Pressure responses of portlandite and H–D isotope effects on pressure-induced phase transitions

The pressure responses of portlandite and the isotope effect on the phase transition were investigated at room temperature from single-crystal Raman and IR spectra and from powder X-ray diffraction using diamond anvil cells under quasi-hydrostatic conditions in a helium pressure-transmitting medium. Phase transformation and subsequent peak broadening (partial amorphization) observed from the Raman and IR spectra of Ca(OH)₂ occurred at lower pressures than those of Ca(OD)₂. In contrast, no isotope effect was found on the volume and axial compressions observed from powder X-ray diffraction patterns. X-ray diffraction lines attributable to the high-pressure phase remained up to 28.5 GPa, suggesting no total amorphization in a helium pressure medium within the examined pressure region. These results suggest that the H–D isotope effect is engendered in the local environment surrounding H(D) atoms. Moreover, the ratio of sample-to-methanol–ethanol pressure medium (i.e., packing density) in the sample chamber had a significant effect on the increase in the half widths of the diffraction lines, even at pressures below the hydrostatic limit of the pressure medium.     

Late Pleistocene vegetation change in Korea and its possible link to East Asian monsoon and Dansgaard–Oeschger (D–O) cycles

Late Pleistocene carbon isotope (δ¹³C) records from a paleolithic sedimentary sequence collected from Baeki, Hongcheon, central Korea, show long-term changes with superimposed short-term isotopic excursions. The δ¹³C value of the sedimentary organic matter, a proxy for past vegetation change, varied from ? 26‰ to ? 23‰ for the period between 30 and 90 ka, with a long-term variation similar to insolation changes. High-amplitude (? 1‰ to approximately ? 1.5‰) fluctuations superimposed on the long-term changes in the δ¹³C values decreased during stronger summer monsoon intervals but increased during the weakened summer monsoon. This millennial-scale pattern is generally similar to Greenland Dansgaard–Oeschger (D–O) cycles. The possible connection between the Hongcheon area, Korea and high latitudes may be explained by atmospheric circulation changing in response to the D–O oscillations in the Northern Hemisphere.     

2D thermomechanical modelling of continent–arc–continent collision

Arc–continent collision is a key process of continental growth through accretion of newly grown magmatic arc crust to older continental margin. We present 2D petrological–thermo-mechanical models of arc–continent collision and investigate geodynamic regimes of this process. The model includes spontaneous slab bending, dehydration of subducted crust, aqueous fluid transport, partial melting of the crustal and mantle rocks and magmatic crustal growth stemming from melt extraction processes. Results point to two end-member types of subsequent arc–continent collisional orogens: (I) orogens with remnants of accretion prism, detached fragments of the overriding plate and magmatic rocks formed from molten subducted sediments; and (II) orogens mainly consisting of the closed back-arc basin suture, detached fragments of the overriding plate with leftovers of the accretion prism and quasi insignificant amount of sediment-derived magmatic rocks. Transitional orogens between these two endmembers include both the suture of the collapsed back-arc basin and variable amounts of magmatic production. The orogenic variability mainly reflects the age of the subducting oceanic plate. Older, therefore colder and denser oceanic plates trigger subduction retreat, which in turn triggers necking of the overriding plate and opening of a backarc basin in which new oceanic lithosphere is formed from voluminous decompression melting of the rising hot asthenosphere. In this case, subducted sediments are not heated enough to melt and generate magmatic plumes. On the other hand, young and less dense slabs do not retreat, which hampers opening of a backarc basin in the overriding plate while subducted sediments may reach their melting temperature and develop trans-lithospheric plumes. We have also investigated the influences of convergence rate and volcanic/plutonic rocks' ratio in newly forming lithosphere. The predicted gross-scale orogenic structures find similarities with some natural orogens, in particular with deeply eroded orogens such as the Variscides in the Bohemian Massif.     

Cyclic and Dynamic Behavior of Sand–Rubber and Clay–Rubber Mixtures

Geotechnical and Geological Engineering - In this paper, the possibility of using fine scrap tyre rubber to improve the mechanical properties of soil subjected to cyclic loading is...     

