Change of structure,phase composition and magnetic properties with the oxidation of titanomagnetites

Summary Phase, structural and magnetic changes, occurring under oxidation and at increased temperatures, are studied on four samples of magnetic fractions. The samples of magnetic fractions, containing titanomagnetites at different oxidation levels, were oxidized at a temperature of 400°C for 1, 60 and 300 mins. With the aid of X-rays and Mössbauer's spectrometry it has been proved that under oxidation non-stoichiometric titanomagnetites and titanomagnetites plus ilmenite and pseudobrookite are formed.     

The magnetic anisotropy of basalts and its variations under oxidation of titanomagnetites

Summary Using four samples of basaltic rocks from the Bohemian Massif, Nos 201, 202, 206 and 218, the curves of rotational moments in a magnetic field of 4 × 10⁵ A/m were studied as a function of the degree of oxidation of titanomagnetites. The amplitudes of the individual harmonics were determined by harmonic analysis for samples oxidized to various degrees. It was found that the proportion of the harmonic A ₁ withsin increases with the degree of oxidation. Simultaneously, the anisotropy of the magnetic susceptibility changes in a field of 60 A/m and the structure changes from linearly parallel to plane parallel.     

The nature of the high values of the anisotropy of magnetic susceptibility of rock samples with polydomain ferromagnetics

Samples of different rocks, which possess high values of the anisotropy of magnetic susceptibility, were studied by the magneto-mineralogical and optical methods and by microprobe analysis. It was established that for the samples, which contain the pseudo-single-domain ferromagnetite elongated particles, the source of the anisotropy of magnetic susceptibility is the distribution anisotropy of not only ferromagnetic grains themselves, but also ferromagnetic patterns in the heterogeneous accessory minerals. For samples with multidomain ferromagnetic materials, the nature of the anisotropy of magnetic susceptibility is caused by the orientation of the ilmenite lamellar phase in the structures of disintegration of titanomagnetites or by the orientation of the ferromagnetic structures of disintegration in iron sulfides.     

Magnetic monitoring of top soils of Merida (Southern Mexico)

This paper focuses on the study of the correlation between magnetic parameters with the level of contamination by heavy metals in urban soils. We report a magnetic investigation of urban soil samples from Merida, state of Yucatan, Southern Mexico. It appears that most of our samples contain ferrimagnetic minerals as the magnetic carriers, probably coming from the titanomagnetites/titanomaghemites series. This is inferred by the acquisition of isothermal remanent magnetization, which shows that most of samples are almost completely saturated at about 200 mT. The S₋₂₀₀ value (factor characterizing stability of remanent magnetization) is between 0.8 and 1.0, characteristic of ferrimagnetic minerals. The susceptibility vs. temperature measurements also point to some titanomaghemites and titanomagnetites as probable responsible for magnetization. On the other hand, measurements of magnetic susceptibility at high and low frequencies helped us to determine the high content of superparamagnetic grains in the majority of the samples, although not all of these showed high values of magnetic susceptibility. We found that the most contaminated samples by Pb and Zn showed the higher saturation isothermal remanent magnetization values, whereas the higher values in magnetic susceptibility correspond to samples contaminated by Cr. Finally, we noted that a high level in Sr decreases the magnetic susceptibility.     

Low-Temperature Oxidation of Magnetite in Loess-Paleosol Sequences: a Correction of Rock Magnetic Parameters

