Isopropylxanthate ions uptake by modified natural zeolite and removal by dissolved air flotation

This work describes a laboratory study concerning the adsorption of isopropylxanthate ions onto modified zeolites particles. The separation of the loaded carrier and their removal, from aqueous solutions, was conducted by flocculation followed by dissolved air flotation, DAF. The zeolite employed was a natural sample (approximately 48% clinoptilolite and 30% mordenite) which was previously treated with sodium ions (activation) and modified with copper ions (Cu–Z) before the xanthate ions uptake. Adsorption capacities (q_m) for Cu–Z were 0.34 meq g^− 1 for the powdered form, and 1.12 meq g^− 1 for the floc form. The adsorption capacity for the floc form appears to involve an enhanced electrostatic adsorption due to the positive sites on the floc surface. In all cases, the isopropylxanthate concentration in the treated water was found to be negligible (< 0.04 mg L^{− 1}). The flotation technique showed to be a fast process, requires a low recycle ratio (20%) in air saturated water, and the treated water ended up with a very low residual turbidity (6.8 NTU). It is believed that this adsorption–flotation technique, here named adsorptive particulate flotation, using activated and modified natural zeolite has a high potential as an alternative for pollutants removal (copper and isopropylxanthate ions) from waste mining effluents.     

Mercury mobilization by oxidative dissolution of cinnabar (α-HgS) and metacinnabar (β-HgS)

Cinnabar (α-HgS) and metacinnabar (β-HgS) dissolved at environmentally significant rates in oxygenated slurry experiments simulating a low-flow fluvial system. Based on SO₄²⁻ production, cinnabar dissolution rates were 2.64 to 6.16 μmol (SO₄²⁻) m^− 2 day^− 1, and metacinnabar dissolution rates were 1.20 to 1.90 μmol (SO₄²⁻) m^− 2 day^− 1. Monodentate-bound thiosulfate (S₂O₃²⁻) was identified as an oxidation product on the HgS surface by ATR-IR spectroscopy based on strong infrared absorption bands in the 1140–1145 cm^− 1 and 1006–1014 cm^− 1 regions. The presence of sulfide oxidation intermediates on the HgS surface indicates that SO₄²⁻ concentration underestimates α-HgS and β-HgS dissolution in this setting. Mercury release rates during dissolution were more than two orders of magnitude less than SO₄²⁻ production, but were significant: 0.47 mg (Hg) m^− 2 y^− 1 from cinnabar [6.45 nmol (Hg) m^− 2 day^− 1], and 0.17 mg (Hg) m^− 2 y^− 1 from metacinnabar [2.29 nmol (Hg) m^− 2 day^− 1]. The Hg mobilized during α-HgS and β-HgS dissolution is sufficient to form natural Au–Hg amalgam in downstream placer settings. The proportion of mercury that is not remobilized during α-HgS and β-HgS dissolution likely adsorbs to the dissolving mercuric sulfide. Adsorption of Hg²⁺ to cinnabar was detected in situ by anodic stripping voltammetry using a cinnabar-modified carbon paste electrode following accumulation of Hg²⁺ on the electrode at open circuit potential.     

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.     

Study on the kinetics of iron oxide leaching by oxalic acid

The presence of iron oxides in clay or silica raw materials is detrimental to the manufacturing of high quality ceramics. Although iron has been traditionally removed by physical mineral processing, acid washing has been tested as it is more effective, especially for extremely low iron (of less than 0.1% w/w). However, inorganic acids such as sulphuric or hydrochloric acids easily contaminate the clay products with SO₄²⁻ and Cl⁻, and therefore should be avoided as much as possible. On the other hand, if oxalic acid is used, any acid left behind will be destroyed during the firing of the ceramic products. The characteristics of dissolution of iron oxides were therefore investigated in this study.The dissolution of iron oxides in oxalic acid was found to be very slow at temperatures within the range 25–60 °C, but its rate increases rapidly above 90 °C. The dissolution rate also increases with increasing oxalate concentration at the constant pH values set within the optimum range of pH2.5–3.0. At this optimum pH, the dissolution of fine pure hematite (Fe₂O₃) (105–140 μm) follows a diffusion-controlled shrinking core model. The rate expression expressed as 1 − (2 / 3)x − (1 − x)^2 / 3 where x is a fraction of iron dissolution was found to be proportional to [oxalate]^1.5.The addition of magnetite to the leach liquor at 10% w/w hematite was found to enhance the dissolution rate dramatically. Such addition of magnetite allows coarser hematite in the range 0.5–1.4 mm to be leached at a reasonable rate.     

