Immiscible phases of magmatic fluid and their relation to Be and Mo mineralization at the Yermakovka F–Be deposit, Transbaikalia, Russia

Melt and fluid inclusions in minerals from the peralkaline granite intrusion and associated mineralized country rocks from the Yermakovka F–Be deposit were studied to characterize the behaviour of trace elements and exsolved fluids in the transition from magmatic to hydrothermal processes. Ore mineralization was mostly due to volatile release from a deep-seated pluton for which crystallization history and fluid exsolution can be tracked by three batches of magma (Gr1→Gr3) intruded at the level of the ore deposition to form the Yermakovka stock. Each batch of the sequential granite group is found to intrude at decreasing temperature (from 840 to 730 °C) and progressively increasing extent of crystallization of magma in the parental pluton. This resulted in the enrichment of the ascending melts in H₂O (3.9 to 6.1 wt.%), F (2.6 to 4.1 wt.%) and some incompatible elements (Zr, Nb, Th, Rb, Pb). Although the earliest evidence for the exsolution of homogeneous fluoride–sulphate brine correlates with the final stage of the Gr2 ascent, the most intensive volatile(s) release from the emplaced magmas is shown to occur during their in situ crystallization, which was associated with the separation of exsolved fluid into immiscible phases, brine and low-salinity solution. Compositions of these fluid phases are determined using atomic emission spectroscopy of the appropriate fluid inclusions opened by a laser microprobe and EMPA and SEM–EDS analyses of daughter crystals. The brine phase is enriched in Mo, Mn, Be (up to 17, 8, and 0.3 g/kg, respectively) and contains perceptible abundances of Ce, La, Pb, Zn, whereas the low-salinity phase is enriched only in Be (up to 0.6 g/kg). The selective mobilization of the metals from the melt into fluids is considered to result from the oxidized state of the melt and fluids, peralkalinity of the melt during crystallization, and high F content of the melt. The immiscible fluid phases are shown to migrate together through the solidifying stock giving rise to the albitized granite that is enriched in molybdenite but devoid of Be minerals. In the country rocks, solutions similar to the brine and low-salinity phases of the magmatic fluid made up separate fluid flows, which produced Be and Mo mineralization and were issued predominantly from the parental pluton. Both types of mineralization are nearly monometallic which suggests that of the metals, jointly transported by the brine, only Mo and, in part, Ce and La precipitated separately at the level where the low-salinity solutions deposited Be ores.     

Magmatic evolution of Li–F, rare-metal granites: a case study of melt inclusions in the Khangilay complex, Eastern Transbaikalia (Russia)

We report compositions of homogenized quartz-hosted melt inclusions from a layered sequence of Li-, F-rich granites in the Khangilay complex that document the range of melt evolution from barren biotite granites to Ta-rich, lepidolite–amazonite–albite granites. The melt inclusions are crystalline at room temperature and were homogenized in a rapid-quench hydrothermal apparatus at 200 MPa before analysis. Homogenization runs determined solidus temperatures near 550 °C and full homogenization between 650 and 750 °C. The compositions of inclusions, determined by electron microprobe and Raman spectroscopy (for H₂O), show regular overall trends of increasing differentiation from the least-evolved Khangilay units to apical units in the Orlovka intrusion. Total volatile contents in the most-evolved melts reach over 11 wt.% (H₂O: 8.6 wt.%, F: 1.6 wt.%, B₂O₃: 1.5 wt.%). Concentrations of Rb range from about 1000 to 3600 ppm but other trace elements could not be measured reliably by electron microprobe. The resulting trends of melt evolution are similar to those described by the whole-rock samples, despite petrographic evidence for albite- and mica-rich segregations previously taken as evidence for post-magmatic metasomatism.

Melt variation trends in most samples are consistent with fractional crystallization as the main process of magma evolution and residual melt compositions plot at the granite minimum in the normative Qz–Ab–Or system. However, melts trapped in the highly evolved pegmatitic samples from Orlovka deviate from the minimum melt composition and show compositional variations in Al, Na and K that requires a different explanation. We suggest that unmixing of the late-stage residual melt into an aluminosilicate melt and a salt-rich dense aqueous fluid (hydrosaline melt) occurred. Experimental data show the effectiveness of this process to separate K (aluminosilicate melt) from Na (hydrosaline melt) and high mobility of the latter due to its low viscosity and relatively low density may explain local zones of albitization in the upper parts of the granite.     