A 2D mixed fracture–pore seepage model and hydromechanical coupling for fractured porous media

A novel two-dimensional mixed fracture–pore seepage model for fluid flow in fractured porous media is presented based on the computational framework of finite-discrete element method (FDEM). The model consists of a porous seepage model in triangular elements bonded by unbroken joint elements, as well as a fracture seepage model in broken joint elements. The principle for determining the fluid exchange coefficient of the unbroken joint element is provided to ensure numerical accuracy and efficiency. The mixed fracture–pore seepage model provides a simple but effective tool for solving fluid flow in fractured porous media. In this paper, examples of 1D and 2D seepage flow in porous media and porous media with a single fracture or multiple fractures are studied. The simulation results of the model match well with theoretical solutions or results obtained by commercial software, which verifies the correctness of the mixed fracture–pore seepage model. Furthermore, combining FDEM mechanical calculation and the mixed fracture–pore seepage model, a coupled hydromechanical model is built to simulate fluid-driven dynamic propagation of cracks in the porous media, as well as its influence on pore seepage and fracture seepage.

     

Sound velocity and elastic properties of Fe–Ni and Fe–Ni–C liquids at high pressure

The sound velocity (V _P) of liquid Fe–10 wt% Ni and Fe–10 wt% Ni–4 wt% C up to 6.6 GPa was studied using the ultrasonic pulse-echo method combined with synchrotron X-ray techniques. The obtained V _P of liquid Fe–Ni is insensitive to temperature, whereas that of liquid Fe–Ni–C tends to decrease with increasing temperature. The V _P values of both liquid Fe–Ni and Fe–Ni–C increase with pressure. Alloying with 10 wt% of Ni slightly reduces the V _P of liquid Fe, whereas alloying with C is likely to increase the V _P. However, a difference in V _P between liquid Fe–Ni and Fe–Ni–C becomes to be smaller at higher temperature. By fitting the measured V _P data with the Murnaghan equation of state, the adiabatic bulk modulus (K _S0) and its pressure derivative (K _S ^′ ) were obtained to be K _S0 = 103 GPa and K _S ^′  = 5.7 for liquid Fe–Ni and K _S0 = 110 GPa and K _S ^′  = 7.6 for liquid Fe–Ni–C. The calculated density of liquid Fe–Ni–C using the obtained elastic parameters was consistent with the density values measured directly using the X-ray computed tomography technique. In the relation between the density (ρ) and sound velocity (V _P) at 5 GPa (the lunar core condition), it was found that the effect of alloying Fe with Ni was that ρ increased mildly and V _P decreased, whereas the effect of C dissolution was to decrease ρ but increase V _P. In contrast, alloying with S significantly reduces both ρ and V _P. Therefore, the effects of light elements (C and S) and Ni on the ρ and V _P of liquid Fe are quite different under the lunar core conditions, providing a clue to constrain the light element in the lunar core by comparing with lunar seismic data.     

Rare graphic textures of cinnabar–stibnite and cinnabar–chalcopyrite pairs and their genesis

We consider the rare graphic textures of cinnabar–stibnite and cinnabar–chalcopyrite pairs from the Khaidarkan Sb–Hg deposit (Kyrgyzstan) and the Idermeg-Bayan-Haan-Uul polysulfide–fluorite complex deposit (Mongolia). They resemble the ridge pattern on finger skin. Typical signs suggest the formation of the cinnabar–stibnite graphic texture in two stages of hypogene mineralization: (1) interstitial replacement of granulated stibnite by cinnabar and (2) local recrystallization of combined aggregates during the dynamic metamorphism of the ores with partial migration of substance and the formation of “ordered” graphic textures. This texture is named “the graphic texture of hypogene recrystallization.”The formation of the cinnabar–chalcopyrite graphic texture, which has been observed for the first time, is attributed to direct hypogene replacement of cinnabar by chalcopyrite. Chalcopyrite crystallization along the contacts of cinnabar grains is accompanied by the growth of the replacement area. It is proposed to name this texture “the graphic texture of hypogene replacement.” The causes of the selective replacement of cinnabar by chalcopyrite, which gave rise to this peculiar texture, remain uncertain.     