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.     

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.     

Kinetics of leaching of oxidized and reduced ilmenite in dilute hydrochloric acid solutions

Ilmenite separated from beach sands of Bangladesh was oxidized for 1 h at 950 °C and then reduced in charcoal for 4 h at 1050 °C. This was followed by leaching in 5% to 15% hydrochloric acid solution in temperature range of 30 to 75 °C for periods of up to 2 h. The results were compared with those obtained by leaching of ilmenite reduced without oxidizing. Oxidation prior to reduction of the ilmenite was found to increase both the extent and the rate of leaching. The residual iron contents after leaching were also found to be lower than that obtained for non-oxidized samples. The kinetic data of leaching of ilmenite reduced after oxidation was found to follow first order reaction model, i.e., G(α) = − ln(1 − α) up to an α value of 0.5 (i.e. up to 50% reduction) and then changed to spherical model, i.e., G(α) = [1 − (1 − α)]³. On the other hand, leaching of ilmenite reduced without oxidizing was found to follow the Ginstling-Brounshtein reaction, i.e., G(α) = 1 − (2/3)α − (1 − α)^2/3 throughout the leaching process. Oxidation of ilmenite prior to reduction was also found to have decreased the activation energy of leaching from 43 kJ/mol, found for samples leached after reduction without oxidizing, to 30 kJ/mol.     

Iron isotopes in acid mine waters and iron-rich solids from the Tinto–Odiel Basin (Iberian Pyrite Belt, Southwest Spain)

The isotopic composition of Fe was determined in water, Fe-oxides and sulfides from the Tinto and Odiel Basins (South West Spain). As a consequence of sulfide oxidation in mine tailings both rivers are acidic (1.45 < pH < 3.85) and display high concentrations of dissolved Fe (up to 420 mmol l^− 1) and sulphates (up to 1190 mmol l^− 1).The δ⁵⁶Fe of pyrite-rich samples from the Rio Tinto and from the Tharsis mine ranged from − 0.56 ± 0.08‰ to + 0.25 ± 0.1‰. δ⁵⁶Fe values for Fe-oxides precipitates that currently form in the riverbed varied from − 1.98 ± 0.10‰ to 1.57 ± 0.08‰. Comparatively narrower ranges of values (− 0.18 ± 0.08‰ and + 0.21 ± 0.14‰) were observed in their fossil analogues from the Pliocene–Pleistocene and in samples from the Gossan (the oxidized layer that formed through exposure to oxygen of the massive sulfide deposits) (− 0.36 ± 0.12‰ to 0.82 ± 0.07‰). In water, δ⁵⁶Fe values ranged from − 1.76 ± 0.10‰ to + 0.43 ± 0.05‰.At the source of the Tinto River, fractionation between aqueous Fe(III) and pyrite from the tailings was less than would be expected from a simple pyrite oxidation process. Similarly, the isotopic composition of Gossan oxides and that of pyrite was different from what would be expected from pyrite oxidation. In rivers, the precipitation of Fe-oxides (mainly jarosite and schwertmannite and lesser amounts of goethite) from water containing mainly (more than 99%) Fe(III) with concentrations up to 372 mmol l^− 1 causes variable fractionation between the solid and the aqueous phase (− 0.98‰ < Δ⁵⁶Fe_{solid–water} < 2.25‰). The significant magnitude of the positive fractionation factor observed in several Fe(III) dominated water may be related to the precipitation of Fe(III) sulphates containing phases.     

Distribution of copper, zinc, lead and cadmium concentrations in stream sediments from the Mapocho River in Santiago, Chile