The fluid regime of ore formation in the Balei gold-bearing ore-magmatic system (eastern Transbaikalia,Russia)

Based on comprehensive studies of fluid inclusions in quartz formed at different stages of hydrothermal process, we consider the physicochemical conditions of formation of epithermal ores (K₁) in the Balei ore field. The limiting parameters of hydrothermal process have been established: 353–131 °C, 150–30 bars, and salt concentrations of 7.6–0.5 wt.%-NaCl equiv. A specific feature of the ore-forming process at the Balei deposits is a rapid drop in temperature and pressure, which is typical of open hydrothermal systems. The temperature increase at the beginning of each stage evidences pulse-like ore formation. The productive stage coincides with the initiation of a drastic decrease in temperature (<225 °C) and salt concentration in the solution. The deposits resulted from the functioning of the common Balei ore-magmatic system at shallow depths with a high permeability of the host rocks. High-K calc-alkalic magmas might have been sources of gold mineralization. The ore formation zone is localized above intrusive bodies near their roof. It is not ruled out that the Balei gold was partly borrowed from the products of the early cycles (J_2-3) of gold mineralization and from the host rocks.     

Processes of formation of fluorite-leucophane-melinophane-eudidymite ores of the Ermakovka F-Be deposit (western Transbaikalia)

Fluorite-leucophane-melinophane-eudidymite ores of zone XVIII of the Ermakovka F-Be deposit were studied by geological, mineralogical, and thermobarogeochemical methods. Contents of Be and impurity elements (Li, Na, Mg, Al, Si, Cl, K, Mn, Fe, Cu, Zn, Nb, Mo, Ag, Sn, W, and Pb) in fluid inclusions in fluorite of this zone have been first determined by LA-ICP-MS. It is shown that fluorite-leucophane-melinophane-eudidymite ores were formed by alkaline high-F low-salt (6.0-12.5 wt.% NaCl equiv) solutions with a relatively low content of Be (0.0002-1.04 g/kg of solution). Fluorite and beryllium minerals were deposited in ores in a wide range of P-T conditions. The early fluorite-phenakite paragenesis formed at high temperatures (480-650 °C) and high pressures (> 3 kbar). At the late low-temperature stage, phenakite was replaced by Na-Be silicates (eudidymite and melinophane-leucophane) at < 220 °C and < 770 bars. The Be-ore deposition was due to the destruction of a predominant beryllium fluoride-carbonate complex as a result of the crystallization of fluorite during the metasomatic replacement of limestones. Eudidymite and melinophane-leucophane formed at low temperatures under high activity of Na and Ca and low activity of Be and F in highly alkaline solutions.     

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

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

High-density early CO2 fluids in the ultrahigh-temperature granulites of Ihouhaouene (In Ouzzal, Algeria)

Fluid inclusion studies in rocks from the Lower Proterozoic granulites from western Hoggar (Algeria) provide new evidence for the hypothesis that a CO₂-rich, H₂O-poor fluid was present during the high-grade metamorphism. CO₂ inclusions represent the main fluid trapped in the Ihouhaouene ultrahigh-temperature (over 1000 °C) and high-pressure (10 to 14 kbar) granulites. The microthermometric and Raman microspectrometric measurements indicate that the carbonic fluid is mainly composed of CO₂ with minor amounts of CH₄ and N₂ detected in some inclusions (< 4 mol% CH₄). Carbonic fluid densities range from 1.18 to 0.57 g/cm³. The highest densities are recorded in superdense carbonic inclusions presenting evidence of the earliest trapping and they correspond to the fluid densities expected for the P–T conditions of the peak of metamorphism in the area previously determined from mineral geothermobarometers. Lower densities of carbonic fluids mainly result from the reequilibration of earlier trapped fluid inclusions during retrograde metamorphism and final uplift of the metamorphic terrane, but a new influx of carbonic fluids during the retrograde event remains possible. Carbonic fluids can be produced in situ from decarbonation reactions in interlayered impure marbles during the prograde event or derived from CO₂ flushing from underlying basic intrusions. The aqueous fluids present large variations of composition (0.5 to 30 wt.% NaCl equivalent) and densities (1.16 to 0.57 g/cm³). They clearly correspond to post-metamorphic fluids because they mainly occur along microfractures, they do not show any evidence of immiscibility with the carbonic fluids and mixed aquo-carbonic inclusions have not been observed. The percolation of aqueous fluids is related to the Pan-African tectonometamorphic event.     