Plavica epithermal Au–Ag–Cu deposit in eastern Macedonia: Geology and 3D model of valuable component distribution in ore

The Plavica Au–Ag–Cu deposit is related to the large Neogene volcanic center, which complicates the paleocaldera in the central Kratovo–Zletovo ore district of eastern Macedonia. Based on the geology, ore mineralogy, wall-rock alteration, and fluid inclusions, the Plavica deposit has been referred to the epithermal high-sulfidation type. The general 3D model of orebody at this deposit is based on its general geological structure and complex distribution of metal contents. The framework of the 3D model, which has been constructed in the ArcGIS System, comprises 195 exploration boreholes 47295.8 m in total length. The 3D model allows to a better understanding of distribution of mineralization and supplements the geological data on the deposit.     

Genesis of the Au–Bi–Cu–As, Cu–Mo ± W, and base–metal Au–Ag mineralization at the Mountain Freegold (Yukon, Canada): constraints from Ar–Ar and Re–Os geochronology and Pb and stable isotope compositions

The genesis of mineralized systems across the Mountain Freegold area, in the Dawson Range Cu–Au?±?Mo Belt of the Tintina Au province was constrained using Pb and stable isotope compositions and Ar–Ar and Re–Os geochronology. Pb isotope compositions of sulfides span a wide compositional range (²⁰⁶Pb/²⁰⁴Pb, 18.669–19.861; ²⁰⁸Pb/²⁰⁴Pb, 38.400–39.238) that overlaps the compositions of the spatially associated igneous rocks, thus indicating a magmatic origin for Pb and probably the other metals. Sulfur isotopic compositions of sulfide minerals are broadly similar and their δ³⁴S (Vienna-Canyon Diablo Troilite (V-CDT)) values range from ?1.4 to 3.6 ‰ consistent with the magmatic range, with the exception of stibnite from a Au–Sb–quartz vein, which has δ³⁴S values between ?8.1 and ?3.1 ‰. The δ³⁴S values of sulfates coexisting with sulfide are between 11.2 and 14.2 ‰; whereas, those from the weathering zone range from 3.7 to 4.3 ‰, indicating supergene sulfates derived from oxidation of hypogene sulfides. The δ¹³C (Vienna Peedee Belemnite (VPDB)) values of carbonate range from ?4.9 to 1.1 ‰ and are higher than magmatic values. The δ¹⁸O (V-SMOW) values of magmatic quartz phenocrysts and magmatic least-altered rocks vary between 6.2 and 10.1 ‰ and between 5.0 and 10.1 ‰, respectively, whereas altered magmatic rocks and hydrothermal minerals (quartz and magnetite) are relatively ¹⁸O-depleted (4.2 to 7.9 ‰ and ?6.3 to 1.5 ‰, respectively). Hydrogen isotope compositions of both least-altered and altered igneous rock samples are D-depleted (from ?133 to ?161 ‰ Vienna-Standard Mean Ocean Water (V-SMOW)), consistent with differential magma degassing and/or post-crystallization exchange between the rocks and meteoric ground water. Zircon from a chlorite-altered dike has a U–Pb crystallization age of 108.7?±?0.4 Ma; whereas, the same sample yielded a whole-rock Ar–Ar plateau age of 76.25?±?0.53 Ma. Likewise, molybdenite Re–Os model ages range from 75.8 to 78.2 Ma, indicating the mineralizing events are genetically related to Late Cretaceous volcano-plutonic intrusions in the area. The molybdenite Re–Os ages difference between the nearby Nucleus (75.9?±?0.3 to 76.2?±?0.3 Ma) and Revenue (77.9?±?0.3 to 78.2?±?0.3 Ma) mineral occurrences suggests an episodic mineralized system with two pulses of hydrothermal fluids separated by at least 2 Ma. This, in combination with geological features suggest the Nucleus deposit represents the apical and younger portion of the Revenue–Nucleus magmatic-hydrothermal system and may suggest an evolution from the porphyry to the epithermal environments.     