The Mapocho river, which crosses downtown Santiago, is one of the most important rivers in contact with a population of about six million inhabitants. Anthropogenic activities, industrialization, farming activities, transport, urbanization, animal and human excretions, domestic wastes and copper mining have affected the river, contaminating it and its sediments with heavy metals. Concentration and distribution of Cu, Zn, Pb and Cd were studied with the purpose of determining their bioavailability and their relation with the characteristics of the sediments. Freshly deposited seasonal sediments were collected from 0–8 cm depths from 6 locations (S₁ to S₆) along the 30-km long channel length, in the four seasons of year on the following dates: May 2001 (D₁, autumn); August 2001 (D₂, winter); October 2001 (D₃, spring) and January 2002 (D₄, summer). The dried samples were sifted to obtain the < 63-μm sediment fraction, since it has been shown that large amounts of heavy metals are bound in the fine-grained fraction of the sediment. Cu and Zn were analyzed by atomic absorption spectrophotometry and Pb and Cd by square wave anodic stripping voltammetry. The highest concentrations of Cu (2850 μg g^− 1) were found in the northern part of the river (S₁, average D₁–D₄), near the mountains and a copper mine, and then decreased downstream to 209 μg g^− 1 (S₆). Total Zn showed an irregular variation, with higher values at S₁ (1290 μg g^− 1) and high values in some winter sampling (1384 μg g^− 1 S₄, S₅–D₂). Pb showed different trends, increasing from S₁ to S₆ (17 to 61 μg g^− 1), with the highest values in the summer samples (83 μg g^− 1, S₄–S₆, D₄), and total Cd increased slightly from mean values of 0.2 and 0.5 μg g^− 1. Partition into five fractions was made using Tessier's analytical sequential extraction technique; the residue was treated with aqua regia for recovery studies, although this step is not part of the Tessier procedure. The results show that Cu, Zn and Pb in the sediments were dependent on the sampling places along the river, and variation in two years was low (D₁–D₄). The highest values of total organic matter, carbonate and conductivity were found in S₆, which has the smallest size particles, while at S₁ the sediments were predominantly sand and contain larger amounts of silica. Cu associated with carbonate decreased gradually from 58% (1771 μg g^− 1, S₁) to 16% (32 μg g^− 1, S₆); Cu bonded to reducible fraction was almost constant (33% to 37%), and Cu associated with oxidizable fraction increased from 7% (S₁) to 34% (S₆), but copper content was lower (214 to 68 μg g^− 1). Zn had a similar fractionation profile. However, Pb bound to oxidizable fraction did not show significant percent variation along the river (20% to 19%), but the amount bounded was 4 to 12 μg g^− 1. The residual fraction increased from 24% to 41% (5 to 25 μg g^− 1, S₁ to S₆). The distribution of Cd in the sediment was almost independent of the sampling stations and was bound to carbonate, reducible and residual fraction in similar proportion. Cu and Zn at S₁ were mainly bound to carbonates and reducible phases with 91% and 73% (2779 and 965 μg g^− 1, respectively), and with a change in the pH and/or the redox potential of the sediment–water system, these contaminants could easily enter the food chain. In S₆ the amount of Cu and Zn in these phases was 50% and 53% (100 to 313 μg g^− 1, respectively).     

Heat flow and lithospheric thermal regime in the Northeast German Basin

New values of surface heat flow are reported for 13 deep borehole locations in the Northeast German Basin (NEGB) ranging from 68 to 91 mW m^− 2 with a mean of 77 ± 3 mW m^− 2. The values are derived from continuous temperature logs, measured thermal conductivity, and log-derived radiogenic heat production. The heat-flow values are supposed free of effects from surface palaeoclimatic temperature variations, from regional as well as local fluid flow and from thermal refraction in the vicinity of salt structures and thus represent unperturbed crustal heat flow. Two-D numerical lithospheric thermal models are developed for a 500 km section along the DEKORP-BASIN 9601 deep seismic line across the basin with a north-eastward extension across the Tornquist Zone. A detailed conceptual model of crustal structure and composition, thermal conductivity, and heat production distribution is developed. Different boundary conditions for the thickness of thermal lithosphere were used to fit surface heat flow. The best fit is achieved with a thickness of thermal lithosphere of about 75 km beneath the NEGB. This estimate is corroborated by seismological studies and somewhat less than typical for stabilized Phanerozoic lithosphere. Modelled Moho temperatures in the basin are about 800 °C; heat flow from the mantle is about 35 to 40 mW m^− 2. In the southernmost part of the section, beneath the Harz Mountains, higher Moho temperatures up to 900 to 1000 °C are shown. While the relatively high level of surface heat flow in the NEGB obviously is of longer wave length and related to lithosphere thickness, changes in crustal structure and composition are responsible for short-wave-length anomalies.     