胶东蓬莱金矿区流体包裹体和氢氧同位素地球化学研究

蓬莱地区金矿床以石英脉型为主,其次是蚀变岩型;成矿条件与著名的玲珑金矿床相似。金主要产于黄铁矿和多金属硫化物石英脉中。流体包裹体研究表明,金矿床中主要存在两种类型的流体包裹体：CO2-H2O包裹体和中低盐度的NaCl—H2O溶液包裹体。CO2-H2O包裹体气相以CO2为主,可含少量CH4、H2S、CO。其中,黄铁绢英岩的石英中含有丰富的CO2-H2O包裹体,而黄铁矿石英脉和多金属硫化物石英脉中富CO2与富H2O的CO2-H2O包裹体共存。显微测温结果显示,黄铁绢英岩中的CO2-H2O包裹体的均一温度范围为230℃～300℃;而黄铁矿和多金属硫化物石英包裹体的均一温度为220℃-390℃,鉴于这些包裹体是从不混溶的CO2-H2O流体中捕获的,因此它们的温度下限220℃～250℃左右,应该看作是它们的形成温度。成矿早期流体为富含挥发份（流体密度0．92～0.985g／cm^3）、中低盐度（4．15％～5.23％NaCleqv）的流体：到主成矿期逐渐演化为温度升高,盐度变化范围大（1.02％～15.5％NaCleqv）,水溶液以NaCl为主,气体仍以CO2为主,但可含少量的CH4、H2S、CO及有机质等的流体（流体密度0.32～0.99g／cm^3）;成矿期后的流体盐度、温度及CO2含量降至最低。本区矿床中石英的占δ^18O值变化在13.8‰-18.3‰,成矿流体的占δ^18O值在4、9‰-10.9‰之间,流体包裹体中占D变化范围很小,从-78‰变化到-101‰,主要集中在-78‰～-88‰之间。由此表明成矿流体以岩浆水为主,伴有大气降水的参与。在主成矿期成矿流体表现出明显的多期、多来源特征。温度降低和流体不混溶是导致金等成矿元素沉淀和富集的重要机制。     

A detailed fluid inclusion study in silicified breccias from the Kombolgie sandstones (Northern Territory, Australia): inferences for the genesis of middle-Proterozoic unconformity-type uranium deposits

The relative chronology and detailed chemistry of paleofluids circulating at the base of the Kombolgie Sub-basin were investigated in the East Alligator River district (Northern Territory, Australia), where world-class unconformity-type uranium deposits are located. The chemistry of fluid inclusions was determined using in-situ analysis (Raman microprobe and laser-induced breakdown spectroscopy [LIBS]) and by observing the melting sequences by microthermometry. This study revealed the occurrence of three distinct fluids: (i) a sodium-rich brine that corresponds to a diagenetic fluid percolating at the bottom of the Kombolgie sandstones at a temperature close to 150±15 °C; (ii) a calcium-rich brine, probably corresponding to a residual brine in evaporitic environment that has evolved by fluid–rock interactions with the basement lithologies; and (iii) a low salinity fluid, heated in the basement, injected into the base of the sandstone cover. H₂ and O₂ and/or traces of CH₄ were detected in the vapor phase of some fluid inclusions, especially in the low salinity ones in quartz breccia samples taken above mineralized areas. Hydraulic brecciation of the sandstone was associated with a pressure decrease favoring fluid mixing and the subsequent cementation of breccias. According to the fluid inclusion study and other geologic constrains, the minimum thickness of the Sub-Kombolgie Basin is estimated at 4 km. Drusy quartz breccias with evidence of fluid mixing are quite common at the base of the Kombolgie Basin, but not necessarily linked to U-mineralization. However, it is proposed that the presence of gases such as H₂ and O₂ in fluid inclusions, which results from water radiolysis, constitutes an indicator of gas linked to significant U concentrations deeper in the basement rocks.     