Low-temperature oxidation under atmospheric conditions affects the magnetic properties of magnetite in natural rocks: the coercivities of magnetite grains increase and other parameters change accordingly. It was recently shown that heating to 150°C largely removes the effects of low-temperature oxidation (van Velzen and Zijderveld, 1995). Heating may therefore serve as a detection tool for the presence of the effect of low-temperature oxidation. In the present study, a collection of loess and paleosol samples from various loess regions of the world is examined for the influence of low-temperature oxidation. In all samples of the collection a decrease of coercivities was found after heating to 150°C. Generally loess samples were affected to a larger extent than paleosol samples. The original range of remanent coercivities(B _cr)of 21-58 mT changed to 20-42 mT after heating. The IRM capacity of the samples decreased from 0 up to 25%. ARM showed changes between a decrease of 10% and an increase of 15%. The grain-size indicative parameter IRM/ARM is considerably influenced by the heating and therefore by low-temperature oxidation. The changes in susceptibility are limited and will not influence the interpretation of large-scale features of the susceptibility record as a paleoclimate proxy. Small variations, however, may be obscured by the varying influence of oxidation in the outcrop, which can significantly modify the rock-magnetic record. Rock-magnetic parameters used to determine magnetic mineral content and grain sizes should be corrected for the effect of low-temperature oxidation. To this end heating to 150°C is recommended. The occurrence of the changes is in itself already an indication for the presence of magnetite. Low-temperature oxidation will not only be due to recent weathering in the outcrop, but also to earlier oxidation processes in the source area, during transport and deposition of the loess and during pedogenesis. Truly fresh sediment samples are only influenced by this earlier oxidation. In that case heating will reveal the degree of ancient low-temperature oxidation, which may be related to climate at the time of deposition and pedogenesis.     

On the complex magnetic behaviour of titanomagnetites

The bulk magnetic properties, including Curie temperature, susceptibility and hysteresis at various temperatures, and the Mössbauer spectra of coarse synthetic members of the titanomagnetite series are compared as a function of titanium content, using some previously reported and some new results. It has been noted previously that the titanium-rich members fail to show the expected “true multidomain” behaviour observed in pure magnetite. One possible explanation is that the behaviour observed may be due to a tendency to inhibit domain wall formation in some titanomagnetites. In this paper we discuss some other possible mechanisms to account for the magnetic properties of such titanomagnetites observable even when domain-wall-related structures do form in them. These mechanisms suggest that magnetocrystalline anisotropy and its temperature dependence in titanomagnetites may be related to local magnetic inhomogeneities, and do not depend only on crystal structure as in the case of classical ferromagnetic materials.     

Experimental modeling of the chemical remanent magnetization and Thellier procedure on titanomagnetite-bearing basalts

The results of the experimental studies on creating chemical and partial thermal remanent magnetizations (or their combination), which are imparted at the initial stage of the laboratory process of the oxidation of primary magmatic titanomagnetites (Tmts) contained in the rock, are presented. For creating chemical remanent magnetization, the samples of recently erupted Kamchatka basalts were subjected to 200-h annealing in air in the temperature interval from 400 to 500°С under the action of the magnetic field on the order of the Earth’s magnetic field. After creation of this magnetization, the laboratory modeling of the Thellier–Coe and Wilson–Burakov paleointensity determination procedures was conducted on these samples. It is shown that when the primary magnetization is chemical, created at the initial stage of oxidation, and the paleointensity determined by these techniques is underestimated by 15–20% relative to its true values.     

Magnetic petrology of eastern North America diabases, I. Olivine-normative dikes from western South Carolina

The oxide mineralogy and magnetic properties were examined in a suite of fifteen olivine-normative diabase dike samples from western South Carolina in an attempt to elucidate their magnetic petrology. Titanomagnetite (1–2 vol.%) is the dominant Fe-Ti oxide mineral. Ilmenite and secondary magnetite are generally present in very minor amounts. Chromite constitutes up to 0.5 vol.%; its abundance and composition correlate with bulk rock Cr. Various types of fine-scale microstructure are evident in titanomagnetite crystals. The most important are patterned anisotropism and the development of trellis-type ilmenite lamellae. Microprobe analyses indicate: (1) titanomagnetite compositions, x, are mostly between 0.4 and 0.55, and (2) low analytical totals are characteristic of most titanomagnetites. Curie temperatures of the diabases are 500–540°C, which are several hundred degrees higher than predicted from the observed titanomagnetite x's (150–300°C). We attribute these higher Curie temperatures to oxidation of the titanomagnetites, which has produced “titanomaghemites” having visible microstructure and yielding low analyses (because they are cation deficient). Natural remanence magnetization and REM (ratio of natural remanence to saturation remanence) vary between 4 and 100 × 10⁻⁴ A m² kg⁻¹ and 0.0019 and 0.032, respectively. These properties inversely correlate with Cr content and demonstrably contrast Cr-rich and Cr-poor samples. Initial susceptibility, saturation magnetization and coercivity values show a two- to three-fold range. Variations in initial susceptibility and coercivities appear to be largely related to the type and extent of oxidation-induced microstructure in the titanomagnetites.     

