High-field cantilever magnetometry as a tool for the determination of the magnetocrystalline anisotropy of single crystals

Cantilever torque magnetometry is utilized widely in physics and material science for the determination of magnetic properties of thin films and semiconductors. Here, we report on its first application in rock magnetism, namely the determination of K₁ and K₂ of single crystal octahedra of natural magnetite. The design of cantilever magnetometers allows optimization for the specific research question at hand. For the present study, a cantilever magnetometer was used that enables measurement of samples with a volume up to 64 mm³. It can be inserted into an electromagnet with a maximum field of 2 T. The cantilever spring is suitable for torque values ranging from 7.5 × 10^− 7 N·m to 5 × 10^− 6 N·m. The torque is detected capacitively; the measured capacitance is converted into torque by using a calibrated feedback coil. The magnetometer allows in-situ rotation of the sample in both directions and is, therefore, also suitable to analyze rotational hysteresis effects.The evaluation of the magnetite anisotropy constants involved Fourier analysis of the torque signal on the magnetite crystals' (001) and (110) planes. The absolute anisotropy constant has been computed using the extrapolation-to-infinite-field method. The value of K₁ at room temperature is determined at − 1.28 × 10⁴ [J m^− 3] (± 0.13, i.e. 10%) and that of K₂ at − 2.8 × 10³ [J m^− 3] (± 0.1, i.e. 2%). These values concur with earlier determinations that could not provide an instrumental error, in contrast with this work.The cantilever magnetometer performs four times faster than other torque magnetometers used for rock magnetic studies. This makes the instrument also suitable for magnetic fabric analysis.     

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.     

Adsorption of NO, SO2 and light hydrocarbons on activated Greek brown coals

Twenty-eight samples of peat, peaty lignites and lignites (of both matrix and xylite-rich lithotypes) and subbituminous coals have been physically activated by pyrolysis. The results show that the surface area of the activated coal samples increases substantially and the higher the carbon content of the samples the higher the surface area.The adsorption capacity of the activated coals for NO, SO₂, C₃H₆ and a mixture of light hydrocarbons (CH₄, C₂H₆, C₃H₈ and C₄H₁₀) at various temperatures was measured on selected samples. The result shows a positive correlation between the surface area and the gas adsorption. In contrast, the gas adsorption is inversely correlated with the temperature. The maximum recorded adsorption values are: NO = 8.22 × 10^− 5 mol/g at 35 °C; SO₂ = 38.65 × 10^− 5 mol/g at 60 °C; C₃H₆ = 38.9 × 10^− 5 mol/g at 35 °C; and light hydrocarbons = 19.24 × 10^− 5 mol/g at 35 °C. Adsorption of C₃H₆ cannot be correlated with either NO or SO₂. However, there is a significant positive correlation between NO and SO₂ adsorptions. The long chain hydrocarbons are preferentially adsorbed on activated lignites as compared to the short chain hydrocarbons.The results also suggest a positive correlation between surface area and the content of telohuminite maceral sub-group above the level of 45%.     

Correlation between dissolved He concentration and Cl in groundwater at Äspö, Sweden

Tunnel excavation at Äspö Island, Sweden, has caused severe groundwater disturbance, gradually extending deeper into the tunnel as present-day Baltic seawater intrudes through fractures connecting to the surface. However, the paleo-hydrogeochemical conditions have remained in the deep highly saline waters that have avoided mixing. A correlation has been observed between dissolved ⁴He concentration and Cl⁻ ion concentration, measured every two years from 1995 to 2001 at Äspö. Groundwater mixing conditions can be examined by the correlations between 1/Cl, ³⁶Cl/Cl, and ³H concentrations. Subsurface production is responsible for the majority of the ³⁶Cl and excess dissolved ⁴He of interstitial groundwater in fractures. The secular equilibrium ratio of ³⁶Cl/Cl in rock was theoretically estimated to be (5.05 ± 0.82) × 10⁻¹⁴ based on the neutron flux intensity, a value comparable to the measured ³⁶Cl/Cl ratio in rock and groundwater. The degassing crustal ⁴He flux was estimated to be 2.9 × 10⁻⁸  1.3 × 10⁻⁶ (ccSTP/cm²a) using the HTO diffusion coefficient for the Äspö diorite. The ⁴He accumulation rate ranges from 6.8 × 10⁻¹⁰ (for the in situ accumulation rate) to 7.0 × 10⁻⁹ (ccSTP/(g_water · a) considering both ⁴He in situ production and the degassing flux, assuming ⁴He is accumulated constantly in groundwater. By comparing the subsurface ³⁶Cl increase with ⁴He concentrations in groundwater, the ⁴He accumulation rate was determined from data for groundwater arriving at the secular equilibrium of ³⁶Cl/Cl. The ⁴He accumulation rate was found to be (1.83 ± 0.72) × 10⁻⁸ ccSTP/(g_water · a) without determining the magnitude of degassing ⁴He flux.     