Magmatic-hydrothermal Evolution and Mineralization Mechanisms of the Wangjiazhuang Cu (-Mo) Deposit in the Zouping Volcanic Basin, Shandong Province, China: Constraints from Fluid Inclusions

The Wangjiazhuang Cu (-Mo) deposit, located within the Zouping volcanic basin in western Shandong Province, China, is unique in this area for having an economic value. In order to expound the metallogenetic characteristics of this porphyry-like hydrothermal deposit, a detailed fluid inclusion study has been conducted, employing the techniques of representative sampling, fluid inclusion petrography, microthermometry, Raman spectroscopy, LA-ICP-MS analysis of single fluid inclusions, as well as cathode fluorescence spectrometer analysis of host mineral quartz. The deposit contains mainly two types of orebodies, i.e. veinlet-dissemination-stockwork orebodies in the K-Si alteration zone and pegmatitic-quartz sulfide veins above them. In addition, minor breccia ore occurs locally. Four types of fluid inclusions in the deposit and altered quartz monzonite are identified: L-type one- or two-phase aqueous inclusions, V-type vapor-rich inclusions with V/L ratios greater than 50%–90%, D-type multiphase fluid inclusions containing daughter minerals or solids and S-type silicate-bearing fluid inclusions containing mainly muscovite and biotite. Ore petrography and fluid inclusion study has revealed a three-stage mineralization process, driven by magmatic-hydrothermal fluid activity, as follows. Initially, a hydrothermal fluid, separated from the parent magma, infiltrated into the quartz monzonite, resulting in its extensive K-Si alteration, as indicated by silicate-bearing fluid inclusions trapped in altered quartz monzonite. This is followed by the early mineralization, the formation of quartz veinlets and dissemination-stockwork ores. During the main mineralization stage, due to the participation and mixing of meteoric groundwater with magmatic-sourced hydrothermal fluid, the cooling and phase separation caused deposition of metals from the hydrothermal fluids. As a result, the pegmatitic-quartz sulfide-vein ores formed. In the late mineralization stage, decreasing fluid salinity led to the formation of L-type aqueous inclusions and chalcopyrite-sulfosalt ore. Coexistence of V-type and D-type inclusions and their similar homogenization temperatures with different homogenization modes suggest that phase separation or boiling of the ore-forming fluids took place during the early and the main mineralization stages. The formation P-T conditions of S-type inclusions and the early and the main mineralization stages were estimated as ca. 156–182 MPa and 450–650°C, 350–450°C, 18–35 MPa and 280–380°C, 8–15 MPa, respectively, based on the microthermometric data of the fluid inclusions formed at the individual stages.     

Fluid inclusions in high pressure/low temperature rocks from the Calabrian Arc (Southern Italy): the burial and exhumation history of the subduction-related Diamante-Terranova unit

The Diamante-Terranova Unit (DIATU), in the Calabrian Arc of southern Italy, is part of an ophiolitic sequence involved in a high pressure/low temperature event (P=8 kbar; T =400 °C) followed by re-equilibration at greenschist facies conditions (P=3 kbar; T =300 °C). The rocks contain two types of quartz–calcite veins – an earlier generation of deformed, folded and faulted veins formed during or before subduction, and a later set of planar, undeformed veins formed during exhumation of the DIATU. The earlier folded quartz–calcite veins contain regularly shaped aqueous inclusions as well as inclusions with a highly irregular dendritic texture. The later planar veins contain only regularly shaped aqueous inclusions similar to those in the earlier veins. In both vein types, all inclusions are demonstrably secondary in origin. Regularly shaped inclusions from both vein types are low salinity (0–5 wt% NaCl). Most contain liquid and vapour and homogenize to the liquid (Th 135–180 °C), whereas others contain only liquid at room temperature. Both the two-phase and monophase inclusions occur in the same fractures and are thought to record the same trapping event, with the monophase inclusions remaining metastable liquid at room temperature. No microthermometric data could be obtained from the dendritic inclusions in the earlier folded veins. Inclusions with the highly irregular dendritic texture found in the earlier veins are similar to those produced experimentally during laboratory-induced deformation of synthetic inclusions in quartz under conditions of internal underpressure, simulating either isobaric cooling or isothermal compression. The occurrence of inclusions with the dendritic texture in the earlier folded veins, and their absence from the later planar veins, suggests that the earlier veins formed before or during subduction and were folded and faulted in a compressional environment and their contained fluid inclusions were modified to produce the dendritic texture. During later uplift of the DIATU, planar veins containing regularly shaped aqueous inclusions formed and some of the fluids forming these veins were also trapped as secondary inclusions in the earlier folded veins. The results of this study provide convincing evidence that inclusions with a highly irregular dendritic morphology represent early inclusions that have survived prograde conditions in a high pressure/low temperature metamorphic environment (but have been texturally modified). The high pressure/low temperature ‘implosion’ texture is preserved over geological time, even after being overprinted by internal overpressure conditions generated during retrograde decompression. We suggest that inclusions that have survived prograde metamorphism are common in high pressure/low temperature rocks, but are often not identified as such due to their morphology which makes their recognition difficult.     