Theoretical analysis of thermomagnetic properties, low-temperature hysteresis and domain structure of titanomagnetites

Magnetic hysteresis of coarse-grained titanomagnetites at room temperature is characterised by low coercive force, low relative remanence, and a high ratio of coercivity of remanence to coercive force. These properties are generally interpreted in terms of multidomain structure. At low temperatures, however, ulvöspinel-rich compositions exhibit hysteresis properties similar to those of single-domain assemblages, and on this basis Radhakrishnamurty and Deutsch have proposed an alternative interpretation of the domain structure of titanomagnetites having x 0.3 in terms of a mixture of single-domain and superparamagnetic particles. Low apparent Curie temperatures are attributed to the effects of thermal agitation above the blocking temperature.

We have examined theoretically the effects of thermal agitation on the low- and high-field thermomagnetic curves and find that observed Curie temperatures in general represent an intrinsic property of the magnetic mineral present, rather than reflecting thermal agitation. The high coercive force and relative remanence at low temperatures for titanomagnetites having x > 0.5 can be explained on the basis of the interaction of domain walls with crystal defects when the large increases in magnetocrystalline anisotropy and magnetostriction with decreasing temperature are taken into account. We discuss the evidence for the existence of domain walls in coarse-grained ulvöspinel-rich titanomagnetites and conclude that multidomain structure is well established.

It is also shown that fine titanomagnetite grains may have more than one blocking temperature. In any temperature interval for which superparamagnetic grains are present they will disproportionately influence susceptibility and low-field hysteresis.     

High magnetic susceptibility produced by thermal decomposition of core samples from the Chelungpu fault in Taiwan

We carried out thermomagnetic susceptibility analyses of fault rocks from core samples from Hole B of the Taiwan Chelungpu Fault Drilling Project (TCDP) to investigate the cause of high magnetic susceptibilities in the fault core. Test samples were thermally and mechanically treated by heating to different maximum temperatures of up to 900 °C and by high-velocity frictional tests before magnetic analyses. Thermomagnetic susceptibility analyses of natural fault rocks revealed that magnetization increased at maximum heating temperatures above 400 °C in the heating cycle, and showed three step increases, at 600 to 550 °C and at 300 °C during the cooling cycle. These behaviors are consistent with the presence of pyrite, siderite and chlorite, suggesting that TCDP gouge originally included these minerals, which contributed to the generation the magnetic susceptibility by thermomechanical reactions. The change in magnetic susceptibility due to heating of siderite was 20 times that obtained by heating pyrite and chlorite, so that only a small fraction of siderite decomposition is enough to cause the slight increase of the susceptibility observed in the fault core. Color measurement results indicate that thermal decomposition by frictional heating took place under low-oxygen conditions at depth, which prevented the minerals from oxidizing to reddish hematite. This finding supports the inference that a mechanically driven chemical reaction partly accounts for the high magnetic susceptibility. A kinetic model analysis confirmed that frictional heating can cause thermal decomposition of siderite and pyrite. Our results show that decomposition of pyrite to pyrrhotite, siderite and, to some extent, chlorite to magnetite is the probable mechanism explaining the magnetic anomaly within the Chelungpu fault zone.     

Notes on the variation of magnetization within basalt lava flows and dikes

Summary The magnetic properties of basaltic rocks are dominated by the contained primary Fe–Ti oxides. At solidus temperature (1000°C) the composition of these primary oxides is restricted to titanomagnetite (Fe_3-xTi_xO₄) and hemoilmenites (Fe_2-yTi_yO₃). The examination of 269 chemical analyses of the primary Fe–Ti oxides in basalts (in sensu lato) gives an average ofx=0.61 (T _c=168°C) for the titanomagnetites andy=0.89 (T _c=–121°C) for the hemoilmenites. If distinction is made between tholeiites, alkali basalts and andesites, a clear difference for thex-values is observed: the average for tholeiitesx=0.64 (T _c=144°C), for alkali basaltsx=0.52 (T _c=253°C), for andesitesx=0.38 (T _c=341°C).Environment of crystallization and cooling rate are major interrelated factors influencing subsequent changes in the mineralogy of the primary Fe–Ti oxides and resulting magnetic properties. This has been tested by studying the variation of magnetization and some of its parameters in three different basalt rock units: a dike, 180 cm, and two lava flows, 3 m and 33 m thick, respectively. Grain size and oxidation state of the titanomagnetites control the variation of magnetization in these basalt units.     

