Solid inclusions of magmatic halite and sylvite in felsic granitoids, Sierra Norte, Córdoba, Argentina

This study provides evidence for the existence of halite and sylvite solid inclusions in igneous quartz and feldspars, the first to be reported in intrusive rocks, and to partially constrain the physicochemical environment that lets halides crystallize under magmatic conditions.Halite and sylvite solid inclusions were found included in quartz and feldspars from a micrographic–granophyric assemblage in a miarolitic aplite and, rarer, in alkali-feldspar from a miarolitic monzogranite. Monzogranite and aplite represent I-type, K-enriched postcollisional rocks of the Late Cambrian–Early Ordovician Sierra Norte–Ambargasta batholith in the Eastern Sierras Pampeanas. Both granitoids fall among the most evolved felsic rocks of the batholith, with aplite approaching haplogranitic compositions. Halite is far more common than sylvite and the presence and distribution of one or both halides are erratic within the felsic intrusive bodies. Halides occur as small skeletal grains, commonly in cross-shaped aggregates of less than 50 μm. No K or Na was found at the detection limits of EDS in either halite or sylvite respectively. Textural relationships suggest that the alkali-chlorides separated from the melt near the minima along the quartz–feldspar cotectics of P_H2O > 160 < 200 MPa in a silica-, and potassium-rich magmatic system at approximately 750–700 °C, prior to the H₂O-vapor saturated miarole-forming stage.Computed ratios for the magmatic volatile phase (MVP) coexisting with melt at the early stage of aplite crystallization are: NaCl/HCl = 0.11–0.97 and KCl/HCl = 0.24–1.62, being the highest range of values (0.79–0.97 and 1.45–1.62, respectively) found in those alkali-chloride-bearing samples. Maximum HCl/ΣCl_(MVP) (0.28 to 0.31) indicates higher total Cl concentration in the MVP of alkali-chloride-bearing aplites, which is much higher in the halite-free aplite samples (HCl/ΣCl_(MVP) = 0.59 to 0.74). One miarolitic monzogranite sample, where halite solid inclusions are present, also yielded the highest ratios for NaCl/HCl_(MVP) (0.91) and KCl/HCl_(MVP) (1.46), and the HCl/ΣCl_(MVP) is 0.30. A high HCl concentration in the fluid phase is suggested by the log f(HF)/f(H₂O) = − 4.75 to − 4.95, log f(HCl)/f(H₂O) = − 3.73 to − 3.86, and log f(HF)/f(HCl) = − 0.88 to − 1.22, computed at 750 °C after biotite composition. The Cl concentrations at 800 °C, computed with a D^v/l_Cl = 0.84 + 26.6P (P at 200 MPa), yielded values within the range of  70 to 700 ppm Cl in the melt and  4000 to 40 000 ppm Cl in the coexisting MVP. The preferential partitioning of Cl in the vapor phase is controlled by the D^v/l_Cl; however, the low concentration of Cl in the melt suggests that high concentrations of Cl are not necessary to saturate the melt in NaCl or KCl.Cl-saturation of the melt and coexisting MVP might have been produced by a drop in Cl solubility due to the near-haplogranitic composition of the granitoids after extreme fractionation, probably enhanced by fluctuating reductions of the emplacement pressure in the brittle monzogranite host. Liquid immiscibility, based in the differential viscosity and density among alkali-chloride saturated hydrosaline melt, aluminosilicate felsic melt, and H₂O-rich volatiles is likely to have crystallized halite and sylvite from exsolved hydrosaline melt. High degrees of undercooling might have been important at the time of alkali-chloride exsolution. The effectiveness of alkali-chloride separation from the melt at magmatic temperatures is in line with the interpretation of “halite subtraction” as a necessary process to understand the origin of the “halite trend” in highly saline fluid inclusions from porphyry copper and other hydrothermal mineralizations, despite the absence of the latter in the Cerro Baritina aplites, where this process preceded the exsolution of halite-undersaturated fluids.Pervasive alteration of the monzogranite country rock as alkali-metasomatic mineral assemblages, the mineral chemistry of some species, and the association of weak molybdenite mineralization are compatible with the activity of alkaline hypersaline fluids, most likely exsolved during the earliest stages of aplite consolidation.     