Comment on “Structural controls on a carbon dioxide-driven mud volcano field in the Northern Apennines (Pieve Santo Stefano, Italy): Relations with pre-existing steep discontinuities and seismicity”

Bonini (2009, Structural controls on a carbon dioxide-driven mud volcano field in the Northern Apennines (Pieve Santo Stefano, Italy): relations with pre-existing steep discontinuities and seismicity. Journal of Structural Geology 31, 44–54) presents a 2D mechanical analysis to infer the failure conditions responsible for the seismicity distribution during an M_w = 4.6 seismic sequence nucleating during 2001 in the Northern Apennines. In my view the mechanical analysis presented in this paper has some weakness or is not well constrained, in particular: 1) the assumption of a dip angle of 50°, is not consistent with the activated structures; 2) the P_f = σ₃ condition, difficult to be attained along a cohesionless fault dipping at 50°; 3) the isotropic stress state, i.e. σ₂ = σ₃, that is not consistent with the active or recent stress field in the area.     

Thermochemical sulphate reduction in the Upper Devonian Cairn Formation of the Fairholme carbonate complex (South-West Alberta, Canadian Rockies): evidence from fluid inclusions and isotopic data

The Fairholme carbonate complex is part of the extensively dolomitized Upper Devonian carbonate reefs in west-central Alberta. The studied formations contain moulds (up to 10 cm in diameter), which are filled partially with (saddle) dolomite, quartz and calcite cements. These cements precipitated from a mixture of brines that acquired high salinity by dissolution of halite and brines derived from evaporated sea water. The fluids were warm (homogenization temperature of primary fluid inclusions of 76 to 200 °C) and saline (20 to 25 wt% NaCl equivalent) and testify to thermochemical sulphate reduction processes. The latter is deduced from S in solid inclusions, CO₂ and H₂S in volatile-rich aqueous inclusions and depleted δ¹³C values down to −26‰ Vienna Pee Dee Belemnite. High ⁸⁷Sr/⁸⁶Sr values (0·7094 to 0·7110) of the cements also indicate interaction of the fluids with siliciclastic sequences. The thermochemical sulphate reduction-related cements probably formed during early Laramide burial. Another (younger) calcite phase, characterized by depleted δ¹⁸O values (−23·9‰ to −13·9‰ Vienna Pee Dee Belemnite), low Na (27 to 37 p.p.m.) and Sr (39 to 150 p.p.m.) concentrations and non-saline (∼0 wt% NaCl equivalent) fluid inclusions, is attributed to post-Laramide meteoric water.     

