Fluid entrapment and reequilibration during subduction and exhumation: A case study from the high-grade Nestos shear zone, Central Rhodope, Greece

A fluid inclusion study on metamorphic minerals of successive growth stages was performed on highly deformed paragneisses from the Nestos Shear Zone at Xanthi (Central Rhodope), in which microdiamonds provide unequivocal evidence for ultrahigh-pressure (UHP) metamorphism. The correlation of fluid inclusion density isochores and fluid inclusion reequilibration textures with geothermobarometric data and the relative chronology of micro- and macro-scale deformation stages allow a better understanding of both the fluid and metamorphic evolution along the P–T–d path. Textural evidence for subduction towards the NE is recorded by the orientation of intragranular NE-oriented fluid inclusion planes and the presence of single, annular fluid inclusion decrepitation textures. These textures occur within quartz “foam” structures enclosed in an earlier generation of garnets with prolate geometries and rarely within recrystallized matrix quartz, and reequilibrated both in composition and density during later stages of exhumation. No fluid inclusions pertaining to the postulated ultrahigh-pressure stage for microdiamond-bearing garnet–kyanite–gneisses have yet been found. The prolate shape of garnets developed during the earliest stages of exhumation that is recorded structurally by (L  S) tectonites, which subsequently accommodated progressive ductile SW shearing and folding up to shallow crustal levels. The majority of matrix kyanite and a later generation of garnet were formed during SW-directed shear under plane-strain conditions. Fluid inclusions entrapped in quartz during this stage of deformation underwent density loss and transformed to almost pure CO₂ inclusions by preferential loss of H₂O. Those inclusions armoured within garnet retained their primary 3-phase H₂O–CO₂ compositions. Reequilibration of fluid inclusions in quartz aggregates is most likely the result of recrystallization along with stress-induced, preferential H₂O leakage along dislocations and planar lattice defects which results in the predominance of CO₂ inclusions with supercritical densities. Carbonic fluid inclusions from adjacent kyanite–corundum-bearing pegmatoids and, the presence of shear-plane-parallel fluid inclusion planes within late quartz boudin structures consisting of pure CO₂-fluid inclusions with negative crystal shapes, bear witness of the latest stage of deformation by NE-directed extensional shear.This study shows that the textures of early fluid inclusions that formed already during the prograde metamorphic path can be preserved and used to derive information about the kinematics of subduction that is difficult to obtain from other sources. The textures of early inclusions, together with later generations of unaltered primary and secondary inclusions in metamorphic index minerals that can be linked to specific deformation stages and even P–T conditions, are a welcome supplement for the reconstruction of a rather detailed P–T–d path.     

The dynamics and thermodynamics of large ash flows

 Ash flow deposits, containing up to 1000 km³ of material, have been produced by some of the largest volcanic eruptions known. Ash flows propagate several tens of kilometres from their source vents, produce extensive blankets of ash and are able to surmount topographic barriers hundreds of metres high. We present and test a new model of the motion of such flows as they propagate over a near horizontal surface from a collapsing fountain above a volcanic vent. The model predicts that for a given eruption rate, either a slow (10–100 m/s) and deep (1000–3000 m) subcritical flow or a fast (100–200 m/s) and shallow (500–1000 m) supercritical flow may develop. Subcritical ash flows propagate with a nearly constant volume flux, whereas supercritical flows entrain air and become progressively more voluminous. The run-out distance of such ash flows is controlled largely by the mass of air mixed into the collapsing fountain, the degree of fragmentation and the associated rate of loss of material into an underlying concentrated depositional system, and the mass eruption rate. However, in supercritical flows, the continued entrainment of air exerts a further important control on the flow evolution. Model predictions show that the run-out distance decreases with the mass of air entrained into the flow. Also, the mass of ash which may ascend from the flow into a buoyant coignimbrite cloud increases as more air is entrained into the flow. As a result, supercritical ash flows typically have shorter runout distances and more ash is elutriated into the associated coignimbrite eruption columns. We also show that one-dimensional, channellized ash flows typically propagate further than their radially spreading counterparts. As a Plinian eruption proceeds, the erupted mass flux often increases, leading to column collapse and the formation of pumiceous ash flows. Near the critical conditions for eruption column collapse, the flows are shed from high fountains which entrain large quantities of air per unit mass. Our model suggests that this will lead to relatively short ash flows with much of the erupted material being elutriated into the coignimbrite column. However, if the mass flux subseqently increases, then less air per unit mass is entrained into the collapsing fountain, and progressively larger flows, which propagate further from the vent, will develop. Our model is consistent with observations of a number of pyroclastic flow deposits, including the 1912 eruption of Katmai and the 1991 eruption of Pinatubo. The model suggests that many extensive flow sheets were emplaced from eruptions with mass fluxes of 10⁹–10¹⁰ kg/s over periods of 10³–10⁵ s, and that some indicators of flow "mobility" may need to be reinterpreted. Furthermore, in accordance with observations, the model predicts that the coignimbrite eruption columns produced from such ash flows rose between 20 and 40 km. Received: 25 August 1995 / Accepted: 3 April 1996     