Insights into Wasatch fault vertical slip rates using the age of sediments in Timpanogos Cave, Utah

Timpanogos Cave, located near the Wasatch fault, is about 357 m above the American Fork River. Fluvial cave sediments and an interbedded carbonate flowstone yield a paleomagnetic and U–Th depositional age of 350 to 780 ka. Fault vertical slip rates, inferred from calculated river downcutting rates, range between 1.02 and 0.46 mm yr^− 1. These slip rates are in the range of the 0–12 Ma Wasatch Range exhumation rate ( 0.5–0.7 mm yr^− 1), suggesting that the long-term vertical slip rate remained stable through mid-Pleistocene time. However, the late Pleistocene (0–250 ka) decelerated slip rate ( 0.2–0.3 mm yr^− 1) and the accelerated Holocene slip rate ( 1.2 mm yr^− 1) are consistent with episodic fault activity. Assuming that the late Pleistocene vertical slip rate represents an episodic slowing of fault movement and the long-term (0–12 Ma) average vertical slip rate, including the late Pleistocene and Holocene, should be  0.6 mm yr^− 1, there is a net late Pleistocene vertical slip deficit of  50–75 m. The Holocene and late Pleistocene slip rates may be typical for episodes of accelerated and slowed fault movement, respectively. The calculated late Pleistocene slip deficit may mean that the current accelerated Wasatch fault slip rate will extend well into the future.     

Fluid inclusion and stable isotope study of the Cobre–Babilonia polymetallic epithermal vein system, Taxco district, Guerrero, Mexico

The Cobre–Babilonia vein system formed during a single major hydrothermal stage and is part of the Taxco district in Guerrero, southern Mexico. Homogenization and ice melting temperatures range from 160 to 290 °C and from − 11.6 to − 0.5 °C, respectively. We determined an approximate thermal gradient of 17 to 20 °C per 100 m using fluid inclusions. A thermal peak marked by the 290 °C isotherm is interpreted as a major feeder channel to the veins. The highest content of Zn + Pb in ore coincides with the 220 and 240 °C isotherms. Salinities of mineralizing fluids range from 0.8 to 15.6 wt.% NaCl equiv, and are distributed in two populations that can be related with barren or ore-bearing vein sections, with 0.8 to 6 wt.% NaCl equiv and 7 to 15.6 wt.% NaCl equiv, respectively. δ¹³C and δ¹⁸O water values from calcite from the Cobre–Babilonia vein system and the Esperanza Vieja and Guadalupe mantos range − 5.4‰ to − 10.4‰ and 9.9‰ to 13.4‰, respectively. δ³⁴S values range from 0‰ to 3.2‰ and − 0.7‰ to − 4.3‰ in sphalerite, − 4‰ to 0.9‰ in pyrite, and − 1.4‰ to − 5.5‰ in galena. Both fluid inclusion and stable isotope data are compatible with magmatic and meteoric sources for mineralizing fluids. Also, sulfur isotope compositions suggest both magmatic and sedimentary sources for sulfur.     

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.     

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.     

Adsorption of oleate on fluorite surface as revealed by atomic force microscopy

The adsorption of oleic acid / oleate on fluorite surface could be visualized using tapping mode of atomic force microscopy (AFM). The natural fluorite crystals were equilibrated with 10^− 3 to 10^− 7 M oleate solutions and their AFM images at each concentration along with height profiles were recorded. Even at low oleate concentration of 1 × 10^− 7 M, concomitant monolayer and bilayer structures were observed. It suggests that normal–normal bonding of hydrocarbon chains takes place before the surface is completely covered by the monolayer. Multi-layer adsorption of oleate was observed at oleate concentrations of above 10^− 4 M. The tapping mode AFM can be utilized to visualize the topography of surfaces adsorbed with surfactant molecules.     