Comparison of methods for the estimation of pyrite oxidation rate in a waste rock pile at Mine Doyon site, Quebec, Canada

Several methods were evaluated and compared for the estimation of pyrite oxidation rates (POR) in waste rock at Mine Doyon, Quebec, Canada. Methods based on data collected in situ, such as the interpretation of temperature and oxygen concentration profiles (TOP) measured in the waste rock pile and pyrite mass balance (PMB) on solid phase samples were compared with the oxygen consumption measurements (OCM) in closed chamber in the laboratory. A 1-D analytical solution to a gas and heat transport equation used temperature and oxygen profiles (TOP) measured in the pile for the preliminary POR estimates at a site close to the slope of the pile (Site 6) and in the core of the pile (Site 7). Resulting POR values were 1.1 × 10^− 9 mol(O₂) kg^− 1 s^− 1 and 1.0 × 10^− 10 mol(O₂) kg^− 1 s^− 1 for the slope site and the core site, respectively. Oxidation rates based on pyrite mass balance (PMB) calculations for solid samples were 2.21 × 10^− 9 mol(O₂) kg^− 1 s^− 1 and 2.03 × 10^− 9 mol(O₂) kg^− 1 s^− 1, respectively, for the same slope and core sites, but the difference between sites was within the error margin. The OCM measurements in the laboratory on fresh waste rock samples yielded higher POR values than field methods, with average oxidation rate of 6.7 × 10^− 8 mol(O₂) kg^− 1 s^− 1. However, the OCM results on weathered and decomposed material from the rock stockpile (average oxidation rate 3.4 × 10^− 9 mol(O₂) kg^− 1 s^− 1) were consistent with results from the field-based estimates. When POR values based on fresh material are excluded, the remaining POR values for all methods range from 1.0 × 10^− 10 to 3.4 × 10^− 9 mol(O₂) kg^− 1 s^− 1. The lowest estimated value (1.0 × 10^− 10 mol(O₂) kg^− 1 s^− 1) was based on TOP estimates in the interior of the pile where oxygen transport was limited by diffusion from the surface. These results suggest that small-scale OCM laboratory experiments may provide relatively representative values of POR in the zones of waste rock piles in which oxygen transport is not dominated by diffusion.     

Magnetic fabric variations in Mesozoic black shales, Northern Siberia, Russia: Possible paleomagnetic implications

A 28-m-long section situated on the coast of the Arctic Ocean, Russia (74°N, 113°E) was extensively sampled primarily for the purpose of magnetostratigraphic investigations across the Jurassic/Cretaceous boundary. The section consists predominantly of marine black shales with abundant siderite concretions and several distinct siderite cemented layers. Low-field magnetic susceptibility (k) ranges from 8 × 10^− 5 to 2 × 10^− 3 SI and is predominantly controlled by the paramagnetic minerals, i.e. iron-bearing chlorites, micas, and siderite. The siderite-bearing samples possess the highest magnetic susceptibility, usually one order of magnitude higher than the neighboring rock. The intensity of the natural remanent magnetization (M₀) varies between 1 × 10^− 5 and 6 × 10^− 3 A/m. Several samples possessing extremely high values of M₀ were found. There is no apparent correlation between the high k and high M₀ values; on the contrary, the samples with relatively high M₀ values possess average magnetic susceptibility and vice versa. According to the low-field anisotropy of magnetic susceptibility (AMS), three different groups of samples can be distinguished. In the siderite-bearing samples (i), an inverse magnetic fabric is observed, i.e., the maximum and minimum principal susceptibility directions are interchanged and the magnetic fabric has a distinctly prolate shape. Triaxial-fabric samples (ii), showing an intermediate magnetic fabric, are always characterized by high M₀ values. It seems probable that the magnetic fabric is controlled by the preferred orientation of paramagnetic phyllosilicates, e.g., chlorite and mica, and by some ferromagnetic mineral with anomalous orientation in relation to the bedding plane. Oblate-fabric samples (iii) are characterized by a bedding-controlled magnetic fabric, and by moderate magnetic susceptibility and M₀ values. The magnetic fabric is controlled by the preferred orientation of phyllosilicate minerals and, to a minor extent, by a ferrimagnetic fraction, most probably detrital magnetite. Considering the magnetic fabric together with paleomagnetic component analyses, the siderite-bearing, and the high-NRM samples (about 15% of samples) were excluded from further magnetostratigraphic research.     