超临界流体中MoO3与WO3溶解度实验探讨

超临界地质流体以其独特的性质对金属成矿元素具有超强的萃取、层析和搬运能力,在热液矿床成矿机制研究中对揭示成矿物质的源、流和汇起着特殊和重要作用。本文利用分析纯H2MoO4在高温下脱水制备了MoO3(白色斜方晶系),在冷封式高压釜中实验测定了417℃超临界条件下,MoO3在纯水中的溶解度分别为7.3(29MPa)、14.2(45MPa)、21.6(55MPa)、27.7(78MPa)、32.5(100MPa)、和34.2(150MPa)mmol/l,热液中钼的存在形式为H2MoO4。依据前人的实验方案,补充测定了WO3在4.0%NaCl水溶液中于450%条件下的溶解度,其值分别为27.51(50MPa)和30.52(100MPa)mmol/l。结合前人研究结果发现,MoO3、WO3的溶解度在临界区域内具有超临界现象,在超临界条件下其溶解度与石英的超临界溶解度行为基本相似,表现为溶解度随体系温度和压力的升高而增大,这对揭示岩浆热液型和石英脉型钨、钼矿床的形成机制具有重要指导作用。     

Cleaning Using CO2‐Based Solvents

Cleaning with hierarchy of CO₂‐based solvents is advantageous from an environmental point of view because CO₂ is non‐flammable, virtually inert, and abundant. After cleaning, the only waste stuffs generated are the contaminants that are removed from the cleaned parts. The technology is especially well suited for precision cleaning applications in which parts have intricate geometries or for applications in which parts are sensitive to water or high temperature. This review will first introduce aqueous cleaning concepts and mechanism, which is helpful to understand how to design cleaning systems using high pressure CO₂. Recent microelectronic processes for cleaning and rising of circuit wafers using CO₂‐based solvents are the main focus of the review. Additional cleaning topics include dry cleaning, separation of dyestuffs, and extraction of contaminations from soils and regeneration of catalysts.     

高温高压下水的剪切粘滞度的平衡分子动力学计算

本项工作用ＴＩＰ４Ｐ模型对水分子进行了平衡分子动力学模拟。根据Ｇｒｅｅｎ－Ｋｕｂｏ理论,计算了温度从６５２Ｋ到８１４Ｋ,密度从０．５３６０ｇ／ｃｍ３到０．８６３８ｇ／ｃｍ３六个不同温度和密度水的剪切粘滞度,并和实验值进行了对比。在所计算的温度和密度范围,平衡分子动力学计算结果与实验值的平均绝对值差别为１５％,好于使用非平衡分子动力学方法获得的粘滞度值。平衡分子动力学的方法将是获得地学中高温高压下流体输运性质的重要途径。     

苏鲁造山带池庄超高压榴辉岩中变质脉:大陆俯冲带超临界流体活动的证据

高压-超高压变质岩中的变质脉能够反映俯冲带变质流体的组成和演化。为了探究大陆俯冲带超临界流体活动及伴随的元素迁移,本文系统地研究了苏鲁造山带南部江苏东海池庄地区的超高压榴辉岩及变质脉。变质脉主要是由石英、石榴石、绿辉石、多硅白云母、蓝晶石、黝帘石、金红石和锆石等矿物组成,与寄主榴辉岩的矿物组成类似。相比于榴辉岩,脉体中的石榴石更加富集重稀土元素(HREE);黝帘石强烈富集轻稀土元素(LREE)。变质脉和榴辉岩中各主要矿物的氧同位素组成在误差范围内一致(石英的δ18O分别为2.42‰和2.79‰;石榴石为-0.30‰和0.010‰;绿辉石为0.25‰和0.071‰),说明变质脉的形成与榴辉岩释放的内部流体有关。综合已有的研究,发现大别-苏鲁造山带不同地区的变质脉和榴辉岩具有极不均一的氧同位素组成,说明在陆壳深俯冲和折返过程中,流体活动有限。利用矿物温压计得到变质脉的峰期变质温压条件为692±65℃和3.6±0.3GPa,脉体中锆石U-Pb定年结果表明锆石的形成时代为218±2.4Ma,指示变质脉形成于深俯冲陆壳折返初期的超高压变质阶段。变质脉中矿物组合和矿物的主微量元素特征说明成脉流体富集Si、Al、Ca、K、LILE、REE和HFSE等元素,表明成脉流体可能是溶解能力极强的超临界流体。     