Geochemical studies of pore fluid in surface sediment on the Daini Atsumi Knoll

We collected sediment samples and pore water samples from the surface sediment on the Daini Atsumi Knoll, and analyzed the sediments for CH₄, C₂H₆, and δ¹³C_CH4, and the pore fluids for CH₄, C₂H₆, δ¹³C_CH4, Cl⁻, SO₄²⁻, δ¹⁸O_H2O, and δD_H2O, respectively. A comparison of the measured concentration and isotopic composition of methane in pore water samples with those in sediment samples revealed that methane was present in the sediment samples at a higher concentration and was isotopically heavier than those in the pore water samples. It suggests that the effect of the release of a sorbed gas bound to organic particles when heated prior to analysis of hydrocarbons was larger than that of the degassing process. A large amount of a sorbed gas would be a significant source of natural gas. Two striking features are the chemical and isotopic composition of the pore water samples taken from the different sites around the Daini Atsumi Knoll. In the KL09, KL10, and KP07 samples, Cl⁻ concentrations in the pore water samples showed depletion to a minimum of 460 mmol/kg, correspond to  17% dilution of seawater, however the latter was not enriched in CH₄. The isotopic compositions of pore water samples suggested the low-Cl⁻ fluids in the pore water were not derived from dissociation of methane hydrate, but were derived from input of meteoric water. In contrast, in the KP05 samples from the north flank of the Daini Atsumi Knoll, pore water were characterized by CH₄ enrichment more than 370 μmol/kg, but not depleted in Cl⁻ concentrations. The observed methane concentration in the KP05 samples is not sufficient for methane hydrate to form in situ, indicating that the existence of methane hydrate in the surface sediment is negligible, as supported by Cl⁻ concentration. Based on the stable carbon isotope ratio of methane in the pore fluid from the KP05 site (δ¹³C_CH4 < − 50‰PDB), methane is thought to be of microbial origin. The pore waters in the surface sediments in the north flank of the Daini Atsumi Knoll were not directly influenced by upward fluid bearing methane of thermogenic origin from a deeper part of the sedimentary layer. However, extremely high methane concentration in the north flank site as compared with the concentration of pore water taken from the normal seafloor suggests that the north flank site is not the normal seafloor. We hypothesize that upward migration of chemically-reduced fluids from a deeper zone of the sedimentary layer reduces chemically-oxidized solutes in the surface sediment. As a consequence methane production replaced sulfate reduction as the microbial metabolism in the reduced environment of the surface sediment.     

Fluid geochemistry in the Ivigtut cryolite deposit, South Greenland

The 1.27 Ga old Ivigtut (Ivittuut) intrusion in South Greenland is world-famous for its hydrothermal cryolite deposit [Na₃AlF₆] situated within a strongly metasomatised A-type granite stock. This detailed fluid inclusion study characterises the fluid present during the formation of the cryolite deposit and thermodynamic modelling allows to constrain its formation conditions.Microthermometry revealed three different types of inclusions: (1) pure CO₂, (2) aqueous-carbonic and (3) saline-aqueous inclusions. Melting temperatures range between − 23 and − 15 °C for type 2 and from − 15 to − 10 °C for type 3 inclusions. Most inclusions homogenise between 110 and 150 °C into the liquid.Stable isotope compositions of CO₂ and H₂O were measured from crushed inclusions in quartz, cryolite, fluorite and siderite. The δ¹³C values of about − 5‰ PDB are typical of mantle-derived magmas. The differences between δ¹⁸O of CO₂ (+ 21 to + 42‰ VSMOW) and δ¹⁸O of H₂O (− 1 to − 21.7‰ VSMOW) suggest low-temperature isotope exchange. δD (H₂O) ranges from − 19 to − 144‰ VSMOW. The isotopic composition of inclusion water closely follows the meteoric water line and is comparable to Canadian Shield brines. Ion chromatography revealed the fluid's predominance in Na, Cl and F. Cl/Br ratios range between 56 and 110 and may imply intensive fluid–rock interaction with the host granite.Isochores deduced from microthermometry in conjunction with estimates for the solidification of the Ivigtut granite suggest a formation pressure of approximately 1–1.5 kbar for the fluid inclusions. Formation temperatures of different types of fluid inclusions vary between 100 and 400 °C. Thermodynamic modelling of phase assemblages and the extraordinary high concentration in F (and Na) may indicate that the cryolite body and its associated fluid inclusions could have formed during the continuous transition from a volatile-rich melt to a solute-rich fluid.     

Paleomagnetic constraints on the paleogeography and oroclinal bending of the Devonian volcanic arc in Kazakhstan