The Fe–C–O–H–N system at 6.3–7.8 GPa and 1200–1400 °C: implications for deep carbon and nitrogen cycles

Interactions in a Fe–C–O–H–N system that controls the mobility of siderophile nitrogen and carbon in the Fe⁰-saturated upper mantle are investigated in experiments at 6.3–7.8 GPa and 1200–1400 °C. The results show that the γ-Fe and metal melt phases equilibrated with the fluid in a system unsaturated with carbon and nitrogen are stable at 1300 °C. The interactions of Fe₃C with an N-rich fluid in a graphite-saturated system produce the ε-Fe₃N phase (space group P6₃/mmc or P6₃22) at subsolidus conditions of 1200–1300 °C, while N-rich melts form at 1400 °C. At IW- and MMO-buffered hydrogen fugacity (fH₂), fluids vary from NH₃- to H₂O-rich compositions (NH₃/N₂?>?1 in all cases) with relatively high contents of alkanes. The fluid derived from N-poor samples contains less H₂O and more carbon which mainly reside in oxygenated hydrocarbons, i.e., alcohols and esters at MMO-buffered fH₂ and carboxylic acids at unbuffered fH₂ conditions. In unbuffered conditions, N₂ is the principal nitrogen host (NH₃/N₂?≤?0.1) in the fluid equilibrated with the metal phase. Relatively C- and N-rich fluids in equilibrium with the metal phase (γ-Fe, melt, or Fe₃N) are stable at the upper mantle pressures and temperatures. According to our estimates, the metal/fluid partition coefficient of nitrogen is higher than that of carbon. Thus, nitrogen has a greater affinity for iron than carbon. The general inference is that reduced fluids can successfully transport volatiles from the metal-saturated mantle to metal-free shallow mantle domains. However, nitrogen has a higher affinity for iron and selectively accumulates in the metal phase, while highly mobile carbon resides in the fluid phase. This may be a controlling mechanism of the deep carbon and nitrogen cycles.     

Mass and magnetic properties for 3D geological and geophysical modelling of the southern Agnew–Wiluna Greenstone Belt and Leinster nickel deposits,Western Australia

Physical property measurements provide a critical link between geological observations and geophysical measurements and modelling. To enhance the reliability of gravity and magnetic modelling in the Yilgarn Craton's Agnew–Wiluna Greenstone Belt, mass and magnetic properties were analysed on 157 new rock samples and combined with an existing corporate database of field measurements. The new samples include sulfide ore, serpentinised and olivine-bearing ultramafic host-rocks, granitoid, and felsic and mafic volcanic and volcaniclastic country rock. Synthesis of the data provides a useful resource for future geophysical modelling in the region. Several rock types in the region have sufficiently distinct physical properties that a discriminant diagram is proposed to facilitate a basic classification of rock types based on physical properties. However, the accumulation of emplacement, metamorphic, hydrothermal and structural processes has complicated the physical properties of the rocks by imposing duplicate and sometimes opposing physical property trends. The data confirm that massive sulfide and ultramafic rocks have the most distinctive mass and magnetic properties but with variability imposed by their complex history. Sulfide content imposes the strongest control on densities, but can only be identified when comprising >10 vol% of the rock. The pyrrhotite-rich Ni-sulfide assemblages generally have similar magnetic properties to the host ultramafic rocks, but can have much lower susceptibilities where the thermal history of the rocks has favoured development of hexagonal pyrrhotite over monoclinic pyrrhotite. In ultramafic rocks that contain <10 vol% sulfides, density and susceptibility are primarily controlled by serpentinisation, with olivine breaking down to serpentine and magnetite in the presence of water. Serpentinisation dramatically lowered densities and increased susceptibilities, but had limited influence on the intensity of remanent magnetisation. All ultramafic rocks contain multidomain magnetite, and most contain low coercivity grains prone to overprinting by in situ viscous remanent magnetisation or drilling-induced isothermal remanent magnetisation during extraction. Despite the low coercivities, Koenigsberger ratios of 1–20 are observed indicating that viscous remanent magnetisation aligned parallel to the present Earth field must be considered in any magnetic modelling. It is also noted that coarser-grained intrusive varieties of all rock types (e.g. granite, gabbro) show remanent magnetisation intensities 1–2 orders of magnitude greater than their extrusive equivalents (felsic and basaltic volcanics).     

Conjunctive K–Ca and Rb–Sr dating of glauconies

The glaucony series (of which glauconitic mica is the K-rich end member) is one of the few widely occurring minerals in the sedimentary record. So their isotopic ages determined mainly by the K–Ar method represent a major database for the geologic time scale. Many K–Ar ages were, however, found to be too young and often also discordant with available corresponding Rb–Sr ages. This discrepancy may reflect the disparate responses of the chemically contrasting daughter elements, Ar and Sr to postdepositional processes, and renders either age equivocal. A potentially promising approach to evaluate the intrinsic potential of glauconies and other K-rich minerals for direct and reliable dating of sediments is the conjunctive use of the chemically very similar K–Ca and Rb–Sr systems. The relationship between K–Ca and Rb–Sr ages may show a coherence or regularity indicative of a geologically meaningful age like in the case of the well known chemically identical dual U–Pb decay systems. As a crucial first step, this report presents the first successful precise K–Ca dating in conjunction with Rb–Sr dating of an Ordovician glauconite using the same sample aliquot, chemical procedure and mass spectrometer.     