Magnetic Anisotropy as an Aid to Identifying CRM and DRM in Red Sedimentary Rocks

To further evaluate the potential of magnetic anisotropy techniques for determining the origin of the natural remanent magnetization (NRM) in sedimentary rocks, several new remanence anisotropy measurement techniques were explored. An accurate separation of the remanence anisotropy of magnetite and hematite in the same sedimentary rock sample was the goal.In one technique, Tertiary red and grey sedimentary rock samples from the Orera section (Spain) were exposed to 13 T fields in 9 different orientations. In each orientation, alternating field (af) demagnetization was used to separate the magnetite and hematite contributions of the high field isothermal remanent magnetization (IRM). Tensor subtraction was used to calculate the magnetite and hematite anisotropy tensors. Geologically interpretable fabrics did not result, probably because of the presence of goethite which contributes to the IRM. In the second technique, also applied to samples from Orera, an anisotropy of anhysteretic remanence (AAR) was applied in af fields up to 240 mT to directly measure the fabric of the magnetite in the sample. IRMs applied in 2 T fields followed by 240 mT af demagnetization, and thermal demagnetization at 90°C to remove the goethite contribution, were used to independently measure the hematite fabric in the same samples. This approach gave geologically interpretable results with minimum principal axes perpendicular to bedding, suggesting that the hematite and magnetite grains in the Orera samples both carry a depositional remanent magnetization (DRM). In a third experiment, IRMs applied in 13 T fields were used to measure the magnetic fabric of samples from the Dome de Barrot area (France). These samples had been demonstrated to have hematite as their only magnetic mineral. The fabrics that resulted were geologically interpretable, showing a strong NW-SE horizontal lineation consistent with AMS fabrics measured in the same samples. These fabrics suggest that the rock's remanence may have been affected by strain and could have originated as a DRM or a CRM.Our work shows that it is important to account for the presence of goethite when using high field IRMs to measure the remanence anisotropy of hematite-bearing sedimentary rocks. It also shows that very high magnetic fields (>10 T) may be used to measure the magnetic fabric of sedimentary rocks with highly coercive magnetic minerals without complete demagnetization between each position, provided that the field magnetically saturates the rock.     

Oxidation of titanomagnetites in mafic and felsic intrusive rocks

We report opaque mineralogical observations and magnetic properties of primary titanomagnetites in Tertiary submarine gabbros from DSDP, Legs 30 and 37 and in a late Archean, continental granitic pluton, the Shelley Lake granite. The titanomagnetites and silicates in all the submarine gabbros have been deuterically oxidized. There is no indication of subsequent low-temperature oxidation, although serpentization of olivines is pervasive in the deeper Leg 37 units. The Leg 30 samples, from a single thick sill, contain abundant coarse (≈100 μm) titanomagnetites with fully developed ilmenite exsolution lamellae. Curie temperatures are 515–550°C; there are no low Curie temperatures that would indicate surviving unoxidized titanomagnetite. The unserpentinized Leg 37 gabbros contain scarce opaques with pure magnetite Curie points that are barely resolvable microscopically; most occur as inclusions in pyroxene. In the Shelley Lake granite, on the other hand, many samples exhibit bimodal blocking-temperature spectra, with blocking temperature peaks at 250–300°C and 550–575°C. The low-blocking-temperature phase is unidentified. No pyrrhotite was seen in thin section. Optically homogeneous grains coexist with fully exsolved neighbours, but the electron microprobe indicates no titanium. The lamellae appear to be haematite, not ilmenite, and the primary composition of the opaques is pure magnetite. The oxidation state of the opaques is very inhomogeneous, even on a fine scale.     