Intrinsic and scattering attenuation in western India from aftershocks of the 26 January, 2001 Kachchh earthquake

176 vertical-component, short period observations from aftershocks of the M_w 7.7, 26 January, 2001 Kachchh earthquake are used to estimate seismic wave attenuation in western India using uniform and two layer models. The magnitudes (M_w) of the earthquakes are less than 4.5, with depths less than 46 km and hypocentral distances up to 110 km. The studied frequencies are between 1 and 30 Hz. Two seismic wave attenuation factors, intrinsic absorption (Q_i^− 1) and scattering attenuation (Q_s^− 1) are estimated using the Multiple Lapse Time Window method which compares time integrated seismic wave energies with synthetic coda wave envelopes for a multiple isotropic scattering model. We first assume spatial uniformity of Q_i^− 1, Q_s^− 1 and S wave velocity (β). A second approach extends the multiple scattering hypothesis to media consisting of several layers characterized by vertically varying scattering coefficient (g), intrinsic absorption strength (h), density of the media (ρ) and shear wave velocity structure. The predicted coda envelopes are computed using Monte Carlo simulation. Results show that, under the assumption of spatial uniformity, scattering attenuation is greater than intrinsic absorption only for the lowest frequency band (1 to 2 Hz), whereas intrinsic absorption is predominant in the attenuation process at higher frequencies (2 to 30 Hz). The values of Q obtained range from Q_t = 118, Q_i = 246 and Q_s = 227 at 1.5 Hz to Q_t ≈ 4000, Q_i ≈ 4600 and Q_s ≈ 33,300 at 28 Hz center frequencies, being Q_t^− 1 a measure of total attenuation. Results also show that Q_i^− 1, Q_s^− 1 and Q_t^− 1 decrease proportional to f^−ν. Two rates of decay are clearly observed for the low (1 to 6 Hz) and high (6 to 30 Hz) frequency ranges. Values of ν are estimated as 2.07 ± 0.05 and 0.44 ± 0.09 for total attenuation, 1.52 ± 0.21 and 0.48 ± 0.09 for intrinsic absorption and 3.63 ± 0.07 and 0.06 ± 0.08 for scattering attenuation for the low and high frequency ranges, respectively. Despite the lower resolution in deriving the attenuation parameters for a two layered crust, we find that scattering attenuation is comparable to or smaller than the intrinsic absorption in the crust whereas intrinsic absorption dominates in the mantle. Also, for a crustal layer of thickness 42 km, intrinsic absorption and scattering estimates in the crust are lower and greater than those of the mantle, respectively.     

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.     

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.     

Origin and evolution of the Steamboat Springs siliceous sinter deposit, Nevada, U.S.A.

Siliceous hot spring deposits from Steamboat Springs, Nevada, U.S.A., record a complex interplay of multiple, changing, primary environmental conditions, fluid overprinting and diagenesis. Consequently these deposits reflect dynamic geologic and geothermal processes. Two surface sinters were examined—the high terrace, and the distal apron-slope, as well as 13.11 m (43 ft) of core material from drill hole SNLG 87-29. The high terrace sinter consists of vitreous and massive-mottled silica horizons, while the distal deposit and core comprise dominantly porous, indurated fragmental sinters. Collectively, the three sinter deposits archive a complete sequence of silica phase diagenetic minerals from opal-A to quartz. X-ray powder diffraction analyses and infrared spectroscopy of the sinters indicate that the distal apron-slope consists of opal-A and opal-A/CT mineralogy; the core yielded opal-A/CT and opal-CT with minor opal-A; and the high terrace constitutes opal-C, moganite, and quartz. Mineralogical maturation of the deposit produced alternating nano–micro–nano-sized silica particle changes. Based on filament diameters of microbial fossils preserved within the sinter, discharging thermal outflows fluctuated between low-temperatures (< 35 °C, coarse filaments) and mid-temperatures ( 35–60 °C, fine filaments). Despite transformation to quartz, primary coarse and fine filaments were preserved in the high terrace sinter. AMS ¹⁴C dating of pollen from three horizons within core SNLG 87-29, from depths of 8.13 to 8.21 m (26′8″ to 26′11″), 10.13 to 10.21 m (33′3″ to 33′6″), and 14.81 to 14.88 m (48′7″ to 48′10″), yielded dates of 8684 ± 64 years, 11,493 ± 70 years and 6283 ±60 years, respectively. In the upper section of the core, the stratigraphically out-of-sequence age likely reflects physical mixing of younger sinter with quartzose sinter fragments derived from the high terrace. Within single horizons, mineralogical and morphological components of the sinter matrix were spatially patchy. Overall, the deposit was modified by sub-surface flow of alkali-chloride thermal fluids depositing a second generation of silica, and periodically, by acidic steam condensate formed during periods when the water table was low. Local faulting produced considerable fracturing of the sinter. Hence, the Steamboat Springs sinter experienced a complex history of primary and secondary hydrothermal, geologic and diagenetic events, and their inter-relationships and effects are locked within the physical, chemical and biological signatures of the deposit.     