Fluid Inclusions of Calcite and Sources of Ore-forming Fluids in the Huize Zn-Pb-(Ag-Ge) District, Yunnan, China

The Huize Zn-Pb- (Ag-Ge) district is a typical representative of the well-known medium-to large-sized carbonate-hosted Zn-Pb- (Ag-Ge) deposits, occurring in the Sichuan-Yunnan-Guizhou Pb-Zn Ore-forming Zone. Generally, fluid inclusions within calcite, one of the major gangue minerals, are dominated by two kinds of small (1-10 um) inclusions including pure-liquid and liquid. The inclusions exist in concentrated groups along the crystal planes of the calcite. The ore-forming fluids containing Pb and Zn, which belong to the Na+-K+-Ca2+-Cl--F--SO42- type, are characterized by temperatures of 164-221℃, medium salinity in 5-10.8 wt% NaCl, and medium pressure at 410×105 to 661×105 Pa. The contents of Na+-K+ and C1--F-, and ratios of Na+/K+-Cl-/F- in fluid inclusions present good linearity. The ratios of Na+/K+ (4.66-6.71) and Cl-/F- (18.21-31.04) in the fluid inclusions of calcite are relatively high, while those of Na+/K+ (0.29-5.69) and Cl-/F- (5.00-26.0) in the inclusions of sphalerite and pyrite are rela     

A Vendian-Cambrian Island Arc System of the Siberian Continent in Gorny Altai (Russia, Central Asia)

An extended Vendian-Cambrian island-arc system similar to the Izu-Bonin-Mariana type is described in the Gorny Altai terrane at the margin of the Siberian continent.

Three different tectonic stages in the terrane are recognized. (1) A set of ensimatic active margins including subducted oceanic crust of the Paleo-Asian ocean, the Uimen-Lebed primitive island arc, oceanic islands and seamounts: the set of rocks is assumed to be formed in the Vendian. (2) A more evolved island arc comprising calc-alkaline volcanics and granites: a fore-arc trough in Middle-late Cambrian time was filled with disrupted products of pre-Middle Cambrian accretionary wedges and island arcs. (3) Collision of the more evolved island arc with the Siberian continent: folding, metamorphism and intrusion of granites occurred in late Cambrian-early Ordovician time.

In the late Paleozoic, the above-mentioned Caledonian accretion-collision structure of the Siberian continent was broken by large-scale strike-slip faults into several segments. This resulted in the formation of a typical mosaic-block structure.     

Magmatic Nature of Mineralizing Fluids in the Solnechnoye Sn Deposit (Russia) Deduced from Isotopic (H,O) Compositions of Tourmaline

In this paper, we present new isotopic (H, O) data of fluids in tourmalines from the large Sn deposit at Solnechnoye (Far East Russia). These data indicate that the deposit formed by fluid‐rock interactions in a hydrothermal system where the mineralizing fluid was mainly magmatic and to a lesser extent meteoric. This is in agreement with a magmatic fluid model. Our interpretation of the new isotopic data is consistent with earlier findings of the studies on fluid‐rock interactions that magmatic fluids form larger Sn deposits than exogenic fluids. We propose that isotopic (H, O) data of fluids in tourmaline, rather than those in quartz, muscovite, or chlorite, support robust interpretation on the nature of mineralizing fluids associated with Sn deposits.     

临界区流体与矿物和岩石在地球内部极端条件下的反应

极端条件下水热化学反应是一个新的科学问题。借助于高温超高压原位直接测量方法、各种谱学方法和同步辐射光源技术研究地球内部流体物质相互作用,可以获得反应过程的产物的分子-原子尺度信息,这些信息可以提供认识极端条件下水和矿物(岩石)反应动力学的新实验途径。地球内部的流体性质随所处高温高压条件发生变化。水的密度、介电常数等物理参数随温度压力变化而改变,在临界态会出现突变。水的性质的剧变会影响水与岩石(矿物)相互作用。文中报道了在极端条件下(20～435℃和23～35MPa)实验测量矿物(钠长石、辉石、石英和阳起石等)和岩石(玄武岩、正长岩)在水溶液里的溶解反应速率的研究结果,发现矿物里各种不同类型金属离子与水反应的速率不同,随温度变化而改变。在升温过程中,进入临界态时,矿物(岩石)与水反应出现一次反应速率的涨落。在恒压升温过程中(临界压力,或略高于临界压力),硅酸盐矿物溶解速率会逐步升高,如硅近临界区(300℃)抵达最大值,然后随升温溶解反应速率减低。地球内部的流体由深处上升到浅处,会从超临界区域进入近临界的气与液的两相不混溶区域。含金属流体里的金属会在气相与液相分离时出现再分配。实验表明:金属Au、Cu、Sn、W、Zn会进入气相,气体可以迁移金属。事实说明:地球内部流体结构和性质从深到浅在不断变化,在跨越临界区时的水的性质异常变化会导致水与矿物(岩石)反应动力学涨落,并且促使金属在临界区出现沉淀和在气液相分离过程中进行再分配及迁移。     