The development of magnetic susceptibility anisotropy through crystallographic preferred orientation in a calcite rock

High-field torque-meter measurements of diamagnetic susceptibility anisotropy of a suite of samples of Carrara marble, axially shortened by amounts up to 50% at (1.5–3.0) · 10⁸ Pa confining pressure and at 20–500°C (mainly 400°C), have been compared with optical measurements of preferred crystallographic orientation. A revised value for the susceptibility anisotropy of calcite has been obtained from studies of single crystals, and it has been shown to be almost independent of the state of intracrystalline plastic strain. From the measured anisotropy of calcite, quantitative comparison of optical and magnetic fabric measurements is possible. It is found that these measurements agree and the implications of the observed progressive development of fabric intensity with strain are discussed.     

Rock magnetic properties and ore microscopy of the iron ore deposit of Las Truchas, Michoacan, Mexico

Iron ore and host rocks have been sampled (90 oriented samples from 19 sites) from the Las Truchas mine, western Mexico. A broad range of magnetic parameters have been studied to characterize the samples: saturation magnetization, Curie temperature, density, susceptibility, remanence intensity, Koenigsberger ratio, and hysteresis parameters. Magnetic properties are controlled by variations in titanomagnetite content, deuteric oxidation, and hydrothermal alteration. Las Truchas deposit formed by contact metasomatism in a Mesozoic volcano-sedimentary sequence intruded by a batholith, and titanomagnetites underwent intermediate degrees of deuteric oxidation. Post-mineralization hydrothermal alteration, evidenced by pyrite, epidote, sericite, and kaolin, seems to be the major event that affected the minerals and magnetic properties. Magnetite grain sizes in iron ores range from 5 to >200 μm, which suggest dominance of multidomain (MD) states. Curie temperatures are 580±5°C, characteristic of magnetite. Hysteresis parameters indicate that most samples have MD magnetite, some samples pseudo-single domain (PSD), and just a few single domain (SD) particles. AF demagnetization and IRM acquisition indicate that NRM and laboratory remanences are carried by MD magnetite in iron ores and PSD–SD magnetite in host rocks. The Koenigsberger ratio falls in a narrow range between 0.1 and 10, indicating the significance of MD and PSD magnetites.     

Titanomagnetites prepared at different oxidation conditions: Influence of magnetite-rich inclusions

Synthetic titanomagnetites prepared at 1300°C at different oxidation potentials, although giving only spinel-type X-ray reflections, were found to contain a small amount of included material with a Curie point above that for the bulk material. Specimens, comprising either dispersed sized grains, or polycrystalline spherical aggregates of grains, develop thermoremanent moments which are dependent upon the presence of the inclusions. The magnetization of the inclusions is revealed by thermal demagnetization experiments, and the experimental results are compared with the effects expected to arise from magnetic shielding by the matrix titanomagnetite.     

Low-temperature oxidation of synthetic Al- and Mg-doped titanomagnetites

Al- and Mg-doped titanomagnetites were synthesized at 1300°C using the gas-mixing technique. A composition, representative of average natural titanomagnetites in ocean floor basalts, was sought.

The samples were ball-milled in acetone to average grain sizes of 0.5 μm and 5 μm and the material was then oxidised, in air, at temperatures below 300°C. This procedure formed titanomaghemite, a cation-deficient titanomagnetite.

Low-temperature oxidation is described as the diffusion of Fe-ions out of the spinel lattice and the process is observed to be distinctly dependent upon grain size.     

Magnetic properties,self-reversal remanence and thermal alteration products of smythite

Summary This study is a follow up of the investigation of some magnetic properties and metastability of greigite in samples obtained from Miocene claystones in the Kruné hory (Erzgebirge) Piedmont basins (Bohemia). Three different methods of upgrading the smythite were applied; the magnetic properties of the concentrates are compared. The thermal conversion of smythite sets in at 200°C while greigite converts at 250°C. The first intermediate products to be formed are iron sulphides, marcasite clearly dominating over pyrite and pyrrhotite. Apart from a Fe³⁺ sulphate with a composition of Fe₂(SO₄)₃, oxidation of these sulphides gives rise to -Fe₂O₃. The result of the subsequent decomposition of the mentioned sulphate is the formation of -Fe₂O₃, which retains the sulphate structure. The final product of the thermal decomposition at 800°C is -Fe₂O₃. In the smythite concentrate the conversion to Fe³⁺ sulphate and -Fe₂O₃ is about twice as intensive as in greigite. No direct conversion to -Fe₂O₃ was found. During the thermal process self-reversals of remanence were observed, in various samples as many as four reversals in the temperature interval from 340 to 590°C. The occurrences of self-reversals of remanence were only observed at high degrees of thermal demagnetization, of the order of 10^–2 down to 10^–3 in the temperature interval of sulphide origin (below 400°C), and of the order of 10^–4 down to 10^–6 in the temperature interval of Fe-oxides origin (above 400°C).Presented at the 3rd Conference on New Trends in Geomagnetism, Castle of Smolenice, Czechoslovakia, June 22–29, 1992     