Oxidation of As-bearing gold ore—a comparison of batch and column experiments

This study deals with the experimental determination of the rate of weathering and As release from Au-bearing sulfide ores of the Mokrsko-West deposit (Czech Republic). The elevated As contents in the ore and the possible As mobilisation must be taken into account due to the close proximity of the deposit to the Vltava River, a source of drinking water for Prague. Crushed and homogenized ore material was divided into four grain-size fractions showing uniform chemical and mineralogical composition and subjected to batch and column leaching experiments. The most important reactions controlling metal leaching include (i) oxidation of sulfides, (ii) carbonate equilibrium and (iii) precipitation of hydrated ferric oxides (HFO). Hydrated ferric oxides were found to be important sorbents of mobilized As. The highest concentration of As in the leachates was obtained from the 64–1000 μm fraction. The oxidation rate in the agitated batch experiment calculated on the basis of sulfate concentrations is an order of magnitude higher (3.8×10⁻⁹ to 4.4×10⁻⁸ mol SO₄²⁻ h⁻¹ g⁻¹) than in the static column experiment (9.6×10⁻¹⁰ to 7.4×10⁻⁹ mol SO₄²⁻ h⁻¹ g⁻¹). The higher oxidation rate of batch experiments is explained by abrasion of oxidation products (mainly HFO) and by further exposition of reaction surfaces of the sulfide grains.     

Electron paramagnetic resonance (EPR) spectroscopy in massive sulphide exploration, Rosebery mine area, western Tasmania, Australia

Electron paramagnetic resonance (EPR) spectroscopy of hot HNO₃ insoluble residues of rock powders is used as a new exploration technique for the volcanic-hosted massive sulphide (VHMS) deposit in the Rosebery mine area. The EPR signal intensities measured in 326.5±5 mT sweeps are strong in the altered rocks, and show a negative correlation with Ca, Na and Sr, and a positive correlation with K/Na, Rb/Sr and (K × Rb)/(Ca × Na × Sr). The EPR intensities measured in 326.5±100 mT sweeps show high values in the footwall pyroclastics, host rocks and hanging wall pyroclastics near and around the Rosebery deposit, and correlate positively with K, Fe, Mn, Ba, F, Rb, Zn, Pb and Zr. The Rosebery deposit and associated footwall alteration zone are located at the intersection of two elongated paramagnetic halos. The first is characterized by strong intensities of [AlO₄]° signals measured at magnetic flux density sweeps over 326.5±5 mT, trends NE–SW, and passes discordantly from the west to the east the White Spur Formation, altered footwall (footwall alteration zone), host rock of the Rosebery deposit, hanging wall and Mount Black Volcanics. The second, largely stratabound, halo is defined by strong intensities of Mn²⁺ sextets observed at magnetic flux density sweeps over 326.5±100 mT, runs N–S following the stratigraphic trend, and outlines the mineralized host rock and footwall alteration zone. It also extends toward the south into the unaltered footwall and hanging wall rocks. The first type of halo is considered to be related to wall rock alteration due to the VHMS mineralization processes as well to later Devonian metamorphism, and the second is thought to be related to massive sulphide mineralization alone.     

11 Å tobermorite from cement bypass dust and waste container glass: A feasibility study

A novel one-step hydrothermal synthesis of 11 Å tobermorite, a cation exchanger, from a unique combination of waste materials is reported. 11 Å tobermorite was prepared from stoicheiometric quantities of cement bypass dust and waste container glass at 100 °C in water. The product also comprised 10 wt.% calcite and trace quartz as residual parent phases from the cement bypass dust. In a batch sorption study at 20 °C the uptakes of Cd²⁺ and Pb²⁺ by the waste-derived tobermorite product were found to be 171 mg g^− 1 and 467 mg g^− 1, respectively, and in both cases the removal process could be described using a simple pseudo-second-order rate model (k₂ = 2.30 × 10^− 5 g mg^− 1 min^− 1 and 5.09 × 10^− 5 g mg^− 1 min^− 1, respectively). The sorption characteristics of the 11 Å tobermorite are compared with those of other waste-derived sorbents and potential applications are discussed.     