Metallogenesis and ore-forming time of the Changtuxili Mn–Ag–Pb–Zn deposit in Inner Mongolia: Evidence from C–O–S isotopes and U–Pb geochronology

This paper reports new geochronological (U–Pb) and isotope (C, O, and S) data to investigate the timing of mineralization and mode of ore genesis for the recently discovered Changtuxili Mn–Ag–Pb–Zn deposit, located on the western slopes of the southern Great Hinggan Range in NE China. The mineralization is hosted by intermediate–acidic lavas and pyroclastic rocks of the Baiyingaolao Formation. Three stages of mineralization are identified: quartz–pyrite (Stage I), galena–sphalerite–tetrahedrite–rhodochrosite (Stage II), and quartz–pyrite (Stage III). δ¹³C and δ¹⁸O values for carbonate from the ore vary from −8.51‰ to −4.96‰ and 3.97‰ to 15.90‰, respectively, which are indicative of a low-temperature alteration environment. δ³⁴S_V-CDT values of sulfides range from −1.77‰ to 4.16‰ and show a trend of equilibrium fractionation (δ³⁴S_Py ​> ​δ³⁴S_Sp ​> ​δ³⁴S_Gn). These features indicate that pyrite, sphalerite, and galena precipitated during the period of mineralization. The alteration mineral assemblage and isotope data indicate that the weakly acidic to weakly alkaline ore-forming fluid was derived largely from meteoric water and the ore-forming elements C and S originated from magma. During the mineralization, a geochemical barrier was formed by changes in the pH of the ore-forming fluid, leading to the precipitation of rhodochrosite. On the basis of the mineralization characteristics, new isotope data, and comparison with adjacent deposits, we propose that the Changtuxili Mn–Ag–Pb–Zn deposit is an intermediate-to low-sulfidation epithermal deposit whose formation was controlled by fractures and variability in the pH of the ore-forming fluid. The surrounding volcanic rocks yield zircon U–Pb ages of 160−146 ​Ma (Late Jurassic), indicating that the mineralization is younger than 146 ​Ma.     

The identified origin of a linear slope near Chi–Chi earthquake rupture combining 2D, 3D resistivity image profiling and geological data

A slope on the west border of the foothill near 921 surface rupture (caused by the 1999 Chi-Chi earthquake) in central Taiwan shows distinctive topographic expression that was prone to be considered as a fault scarp formed by a preexisting active fault. The 2D and 3D resistivity images clearly delineate rock surfaces which show steep, deep, gentle, and subvertical displacement beneath the slope, the toe of slope, the non-lateritic terrace, and 921 surface rupture, respectively, which can be attributed to the significant contrast of resistivity between gravel and rock. The horizontal sand bed and clast-supported gravel were deposited in a fluvial environment, whereas wedge-shaped gravel and colluvium were scarp-induced colluvial deposits in the trench profile. The layers shown in the depth of excavation, except for rock, has no offset or disturbance by fault ever since at least 2,480 ± 50 year B.P., based on carbon 14 dating of charcoal sample at the bottom of trench profile. According to information from two boreholes close to the slope, an over 20-m-thick marker bed with transported shell fragments, was found for correlation. This correlation further implies the slope was not formed by fault. On the other hand, two boreholes which are far from the slope and located on the flat non-lateritic terrace frequently show fractured and sheared features. By comparison, the locations around these two boreholes indicate a reverse fault or faults that occurred before the deposition of gravel. Later on, the paleostream was developed along the foot of fault scarp that was subjected to erosion and led to subsequent retrogression or retreat of the slope. Consequently, the incision of paleostream is believed to be responsible for the high relief of rock surface around the slope. Furthermore, from resistivity and borehole data, the rock surface underlying terrace is gentle where no faults occur after the deposition of gravel. The result of RIP crossing the 921 surface rupture displays about 10 m difference in elevation of rock surface on both sides, which is greater than that of 3–4 m caused by Chi-Chi earthquake. This indicates that the 921 surface rupture is a preexisting thrust fault that resulted from several thrusting events since terrace gravel was deposited. So it is not necessary to establish an extra restricted zone for construction in study area, except close to the 921 surface rupture.     