Metal Ion Extraction with Bipyridine Derivatives as Chelating Ligands in Supercritical Carbon Dioxide

Three fluorinated bipyridine ligands have been designed and synthesized as chelating agents for the extraction of metal ions in supercritical CO₂ (sc‐CO₂). The ligand solubilities in sc‐CO₂ were investigated at different temperatures and pressures, and the measured data have been correlated using a semiempirical model. The calculated results showed satisfactory agreement with the experimental data. Based on these data, metal ion extraction with the three compounds as chelating agents in sc‐CO₂ was performed from spiked filter paper, whereby ligand 1 showed the highest extraction efficiency, especially for Ni²⁺ and Cu²⁺. The extraction constants, K_ex, of the three chelating ligands were seen to increase with increasing extraction efficiency for the same metal ion in the same extraction system.     

Contact angles in CO2-water-coal systems at elevated pressures

Injection of carbon dioxide into coal seams is considered to be a potential method for its sequestration away from the atmosphere. However, water present in coals may retard injection: especially if carbon dioxide does not wet the coal as well as water. Thus contact angles in the coal-water-CO₂ system were measured using CO₂ bubbles in water/coal systems at 40 °C and pressures up to 15 MPa using five bituminous coals. At low pressures, in this CO₂/water/coal system, receding contact angles for the coals ranged between 80° to 100°; except for one coal that had both high ash yield and low rank, with a contact angle of 115°, indicating that it was hydrophilic. With increasing pressure, the receding contact angles for the different coals decreased, indicating that they became more CO₂-wetting. The relationship between contact angle and pressure was approximately linear. For low ash or high rank coals, at high pressure the contact angle was reduced to 30-50°, indicating the coals became strongly CO₂-wetting; that is CO₂ fluids will spontaneously penetrate these wet coals. In the case of the coal that was both high ash and hydrophilic, the contact angle did not drop to 90° even at the highest pressures used. These results suggest that CO₂ will not be efficiently adsorbed by all wet coals equally well, even at high pressure. It was found that at high pressures (> 2 MPa) the rate of penetration of carbon dioxide into the coals increased rapidly with decreasing contact angle, independently of pressure. Injecting CO₂ into wet coals that have both low rank and high ash will not trap CO₂ as well as injecting it into high rank or low ash coals.     

Impact of experimental parameters for manometric equipment on CO2 isotherms measured: Comment on “Inter-laboratory comparison II: CO2 isotherms measured on moisture-equilibrated Argonne premium coals at 55°C and up to 15 MPa” by Goodman et al. (2007)

Modelling the sorption properties of coals for carbon dioxide under supercritical conditions is necessary for accurate prediction of the sequestering ability of coals in seams. We present recent data for sorption curves of three dry Argonne Premium coals, for carbon dioxide, methane and nitrogen at two different temperatures at pressures up to 15 MPa. The sorption capacity of coals tends to decrease with increasing temperature. An investigation into literature values for sorption of nitrogen and methane by charcoal also show sorption capacities that decrease dramatically with increasing temperature. This is inconsistent with expectations from Langmuir models of coal sorption, which predict a sorption capacity that is independent of temperature. We have successfully fitted the isotherms using a modified Dubinin–Radushkevich equation that uses gas density rather than pressure. A simple pore-filling model that assumes there is a maximum pore width that can be filled in supercritical conditions and that this maximum pore width decreases with increasing temperature, can explain this temperature dependence of sorption capacity. It can also explain why different supercritical gases give apparently different surface sorption capacities on the same material. The calculated heat of sorption for these gases on these coals is similar to those found for these gases on activated carbon.