The aqueous geochemistry of Zr and the solubility of some Zr-bearing minerals

Literature data on the thermodynamics of complexation of Zr with inorganic species, at 25°C, have been critically reviewed. The preponderance of published complexation constants deal with F⁻ and OH⁻ ions. Stability constants for the complexation reactions are relatively independent of ionic strength and thus recomended values for each ligand type are averages of the most reliable data. Complexation constants under elevated conditions (T 250°C andP_v = P_H2O) have been predicted for various Zr complexes (F⁻, Cl⁻, SO₄²⁻ and OH⁻) using Helgeson's electrostatic approach. Predominance diagrams (calculated for simple systems with these constants) suggest that, over a wide range of pH conditions, Zr(OH)_4(aq) will dominate the aqueous geochemistry of Zr except under very high activities of competing ligands (e.g., F⁻, SO₄²⁻).The solubilities of vlasovite [Na₂ZrSi₄O₁₁] and weloganite [Sr₃Na₂Zr(CO₃)₆·3H₂O have been measured in KCI solutions (0.5–1.0 M) at 50°C. Weloganite dissolution is complicated by the predictable precipitation of strontianite (SrCO₃) whereas vlasovite dissolves incongruently. Solubility products for the dissolution of welonganite and vlasovite are determined to be −28.96±0.14 and −20.40±1.18, respectively. Concentrations of Zr up to 10⁻³ m were present in the experimental solutions; the presence of large amounts of Zr in aqueous solutions support the possibility of extensive remobilization of Zr during hydrothermal mineralization.     

Iron speciation in interaction with organic matter: Modelling and experimental approach

The present study aims to model iron speciation when interacting with natural organic matter. Experimental data for iron speciation were achieved with insolubilized humic acid as an organic matter analogue for 1.8 × 10^− 3 M and 1.8 × 10^− 4 M iron concentrations and 2–5 pH range. Combining EPR spectroscopy and chemical analysis allowed us to fit NICA-Donnan model parameters for both organic complexation of iron and oxides precipitation.     

A method for determining both diffusion and sorption coefficients of rock medium within a few days by adopting a micro-reactor technique

Migration properties characterized by physico-chemical factors such as distribution coefficient (K_d) and diffusion coefficient (D_e) are of great concern in performance assessment of high-level radioactive waste disposal in a deep geologic environment. These coefficients are normally obtained with different sample geometries using conventional methods, i.e., crushed samples by the batch sorption method for K_d determination and block samples by the through-diffusion method for D_e. A size dependence on both K_d and D_e has been reported and an additional correction due to size difference is required to maintain consistency of the data set. A fast method was developed, hereafter referred to as the micro-channel method, to determine both the sorption coefficient (R_d) and D_e using non-crushed rock sample by adopting the micro-reactor technique. In this method, a radionuclide solution is injected into a micro-channel (20 mm length, 4 mm width, 160 μm depth), which is in contact with a plate-shaped rock sample. A part of the injected radionuclide can diffuse into the rock matrix and/or adsorb on the rock surface and this results in an inlet-outlet concentration difference. A breakthrough curve is easily obtained with a short observation period because the injection amount is extremely small and is comparable to that escaping by diffusion into the matrix. The breakthrough curve is analyzed by a two-dimensional diffusion-advection equation to evaluate R_d and D_e.In the present study, tritiated water (specific activity, 1.2 × 10⁴ Bq/mL; pH, 6) was injected into the micro-channel, and the breakthrough curve of ³H obtained. A series of experiments was carried out by changing the flow rate of the tritiated water (2.6 × 10⁻⁵–7.7 × 10⁻⁴ m/s). Rock samples were biotite granite from the Makabe area, Japan. The diffusion coefficient evaluated by least squares fitting to the numerical solutions (D_e = 1.5 × 10⁻¹¹ m²/s) agreed well with that obtained by the through-diffusion method (1.3 × 10⁻¹¹ m²/s). The breakthrough curve of Cs ([Cs] = 1.0 × 10⁻⁷ mol/L, pH 6) labeled with ¹³⁴Cs (specific activity adjusted to 4.9 × 10¹ Bq/mL) was also obtained. A nearly constant R_d value (5.5 × 10⁻² m³/kg) was found when the flow rate was less than 2.5 × 10⁻⁴ m/s. This implied that the sorption equilibrium is reached and K_d is obtained by the present method. This value was almost identical to K_d obtained by the batch sorption method (5.0 × 10⁻² m³/kg), but the testing period was very different; 1 day and 7 days, respectively. It is concluded that application of the micro-channel method provided advantages when compared with the conventional methods.     