An early Paleoproterozoic high-K intrusive complex in southwestern Tarim Block, NW China: Age, geochemistry, and tectonic implications

Systematic geochronologic, geochemical, and Nd isotopic analyses were carried out for an early Paleoproterozoic high-K intrusive complex exposed in southwestern Tarim, NW China. The results provide a better understanding of the Paleoproterozoic tectonic evolution of the Tarim Block. Zircon U–Pb age dating indicates two Paleoproterozoic magmatic episodes occurring at ca. 2.41 Ga and ca. 2.34 Ga respectively, which were followed by a ca. 1.9 Ga metamorphic event. The 2.41 Ga granodiorite–adamellite suite shares characteristics of late to post-orogenic metaluminous A-type granites in its high alkalinity (Na₂O + K₂O = 7.6–9.3%), total REE (410–788 ppm), Zr (370–660 ppm), and Y (21.7–58.4 ppm) contents. εNd(t) values for the suite range from − 3.22 to − 4.71 and accordingly the Nd modal ages (T_2DM) vary between 3.05 Ga and 3.17 Ga. Based on geochemical data, the 2.34 Ga suite can be subdivided into two sub-suites, namely A-type and S-type. However, both types have comparable Nd isotope compositions (εNd(t) ≈ − 0.41 to − 2.08) and similar narrow T_2DM ranges (2.76–2.91 Ga).Geochemical and Nd isotopic data for the high-K intrusive complex, in conjunction with the regional geological setting, suggest that both the 2.41 Ga suite and the 2.34 Ga A-type sub-suite might have been produced by partial melting of the Archean mafic crust in a continental rift environment. The S-type sub-suite is thought to have formed by partial melting of felsic pelites and/or metagreywackes recycled from Archean crust (TTG?). Gabbro enclaves with positive εNd(t) value (2.15) have been found to be intermingling within the 2.34 Ga suite; ca. 2.34–2.36 Ga gabbroic dykes and adamellites have previously been documented in eastern Tarim. These observations indicate that the high-K intrusions may reflect the emergence of depleted mantle upwelling beneath the Tarim Block at that time. We suggest a three-stages model for the Precambrian crustal evolution in the Tarim Block: (1) the formation of proto-crust (TTG) by ca. 2.5 Ga, (2) episodes of felsic magmatism possibly occurring in continental rift environments at ca. 2.41 Ga and ca. 2.34–2.36 Ga, and (3) ca. 1.9 Ga metamorphism that may represent the solidification of the Precambrian basement of the Tarim Block.     

Mercury in itabirite-hosted soft hematite ore in the Quadrilátero Ferrífero of Minas Gerais

Mercury contents in Precambrian banded iron formation-hosted hematite ores are virtually unknown. In an attempt to provide information on the abundance and distribution of Hg in Fe ore, we present analyses for Hg in samples of high-grade soft hematite ore from Gongo Soco, Minas Gerais, Brazil. Bulk samples contain from <  5 to 25  ppb Hg without obvious correlation with major elements. Granulometric fractions of follow-up samples have amounts of Hg from 6 to 48  ppb and display positive linear correlations with total Mn as MnO (r = 0.87), LOI (r = 0.87) and SiO₂ (r = 0.76), as well as a negative linear correlation with total Fe as Fe₂O₃ (r = −  0.87). The correlations suggest that Hg is associated with a hydrated ferruginous groundmass bearing residual Mn, Al and Si, which replaced gangue minerals in itabirite in the process of formation of the Gongo Soco soft hematite ore.     

