yield lower Δ₄₇ and heavier δ¹⁸O values than predicted by experimental calibrations of thermodynamic equilibrium in inorganic calcite. The amplitudes of these isotopic disequilibria vary between samples, but there is clear correlation between the amount of Δ₄₇ disequilibrium and that of δ¹⁸O. Even pool carbonates believed to offer excellent conditions for equilibrium precipitation of calcite display out-of-equilibrium δ¹⁸O and Δ₄₇ values, probably inherited from prior degassing within the cave system.In addition to these modern observations, clumped-isotope analyses of a flowstone from Villars cave (France) offer evidence that the amount of disequilibrium affecting Δ₄₇ in a single speleothem can experience large variations at time scales of 10 kyr. Application of clumped-isotope thermometry to speleothem records calls for an improved physical understanding of DIC fractionation processes in karst waters, and for the resolution of important issues regarding equilibrium calibration of Δ₄₇ in inorganic carbonates.