Secular change of permeability in the fracture zone near the Nojima fault estimated using strain changes due to water injection experiments

Water injection experiments were performed in 1997, 2000 and 2003 at the 1800 m borehole near the fracture zone of the 1995 Hyogo-ken Nanbu earthquake. During these experiments, a contraction of about 10^− 8–10^− 7 was observed with three-component strainmeters at a bottom of the 800 m borehole, 70 m southwest of the 1800 m borehole. We estimated hydraulic properties of the fracture zone near the Nojima fault by using the strain data to investigate a healing of the fault during the postseismic stage. We calculated pore pressure changes due to the water injection using Darcy's equation and obtained strain changes due to the pore pressure changes as elastic deformations of the crust. The calculated strain changes have a nearly agreement with the observed strain changes. Hydraulic conductivity in 1997, 2000 and 2003 was determined to be 0.9 ± 0.2 × 10^− 6, 0.8 ± 0.2 × 10^− 6 and 0.4 ± 0.1 × 10^− 6 m/s, respectively. The reduced hydraulic conductivities in 2000 and 2003 suggest that the fractures had been healing.     

Application of I / I to define the source of hydrocarbons of the Pol-Chuc, Abkatún and Taratunich–Batab oil reservoirs, Bay of Campeche, southern Mexico

Homogeneous ¹²⁹I / ¹²⁷I ratios from 6.51 ± 1.36 × 10^− 14 to 12.6 ± 1.49 × 10^− 14 were measured in formation brine at the Pol-Chuc, Abkatún, Taratunich–Batab off-shore oil reservoirs, Bay of Campeche in S-Mexico. Cosmogenic production could account for a homogeneous, Late Cretaceous/Paleocene time period (71.3 ± 5.3 to 56.3 ± 2.9 Ma) for the sedimentation and burial of organic material in the source formation. As the actual reservoir column is formed by Paleocene to Kimmeridgian sediments, the lower part of the lithological column must have received hydrocarbons that migrated downward from an initial source rock (Upper Cretaceous?) during a post-Paleocene event, probably during Miocene. Cosmogenic production from Tithonian shales can be excluded, as ¹²⁹I would have been decayed. As an alternative or complementary process, the subsurface, radiogenic production of ¹²⁹I / ¹²⁷I by ²³⁸U-fission in Uranium-enriched sediments should also be considered to explain the present, low ¹²⁹I / ¹²⁷I ratios.     

Rates of Deglaciation during the Last Glaciation and Holocene in the Cordillera Vilcanota-Quelccaya Ice Cap Region, Southeastern Perú

Moraine chronology is combined with digital topography to model deglacial rates of paleoglacier volumes in both the Huancané Valley on the west side of the Quelccaya Ice Cap and the Upismayo Valley on the northwest side of the Cordillera Vilcanota. The fastest rates of deglaciation (39×10⁻⁵ to 114×10⁻⁵ km³ yr⁻¹ and 112×10⁻⁵ to 247×10⁻⁵ km³ yr⁻¹ for each valley, respectively) were calculated for the most recent paleoglaciers, corresponding to the last few centuries. These results are consistent with observations in the Venezuelan Andes showing high rates of deglaciation since the Little Ice Age. These rates also fall within the range of 20th century rates of deglaciation measured on the Quelccaya Ice Cap (29×10⁻⁵ to 220×10⁻⁵ km³ yr⁻¹, Brecher and Thompson, 1993; Thompson, 2000). These results imply that rates of deglaciation may fluctuate significantly over time and that high rates of deglaciation may not be exclusive to the late 20th century. Equilibrium line altitude (ELA) depressions for the ice volumes of the last glaciation modeled here were computed as 230 m for the Quelccaya Ice Cap and 170 m for the Cordillera Vilcanota. Maximum ELA depressions are lower than previously published: <500 m for the Cordillera Vilcanota and <400 m for the Quelccaya Ice Cap. These lower values could imply a topographic control over paleoglacier extent.     

As–(Ag) sulphide veins in the Spanish Central System: further evidence for a hydrothermal event of Permian age