Experimental constraints on Pt, Pd and Au partitioning and fractionation in silicate melt–sulfide–oxide–aqueous fluid systems at 800 °C, 150 MPa and variable sulfur fugacity

We have performed experiments to constrain the effect of sulfur fugacity (fS₂) and sulfide saturation on the fractionation and partitioning behavior of Pt, Pd and Au in a silicate melt–sulfide crystal/melt–oxide–supercritical aqueous fluid phase–Pt–Pd–Au system. Experiments were performed at 800 °C, 150 MPa, with oxygen fugacity (fO₂) fixed at approximately the nickel–nickel oxide buffer (NNO). Sulfur fugacity in the experiments was varied five orders of magnitude from approximately log fS₂ = 0 to log fS₂ = −5 by using two different sulfide phase assemblages. Assemblage one consisted initially of chalcopyrite plus pyrrhotite and assemblage two was loaded with chalcopyrite plus bornite. At run conditions pyrrhotite transformed compositionally to monosulfide solid solution (mss), chalcopyrite to intermediate solid solution (iss), and in assemblage two chalcopyrite and bornite formed a sulfide melt. Run-product silicate glass (i.e., quenched silicate melt) and crystalline materials were analyzed by using both electron probe microanalysis and laser ablation inductively coupled plasma mass spectrometry. The measured concentrations of Pt, Pd and Au in quenched silicate melt in runs with log fS₂ values ranging from approximately 0.0 to −5.0 do not exhibit any apparent dependence on fS₂. The measured Pt, Pd and Au concentrations in mss do vary as a function of fS₂. The measured Pt, Pd and Au concentrations in iss do not appear dependent on fS₂. The data suggest that fS₂, working in concert with fO₂, via the determinant role that these variables play in controlling the magmatic sulfide phase assemblage and the solubility of Pt, Pd and Au as lattice bound components in magmatic sulfide phases, is a controlling factor on the budgets of Pt, Pd and Au during the evolution of magmatic systems.     

Methane-derived authigenic carbonates from the northern Gulf of Mexico — MD02 Cruise

Authigenic carbonates were sampled in piston cores collected from both the Tunica Mound and the Mississippi Canyon area on the continental slope of the northern Gulf of Mexico during a Marion Dufresne cruise in July 2002. The carbonates are present as hardgrounds, porous crusts, concretions or nodules and shell fragments with or without carbonate cements. Carbonates occurred at gas venting sites which are likely to overlie gas hydrates bearing sediments. Electron microprobe, X-ray diffraction (XRD) and thinsection investigations show that these carbonates are high-Mg calcite (6–21 mol% MgCO₃), with significant presence of framboidal pyrite. All carbonates are depleted in ¹³C (δ¹³C = − 61.9 to − 31.5‰ PDB) indicating that the carbon is derived mainly from anaerobic methane oxidation (AMO). Age estimates based on ¹⁴C dating of shell fragments and on regional sedimentation rates indicate that these authigenic carbonates formed within the last 1000 yr in the Mississippi Canyon and within 5500 yr at the Tunica Mound. The oxygen isotopic composition of carbonates ranges from + 3.4 to + 5.9‰ PDB. Oxygen isotopic compositions and Mg²⁺ contents of carbonates, and present in-situ temperatures of bottom seawater/sediments, show that some of these carbonates, especially from a core associated with underlying massive gas hydrates precipitated in or near equilibrium with bottom-water. On the other hand, those carbonates more enriched in ¹⁸O are interpreted to have precipitated from ¹⁸O-rich fluids which are thought to have been derived from the dissociation of gas hydrates. The dissociation of gas hydrates in the northern Gulf of Mexico within the last 5500 yr may be caused by nearby salt movement and related brines.     

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.     

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.     