Formation of gold–silver sulfides and native gold in Fe–Ag–Au–S system

We carried out experiments on crystallization of Fe-containing melts FeS₂Ag_0.1–0.1xAu_0.1x (x = 0.05, 0.2, 0.4, and 0.8) with Ag/Au weight ratios from 10 to 0.1. Mixtures prepared from elements in corresponding proportions were heated in evacuated quartz ampoules to 1050 ºC and kept at this temperature for 12 h; then they were cooled to 150 ºC, annealed for 30 days, and cooled to room temperature. The solid-phase products were studied by optical and electron microscopy and X-ray spectroscopy. The crystallization products were mainly from iron sulfides: monoclinic pyrrhotite (Fe_0.47S_0.53 or Fe₇S₈) and pyrite (Fe_0.99S_2.01). Gold–silver sulfides (low-temperature modifications) are present in all synthesized samples. Depending on Ag/Au, the following sulfides are produced: acanthite (Ag/Au = 10), solid solutions Ag_2–xAu_xS (Ag/Au = 10, 2), uytenbogaardtite (Ag/Au = 2, 0.75), and petrovskaite (Ag/Au = 0.75, 0.12). They contain iron impurities (up to 3.3 wt.%). Xenomorphic micro- (<1–5 μm) and macrograins (5–50 μm) of Au–Ag sulfides are localized in pyrite or between the grains of pyrite and pyrrhotite. High-fineness gold was detected in the samples with initial ratio Ag/Au ≤ 2. It is present as fine and large rounded microinclusions or as intergrowths with Au–Ag sulfides in pyrite or, more seldom, at the boundary of pyrite and pyrrhotite grains. This gold contains up to 5.7 wt.% Fe. Based on the sample textures and phase relations, a sequence of their crystallization was determined. At ~1050 ºC, there are probably iron sulfide melt L₁ (Fe,S ? Ag,Au), gold–silver sulfide melt L₂ (Au,Ag,S ? Fe), and liquid sulfur L_S. On cooling, melt L₁ produces pyrrhotite; further cooling leads to the crystallization of high-fineness gold (macrograins from L₁ and micrograins from L₂) and Au–Ag sulfides (micrograins from L₁ and macrograins from L₂). Pyrite crystallizes after gold–silver sulfides by the peritectic reaction FeS + L_S = FeS₂ at ~743 ºC. Elemental sulfur is the last to crystallize. Gold–silver sulfides are stable and dominate over native gold and silver, especially in pyrite-containing ores with high Ag/Au ratios.     

OH defects in quartz in the system quartz–albite–water and granite–water between 5 and 25?kbar

The incorporation of OH defects in quartz from the systems quartz–water, quartz–albite–water and granite–water at pressures between 5 and 25?kbar and temperatures between 800 and 1,000?°C was investigated by IR spectroscopy. The two most important OH absorption features can be assigned to hydrogarnet defects (absorption band at 3,585?cm^?1) and coupled substitutions involving Al³⁺ (Al–H defects, absorption bands at 3,310, 3,378 and 3,430?cm^?1). Al incorporation in quartz is controlled by mineral/melt partitioning (D _Al ^Qz/Melt ?=?0.01) and exhibits a negative pressure dependence. This trend is not clearly reflected by the concentration of Al–H defects, which shows positive deviations from the theoretical 1:1 correlation of Al/H for some samples. In contrast to the Al–H defects, formation of hydrogarnet defects appears to be positively correlated to pressure and water activity, and may be used a petrological indicator. The overall water concentration exhibits only minor changes with pressure and temperature, but a clear correlation of water activity (controlled by various amounts of dissolved salts) and hydrogarnet substitution could be established.     

Structure and Evolution of Ancient and Modern Tectonic–Sedimentary Systems

Geotectonics - The article discusses the ratio of the size and spatial position of ancient and modern areas of geodynamic processes (tectonic-sedimentary systems) and the resulting geological...