The Spanish Central System (SCS) has been subjected to repeated deformation and fluid flow events which have produced both sulphide-bearing and barren vein systems. Although several hydrothermal episodes took place between 300 and 100 Ma, fluid circulation during the Permian was especially important, giving rise to a range of different types of deposits. This study presents a multidisciplinary approach leading to the characterisation of the chemistry and age of the hydrothermal fluids that produced the As–(Ag) mineralised stockwork of Mónica mine (Bustaviejo, Madrid). Fluid inclusion data indicate the presence of two different fluids. An initial ore stage (I) formed from a low- to moderate salinity (3–8 wt.% eq. NaCl) H₂O–NaCl–CO₂–CH₄ fluid, at minimum trapping temperature of 350±15 °C and 0.3 kbar. A second H₂O–NaCl fluid is found in three types of fluid inclusions: a high temperature and low salinity type (340±20 °C; 0.8–3.1 wt.% eq. NaCl) also associated to ore stage I, a moderate temperature and very low salinity type (160–255 °C; 0–1.5 wt.% eq. NaCl) represented in ore stage III, and a very low temperature and hypersaline type (60–70 °C; 30–35 wt.% NaCl), unrelated to the mineralising stages and clearly postdating the previous types. ⁴⁰Ar–³⁹Ar dating on muscovite from the early As–Fe stage (I) has provided an age of 286±4 Ma, synchronous with the late emplacement phases of La Cabrera plutonic massif (288±5 Ma) and with other Permian hydrothermal events like Sn–W skarns and W–(Sn) sulphide veins. δ¹⁸O of water in equilibrium with stage I quartz (5.3–7.7‰), δD of water in equilibrium with coexisting muscovite (−16.0‰ to −2.0‰), and sulphide δ³⁴S (1.5–3.6‰) values are compatible with waters that leached metamorphic rocks. The dominant mechanism of the As–(Ag) deposition was mixing and dilution processes between aqueous–carbonic and aqueous fluids for stage I (As–Fe), and nearly isobaric cooling processes for stages II (Zn–Cu–Sn) and III (Pb–Ag). The origin and hydrothermal evolution of As–(Ag) veins is comparable to other hydrothermal Permian events in the Spanish Central System.     

Earth''s earliest continental lithosphere, hydrothermal flux and crustal recycling

The Kaapvaal craton in southern Africa and the Pilbara craton of northwestern Australia are the largest regions on Earth to have retained relatively pristine mid-Archaean rocks (3.0–4.0 Ga).The Kaapvaal craton covers about 1.2×10⁶ km², and varies in lithospheric thickness between 170 and 350 km. At surface, the craton can be subdivided into a number of Archaean sub-domains; some of the subdomains are also well defined at depth, and local variations in tomography of the lithosphere correspond closely with subdomain boundaries at surface.The Archaean history of the Kaapvaal craton spans about 1 Gyr and can be conveniently subdivided into two periods, each of about the same length as the Phanerozoic. The first period, from circa 3.7-3.1 Ga, records the initial separation of the cratonic lithosphere from the asthenosphere, terminating with a major pulse of accretion tectonics between 3.2 and 3.1 Ga, which includes the formation of “paired metamorphic belts”. This period of continental growth can be compared to plate tectonic processes occurring in modern-day oceanic basins. However, the difference is that in the mid-Archaean, these oceanic processes appear to have occurred in shallower water depths than the modern ocean basins. The second period, from circa 3.1-2.6 Ga, records intra-continental and continental-edge processes: continental growth during this period occurred predominantly through a combination of tectonic accretion of crustal fragments and subduction-related igneous processes, in much the same way as has been documented along the margins of the Pacific and Tethys oceans since the Mesozoic.The intra-oceanic processes resulted in small, but deep-rooted continental nucleii; the first separation of this early continental lithosphere could only have occurred when the mean elevation of mid-oceanicridges sank below sea-level. Substantial recycling of continental lithosphere into the mantle must have occurred during this period of Earth history. During the second period, at least two large continental nucleii amalgamated during collisional processes which, together with internal chemical differentiation processes, created the first stable continental landmass. This landmass, which is known to have been substantially bigger than its present outline, may have been part of the Earth's first supercontinent.The oldest known subdomains of the craton include the oceanic-like rocks of the Barberton greenstone belt. The comagmatic mafic-ultramafic rocks (3.48–3.49 Ga) of this belt represent a remnant of very early oceanic-like lithosphere (known as the Jamestown Ophiolite Complex), which was obducted, approximately 45 Ma after its formation, onto a volcanic arc-like terrain by processes similar to those which have emplaced modern ophiolites at convergent margins of Phanerozoic continents. The early metamorphic history, metamorphic mineralogy, oxygen isotope profiles and degree of hydration of the 3.49 Ga Jamestown Ophiolite Complex are similar to present day subseafloor hydrothermal systems. The ratio of ΔMg to ΔSi for hydrothermally altered igneous rocks, both present day and Archaean, are remarkably uniform at −5(±0.9) and the same as that of hydrothermal fluids venting on the present-day East Pacific Rise. This observation suggests that the process of Mg exchange for Si in hydrothermal systems was commonplace throughout Earth's history.The chemistry of vent fluids and hydrothermally altered igneous rocks was combined with an inventory of ³He in the mantle to model Earth's total hydrothermal flux. An Archaean flux (at 3.5 Ga) of about 10 times present day was accompanied by a correspondingly greater abundance of Mg(OH), SiO₂, carbonate and Fe---Mn metasomatic rock types as well as massive sulphides. Assuming a constant column of seawater since the Archaean, the average residence time of seawater in the oceanic crust was 1.65−8.90×10⁵ years in the Archaean. Assuming that ³He and heat are transported from the mantle in silicate melts in uniform proportions, the model stipulates that accretion of oceanic crust decreased from about 3.43−6.5×10¹⁷ g/yr to a present-day rate of 0.52−0.8×10¹⁷ g/yr, with a drop in heat flow from 1.4−2.6×10²⁰ cal/yr to 2.1−3.2×10¹⁹ cal/year.The total amounts of SiO₂ and Fe mobilised in marine hydrothermal systems since 3.5 Ga is less than their masses in the present exosphere reservoirs (crust, hydrosphere, atmosphere). The total amounts of Mg, K, CO₂, Ca and Mn are greater than their respective masses in exosphere reservoirs; therefore, they must have been recycled into mantle. The total mass of recycled hydrothermal components is small compared to the mass of the mantle. The flux of volatiles in hydrothermal systems is large compared to their volume in the atmosphere suggesting that the CO₂ and O₂ budgets of the atmosphere have been influenced by hydrothermal processes, especially in the Archaean.     