Geochemistry and Nd–Sr isotopic studies of Late Mesozoic granitoids in the southeastern Hubei Province, Middle–Lower Yangtze River belt, Eastern China: Petrogenesis and tectonic setting

A geochemical and isotopic study was carried out for the Mesozoic Yangxin, Tieshan and Echeng granitoid batholiths in the southeastern Hubei Province, eastern China, in order to constrain their petrogenesis and tectonic setting. These granitoids dominantly consist of quartz diorite, monzonite and granite. They are characterized by SiO₂ and Na₂O compositions of between 54.6 and 76.6 wt.%, and 2.9 to 5.6 wt.%, respectively, enrichment in light rare earth elements (LREE) and large ion lithophile elements (LILE), and relative depletion in Y (concentrations ranging from 5.17 to 29.3 ppm) and Yb (0.34–2.83 ppm), with the majority of the granitoids being geochemically similar to high-SiO₂ adakites (HSA). Their initial Nd (ε_Nd = − 12.5 to − 6.1) and Sr ((⁸⁷Sr/⁸⁶Sr)_i = 0.7054–0.7085) isotopic compositions, however, distinguish them from adakites produced by partial melting of subducted slab and those produced by partial melting of the lower crust of the Yangtze Craton in the Late Mesozoic. The granitoid batholiths in the southeastern Hubei Province exhibit very low MgO ranging from 0.09 to 2.19 wt.% with an average of 0.96 wt.%, and large variations in negative to positive Eu anomalies (Eu/Eu = 0.22–1.4), especially the Tieshan granites and Yangxin granite porphyry (Eu/Eu = 0.22–0.73). Geochemical and Nd–Sr isotopic data demonstrate that these granitoids originated as partial melts of an enriched mantle source that experienced significant contamination of lower crust materials and fractional crystallization during magma ascent. Late Mesozoic granitoids in the southeastern Hubei Province of the Middle–Lower Yangtze River belt were dominantly emplaced in an extensional tectonic regime, in response to basaltic underplating, which was followed by lithospheric thinning during the early Cretaceous.     

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.     

Magnitude of σ1, σ2, and σ3 at mid-crustal levels in an orogenic belt: Microboudin method applied to an impure metachert from Turkey

We revised an equation for estimating palaeostress magnitude using the microboudin technique by incorporating the influence of time on the fracture strength of minerals. The equation was used to estimate triaxial palaeostresses from a rare sample of metachert from Turkey that contains microboudinaged, columnar tourmaline grains in a wide range of orientations within the foliation plane. The estimated principal palaeostresses are σ₁ = 605 MPa, σ₂ = 598 MPa, and σ₃ = 597 MPa. As the microboudinage is considered to have occurred immediately before the rock encountered the brittle-plastic transition during exhumation, these stress values correspond to conditions at approximately 18 km depth and 300 °C within a Cretaceous orogenic belt.     

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%.     

The 1980, 1997 and 1998 Azores earthquakes and some seismo-tectonic implications

We have studied the focal mechanisms of the 1980, 1997 and 1998 earthquakes in the Azores region from body-wave inversion of digital GDSN (Global Digital Seismograph Network) and broadband data. For the 1980 and 1998 shocks, we have obtained strike–slip faulting, with the rupture process made up of two sub-events in both shocks, with total scalar seismic moments of 1.9 × 10¹⁹ Nm (M_w = 6.8) and 1.4 × 10¹⁸ Nm (M_w = 6.0), respectively. For the 1997 shock, we have obtained a normal faulting mechanism, with the rupture process made up of three sub-events, with a total scalar seismic moment of 7.7 × 10¹⁷ Nm (M_w = 5.9). A common characteristic of these three earthquakes was the shallow focal depth, less than 10 km, in agreement with the oceanic-type crust. From the directivity function of Rayleigh (LR) waves, we have identified the NW–SE plane as the rupture plane for the 1980 and 1998 earthquakes with the rupture propagating to the SE. Slow rupture velocity, about of 1.5 km/s, has been estimated from directivity function for the 1980 and 1998 earthquakes. From spectral analysis and body-wave inversion, fault dimensions, stress drop and average slip have been estimated. Focal mechanisms of the three earthquakes we have studied, together with focal mechanisms obtained by other authors, have been used in order to obtain a seismotectonic model for the Azores region. We have found different types of behaviour present along the region. It can be divided into two zones: Zone I, from 30°W to 27°W; Zone II, from 27°W to 23°W, with a change in the seismicity and stress direction from Zone I. In Zone I, the total seismic moment tensor obtained corresponded to left-lateral strike–slip faulting with horizontal pressure and tension axes in the E–W and N–S directions, respectively. In Zone II, the total seismic moment tensor corresponded to normal faulting, with a horizontal tension axis trending NE–SW, normal to the Terceira Ridge. The stress pattern for the whole region corresponds to horizontal extension with an average seismic slip rate of 4.4 mm/yr.     