Numerical modelling, incorporating coupling between surface processes and induced flow in the lower continental crust, is used to address the Quaternary evolution of the Gulf of Corinth region in central Greece. The post-Early Pleistocene marine depocentre beneath this Gulf overlies the northern margin of an older (Early Pleistocene and earlier) lacustrine basin, the Proto Gulf of Corinth Basin or PGCB. In the late Early Pleistocene, relief in this region was minimal but, subsequently, dramatic relief has developed, involving the creation of  900 m of bathymetry within the Gulf and the uplift by many hundreds of metres of the part of the PGCB, south of the modern Gulf, which forms the Gulf's main sediment supply. It is assumed that, as a result of climate change around 0.9 Ma, erosion of this sediment source region and re-deposition of this material within the Gulf began, both processes occurring at spatial average rates of  0.2 mm a^− 1. Modelling of the resulting isostatic response indicates that the local effective viscosity of the lower crust is  4 × 10¹⁹ Pa s, indicating a Moho temperature of  560 °C. It predicts that the  10 mm a^− 1 of extension across this  70 km wide model region, at an extensional strain rate of  0.15 Ma^− 1, is partitioned with  3 mm a^− 1 across the sediment source,  2 mm a^− 1 across the depocentre, and  5 mm a^− 1 across the ‘hinge zone’ in between, the latter value being an estimate of the extension rate on normal faults forming the major topographic escarpment at the southern margin of the Gulf. This modelling confirms the view, suggested previously, that coupling between this depocentre and sediment source by lower-crustal flow can explain the dramatic development in local relief since the late Early Pleistocene. The effective viscosity of the lower crust in this region is not particularly low; the strong coupling interpreted between the sediment source and depocentre results instead from their close proximity. In detail, the effective viscosity of the lower crust is expected to decrease northward across this model region, due to the northward increase in exposure of the base of the continental lithosphere to the asthenosphere; in the south the two are separated by the subducting Hellenic slab. The isostatic consequences of such a lateral variation in viscosity provide a natural explanation for why, since  0.9 Ma, the modern Gulf has developed asymmetrically over the northern part of the PGCB, leaving the rest of the PGCB to act as its sediment source.     

Dynamic recrystallization near the brittle-plastic transition in naturally and experimentally deformed quartz aggregates

The electron backscattering diffraction technique (EBSD) was used to analyze bulging recrystallization microstructures from naturally and experimentally deformed quartz aggregates, both of which are characterized by porphyroclasts with finely serrated grain boundaries and grain boundary bulges set in a matrix of very fine recrystallized grains. For the Tonale mylonites we investigated, a temperature range of 300–380 °C, 0.25 GPa confining pressure, a flow stress range of ~ 0.1–0.2 GPa, and a strain rate of ~ 10^− 13 s^− 1 were estimated. Experimental samples of Black Hills quartzite were analyzed, which had been deformed in axial compression at 700 °C, 1.2–1.5 GPa confining pressure, a flow stress of ~ 0.3–0.4 GPa, a strain rate of ~ 10^− 6 s^− 1, and to 44% to 73% axial shortening. Using orientation imaging we investigated the dynamic recrystallization microstructures and discuss which processes may contribute to their development. Our results suggest that several deformation processes are important for the dismantling of the porphyroclasts and the formation of recrystallized grains. Grain boundary bulges are not only formed by local grain boundary migration, but they also display a lattice misorientation indicative of subgrain rotation. Dynamic recrystallization affects especially the rims of host porphyroclasts with a hard orientation, i.e. with an orientation unsuitable for easy basal slip. In addition, Dauphiné twins within porphyroclasts are preferred sites for recrystallization. We interpret large misorientation angles in the experimental samples, which increase with increasing strain, as formed by the activity of fluid-assisted grain boundary sliding.     

Thermal conductivity of Higher Himalayan Crystallines from Garhwal Himalaya, India

We report the measurements of thermal conductivity for some Higher Himalayan Crystalline rocks from Joshimath and Uttarkashi areas of the Garhwal Himalaya. Seventy-three rock samples including gneiss, metabasic rock and quartzite were measured. Gneissic rocks, which include augen gneiss, banded gneiss, felsic gneiss and fine-grained gneiss, exhibit a wide range in conductivity, from 1.5 to 3.6 Wm^− 1K^− 1 for individual samples, and 2.1 to 2.7 Wm^− 1K^− 1 for the means. Among these, augen gneisses and banded gneisses show the largest variability. Of all the rock types, quartzites (mean 5.4 Wm^− 1K^− 1) and metabasic rocks (mean 2.1 Wm^− 1K^− 1) represent the highest and lowest mean values respectively. The range in conductivity observed for gneissic rocks is significantly higher than that generally found in similar rock types in cratonic areas. The rock samples have very low porosity and exhibit feeble anisotropy, indicating that they do not contribute to the variability in thermal conductivity. Besides variations in mineralogical composition, the heterogeneous banding as well as intercalations with metabasic rocks and quartz veins, a common occurrence in structurally complex areas, appears to cause the variability in conductivity. The study therefore brings out the need for systematic characterization of thermophysical properties of major rock types comprising the Himalayan region for lithospheric thermal modeling, assessment of geothermal energy and geo-engineering applications in an area. The dataset constitutes the first systematic measurements on the Higher Himalayan Crystalline rocks.