Source parameters of the ML 4.1 earthquake of November 08, 2006, southeast Beni-Suef, northern Egypt

In the early morning hours on Wednesday November 08, 2006 at 04:32:10(GMT) a small earthquake of M_L 4.1 has occurred at southeast Beni-Suef, approximately 160 km SEE of Cairo, northern Egypt. The quake has been felt as far as Cairo and its surroundings while no casualties were reported. The instrumental epicentre is located at 28.57°N and 31.55°E. Seismic moment is 1.76 E14 Nm, corresponding to a moment magnitude M_w 3.5. Following a Brune model, the source radius is 0.3 km with an average dislocation of 1.8 cm and a 2.4 MPa stress drop. The source mechanism from a first motion fault plane solution shows a left-lateral strike-slip mechanism with a minor dip-slip component along fault NNW striking at 161°, dipping 52° to the west and rake −5°. Trend and plunging of the maximum and minimum principle axes P/T are 125°, 28°, 21°, and 23°, respectively. A comparison with the mechanism of the October, 1999 event shows similarities in faulting type and orientation of nodal planes.Eight small earthquakes (3.0  M_L < 5.0) were also recorded by the Egyptian National Seismological Network (ENSN) from the same region. We estimate the source parameters and fault mechanism solutions (FMS) for these earthquakes using displacement spectra and P-wave polarities, respectively. The obtained source parameters including seismic moments of 4.9 × 10¹²–5.04 × 10¹⁵ Nm, stress drops of 0.2–4.9 MPa and relative displacement of 0.1–9.1 cm. The azimuths of T-axes determined from FMS are oriented in NNE–SSW direction. This direction is consistent with the present-day stress field in Egypt and the last phase of stress field changes in the Late Pleistocene, as well as with recent GPS measurements.     

Dynamic recrystallization of wet synthetic polycrystalline halite: dependence of grain size distribution on flow stress, temperature and strain

It is often observed that dynamic recrystallization results in a recrystallized grain size distribution with a mean grain size that is inversely related to the flow stress. However, it is still open to discussion if theoretical models that underpin recrystallized grain size–stress relations offer a satisfactorily microphysical basis. The temperature dependence of recrystallized grain size, predicted by most of these models, is rarely observed, possibly because it is usually not systematically investigated. In this study, samples of wet halite containing >10 ppm water (by weight) were deformed in axial compression at 50 MPa confining pressure. The evolution of the recrystallized grain size distribution with strain was investigated using experiments achieving natural strains of 0.07, 0.12 and 0.25 at a strain rate of 5×10⁻⁷ s⁻¹ and a temperature of 125 °C. The stress and temperature dependence of recrystallized grain size was systematically investigated using experiments achieving fixed strains of 0.29–0.46 (and one to a strain of 0.68) at constant strain rates of 5×10⁻⁷–1×10⁻⁴ s⁻¹ and temperatures of 75–240 °C, yielding stresses of 7–22 MPa. The microstructures and full grain size distributions of all samples were analyzed. The results showed that deformation occurred by a combination of dislocation creep and solution-precipitation creep. Dynamic recrystallization occurred in all samples and was dominated by fluid assisted grain boundary migration. During deformation, grain boundary migration results in a competition between grain growth due to the removal of grains with high internal strain energy and grain size reduction due to grain dissection (i.e. moving boundaries that crosscut or consume parts of neighbouring grains). At steady state, grain growth and grain size reduction processes balance, yielding constant flow stress and recrystallized grain size that is inversely related to stress and temperature. Evaluation of the recrystallized grain size data against the different models for the development of mean steady state recrystallized grain size revealed that the data are best described by a model based on the hypothesis that recrystallized grain size organizes itself in the boundary between the (grain size sensitive) solution-precipitation and (grain size insensitive) dislocation creep fields. Application of a piezometer, calibrated using the recrystallized grain size data, to natural halite rock revealed that paleostresses can vary significantly with temperature (up to a factor of 2.5 for T=50–200 °C) and that the existing temperature independent recrystallized grain size–stress piezometer may significantly underestimate flow stresses in natural halite rock.     