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.     

Organic geochemistry and petrology of barren and Mo–Ni–PGE mineralized marine black shales of the Lower Cambrian Niutitang Formation (South China)

Marine black shales of the Lower Cambrian Niutitang Formation in southern China host Mo–Ni–platinum group elements (PGE) mineralization confined to a phosphate- and pyrite-rich stratiform body (max. 20-cm thick). The H/C atomic ratio, carbon isotopic composition, FTIR spectra of bulk organic matter, and spectra of extractable part of organic matter indicate similar sources and thermal evolution of organic matter in barren and mineralized black shales.The morphology and relative abundance of organic particles in barren and mineralized shales are different. In barren black shales, organic particles comprise only elongated bodies and laminae 2–10 μm across or elongated larger bodies (> 10 μm) with R_max = 2.96–5.21% (Type I particles). Mineralized black shales contain Type I particles in rock matrix (90–95 vol%), small veinlets or irregular organic accumulations (Type II particles, 1–5 vol%) that display weak to well developed mosaic texture and a variable reflectance (R_max = 3.55–8.65%), and small (< 1 to 5 μm) rounded or irregular Type III organic particles (1–4 vol%) distributed within phosphate nodules and sulphide rip-up clasts. Type III particles show similar reflectance as particles of Type I in rock matrix. Type I particles are interpreted as remnants of in situ bacterially reworked organic matter of cyanobacteria/algal type, Type II as solidified products or oil-derived material (migrabitumen), and Type III particles as remnants of original organic matter in phosphatized or sulphidized algal/microbial oncolite-like bodies. Equivalent vitrinite reflectances of Type I and III particles in barren and mineralized rocks are similar and correspond to semi-anthracite and anthracite. Micro-Raman spectra of organic particles in rocks display a wide belt in the area of 1600 cm^− 1 (G belt) and approximately the same belt in the area of 1350 cm^− 1 (D belt). The ratio of integrated areas of the two belts correlate with R_max values.The Mo–Ni–PGE mineralized body is interpreted as to represent a remnant of phosphate- and sulphide-rich subaquatic hardground supplied with organic material derived from plankton and benthic communities as well as with algal/microbial oncolite-like bodies that originated in wave-agitated, shallow-water, nearshore environment.     

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.     

A comparative study on the dissolution and solubility of hydroxylapatite and fluorapatite at 25 °C and 45 °C

Dissolution of the synthetic hydroxylapatite (HAP) and fluorapatite (FAP) in pure water was studied at 25 °C and 45 °C in a series of batch experiments. The XRD, FT-IR and SEM analyses indicated that the synthetic, microcrystalline HAP and FAP with apatite structure used in the experiments were found to have no obvious variation after dissolution except that the existence of OH groups in FT-IR spectra for FAP after 2880 h dissolution was observed. During the HAP dissolution (0–4320 h), the aqueous calcium and phosphate concentrations reached the maxima after 120 h and then decreased slowly with time. For the FAP dissolution in pure water, after a transient time of 1440 h (< 60 d), element concentrations and pH became constant suggesting attainment of a steady-state between the solution and solid. During early stages of the FAP dissolution reaction (< 72–120 h), mineral components were released in non-stoichiometric ratios with reacted solution ratios of dissolved Ca:P, Ca:F and P:F being lower than mineral stoichiometric ratios of Ca₅(PO₄)₃F, i.e., 1.67, 5.0 and 3.0, respectively. This indicated that F were preferentially released compared to Ca from the mineral structure. The mean K_sp values were calculated by using PHREEQC for HAP of 10^− 53.28 (10^− 53.02–10^− 53.51) and for FAP of 10^− 55.71 (10^− 55.18–10^− 56.13) at 25 °C, the free energies of formation ΔG_f^o[HAP] and ΔG_f^o[FAP] were calculated to be − 6282.82 kJ/mol and − 6415.87 kJ/mol, respectively.