A deformed Pliocene-Quaternary alluvial and red paleosol succession in the Eastern Betics: Paleomagnetic,rock-magnetic and sedimentological pilot study

Summary An integrated pilot paleomagnetic and sedimentological study has been conducted in the Neogene-Quaternary infilling materials of the Bajo Segura Basin (Eastern Betics, SE Spain). The studied sediments belong to the youngest (late Pliocene-Quaternary) lithostratigraphic unit of the basin (P-Q unit). The statistical analysis of tectonic striations and stylolitic dissolutions on the conglomerate limestone clasts indicates a NNW-SSE maximum compression direction. This is in accordance with the principal susceptibility axes, determined from the anisotropy of magnetic susceptibility measurements (AMS) of the interbedded siltstones where the Kmax axis group in a subhorizontal N 080° E direction.A total of 45 core samples have been collected from 16 stratigraphic siltstone levels encompassing the described section at Crevillente with the aim to establish a magnetochronology. Upwards in the section the NRM intensity and bulk susceptibility vary from 10^–2 to 10^–3 A/m and from 1550 to 100 × 10^–6 SI, respectively. The mean characteristic remanent magnetization (ChRM) after bedding correction (Dec/Inc = 10°/60°, ₉₅ = 8.7°, k = 15.9) is deviated slightly towards the E from the reference N direction, and could reflect a deflection related to the observed magnetic fabric although no clear correlation exists with AMS parameters. The derived magnetostratigraphy reveals only one reversal boundary within the upper third of the section, delimiting an upper reversal magnetozone which has been tentatively correlated with the Olduwai subchron close to the Plio-Pleistocene boundary.Pilot and preliminary rock-magnetic experiments and standard X-ray difraction (XRD) analysis have been performed on typical samples in order to establish the carriers of magnetization and characterize the sedimentological and magnetic-acquisition processes in these sediments. Magnetic carriers seem to be dominated by magnetite with a relative grain size within the PSD state (pseudo single-domain) threshold, but closer to the MD (multi domain) threshold, which favours the detrital origin for the magnetite.     

Changes in Magnetic Properties of Baked Archaeological Samples. Implications for Palaeointensity Determination

Rock magnetic investigations of archaeological materials of burnt clay from Eneolithic ovens (4500 years BC) showed particular changes with time in the magnetic mineralogy of samples, stored under normal conditions. Our results indicate that well-burnt clay from the archaeological materials contains a significant amount of very fine magnetic grains, which could notably influence the rock magnetic properties and behavior at room temperature. The main observations after 4 years of storage under laboratory conditions are as follows: 1) decrease in the final unblocking temperature of NRM from 600–620°C to 580°C and 2) increase in the capacity of laboratory TRM acquisition. The most probable mechanism responsible for the observed changes is supposed to be fast low-temperature oxidation of the finest (superparamagnetic) grains and the development of the maghemite shell in coarser single-domain grains. The Thellier palaeointensity experiments, carried out at the beginning of the study, showed very good results, which satisfy all acceptance criteria, applied to evaluation of the results, quite well. Palaeointensity determinations repeated 4 years later on samples from the same material showed the experimental results to be of significantly inferior quality. The main difference is the presence of the significant deviation (change in the slope) on the Arai diagram after T>350–400°C. The calculated palaeointensity is either higher than the one obtained before, or similar, but evaluated with large uncertainty. Therefore, we conclude that the possibility to obtain biased palaeointensity values increases during short-time storage (i.e. several years) due to the low-temperature changes of the material.