Geochemistry and evolution of ore-forming fluids of the Yueshan Cu–Au skarn- and vein-type deposits, Anhui Province, South China

The Yueshan mineral belt is geotectonically located at the centre of the Changjiang deep fracture zone or depression of the lower Yangtze platform. Two main types of ore deposits occur in the Yueshan orefield: Cu–Au–(Fe) skarn deposits and Cu–Mo–Au–(Pb–Zn) hydrothermal vein-type deposits. Almost all deposits of economic interest are concentrated within and around the eastern and northern branches of the Yueshan dioritic intrusion. In the vicinity of the Zongpu and Wuhen intrusions, there are many Cu–Pb–Zn–Au–(S) vein-type and a few Cu–Fe–(Au) skarn-type occurrences.Fluid inclusion studies show that the ore-forming fluids are characterised by a Cl⁻(S)–Na⁺–K⁺ chemical association. Hydrothermal activity associated with the above two deposit types was related to the Yueshan intrusion. The fluid salinity was high during the mineralisation processes and the fluid also underwent boiling and mixed with meteoric water. In comparison, the hydrothermal activity related to the Zongpu and Wuhen intrusions was characterised by low salinity fluids. Chlorine and sulphur species played an important role in the transport of ore-forming components.Hydrogen- and oxygen-isotope data also suggest that the ore-forming fluids in the Yueshan mineral belt consisted of magmatic water, mixed in various proportions with meteoric water. The enrichment of ore-forming components in the magmatic waters resulted from fluid–melt partitioning. The ore fluids of magmatic origin formed large Cu–Au deposits, whereas ore fluids of mixed magmatic-meteoric origin formed small- to medium-sized deposits.The sulphur isotopic composition of the skarn- and vein-type deposits varies from − 11.3‰ to + 19.2‰ and from + 4.2‰ to + 10.0‰, respectively. These variations do not appear to have been resulted from changes of physicochemical conditions, rather due to compositional variation of sulphur at the source(s) and by water–rock interaction. Complex water–rock interaction between the ore-bearing magmatic fluids and sedimentary wall rocks was responsible for sulphur mixing. Lead and silicon isotopic compositions of the two deposit types and host rocks provide similar indications for the sources and evolution of the ore-forming fluids.Hydrodynamic calculations show that magmatic ore-forming fluids were channelled upwards into faults, fractures and porous media with velocities of 1.4 m/s, 9.8 × 10^− 1 to 9.8 × 10^− 7 m/s and 3.6 × 10^− 7 to 4.6 × 10^− 7 m/s, respectively. A decrease of fluid migration velocity in porous media or tiny fractures in the contact zones between the intrusive rocks and the Triassic sedimentary rocks led to the deposition of the ore-forming components. The major species responsible for Cu transport are deduced to have been CuCl, CuCl₂⁻, CuCl₃²⁻ and CuClOH, whereas Au was transported as Au₂(HS)₂S²⁻, Au(HS)₂⁻, AuHS and AuH₃SiO₄ complexes. Cooling and a decrease in chloride ion concentration caused by fluid boiling and mixing were the principal causes of Cu deposition. Gold deposition was related to decrease of pH, total sulphur concentration and fO₂, which resulted from fluid boiling and mixing.Geological and geochemical characteristics of the two deposit types in the Yueshan mineral belt suggest that there is a close genetic relationship with the dioritic magmatism. Geochronological data show that the magmatic activity and the mineralisation took place between 130 and 136 Ma and represent a continuous process during the Yanshanian time. The cooling of the intrusions and the mineralisation event might have lasted about 6 Ma. The cooling rate of the magmatic intrusions was 80 to 120 °C my^− 1, which permitted sufficient heat supply by magma to the ore-forming system.