Evolution of mineralizing fluids in the Zn–Pb–Cu(–Ag ± Au) skarn and epithermal deposits of the world-class San Martín district, Zacatecas, Mexico

Mineralizing fluids at the San Martín skarn show an evolution characterized by prograde and retrograde associations. The prograde mineral associations consist of (1) a massive garnet zone, (2) a tremolite ± garnet zone, and (3) a late association of quartz, sphalerite, calcite and fluorite lining the vugs in the garnet zone. The fluids of the prograde associations exhibit decreasing temperatures of homogenization (Th) and variable salinities. The fluids of the massive garnet zone have salinities of 36 wt.% NaCl equiv. and Th of 645 to 570 °C, corresponding to pressures of 1055 bar. At the tremolite ± garnet zone, Th range from 438 to 354 °C. In the late association at the endoskarn, the following evolution can be drawn: (a) salinities of 50 to 42 wt.% NaCl equiv., and Th of 455 to 346 °C in quartz, (b) salinities of 46 wt.% NaCl equiv., and Th of 415 to 410 °C in sphalerite, (c) salinities of 50 to 37 wt.% NaCl equiv., and Th of 479 to 310 °C in calcite, (d) salinities of 33 to 28 wt.% NaCl equiv. and of 24 to 22 wt.% KCl in fluorite, and (e) two types of fluids with salinities of 2 and 39 wt.% NaCl equiv. and Th 344 and 300 °C, respectively, in later saccharoidal quartz segregations. The retrograde mineral associations comprise pervasive propylitic alteration to carbonization, and mantos with sulfides. Fluids in epidote have salinities of 7.6 wt.% NaCl equiv. and Th of 287 to 252 °C, and in calcite have salinities of 9.2 to 1 wt.% NaCl equiv. and Th of 188 to 112 °C. Fluids in the sulfide assemblages in the mantos have salinities of 8 to 3 wt.% NaCl equiv. and Th 300 °C, with corresponding pressures of 94 bar. Fluids in late epithermal veins close to the intrusive body have salinities of 10 to 5 wt.% NaCl equiv. and Th of 275 to 200 °C, and distal veins show salinities of 2 to 1 wt.% NaCl equiv. and Th of 160 °C.     

Diurnal soil water dynamics in the shallow vadose zone (field site of China University of Geosciences,China)

Because of the relatively low soil moisture in arid or semi-arid regions, water vapour movement often predominates in the vadose zone and affects the partitioning of energy among various land surface fluxes. In an outdoor sand bunker experiment, the soil water content at 10 and 30 cm depth were measured at hourly intervals for 2.5 days during October 2004. It was found that the soil moisture reached the daily maximum value (5.9–6.1% at 10 cm and 11.9–13.1% at 30 cm) and minimum value (4.4–4.5% at 10 cm and 10.4–10.8% at 30 cm) at midday (0–1 p.m. for 10 cm and 2–3 p.m. for 30 cm) and before dawn (2–3 a.m. for 10 cm and 4–5 a.m. for 30 cm), respectively. The modified HYDRUS-1D code, which refers to the coupled water, water vapour and heat transport in soil, was used to simulate the moisture and water vapour flow in the soil. The numerical analyses provided insight into the diurnal movement of liquid water and water vapour driven by the gradients of pressure heads and temperatures in the subsurface zone. The simulated temperature and water content were in good agreement with the measured values. The spatial–temporal distribution of liquid water flux, water vapour flux and soil temperature showed a detailed diurnal pattern of soil water dynamics in relatively coarse sand. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Impure marbles from the UHP Brossasco-Isasca Unit (Dora-Maira Massif, western Alps): evidence for Alpine equilibration in the diamond stability field and evaluation of the X(CO2) fluid evolution

Two impure ultrahigh-pressure (UHP) marbles, a calcite marble with the peak assemblage Grt + Phe + Cpx + Rt + (Arg) and a dolomite marble with the peak assemblage Crn + Chl + Rt + Dol (±Arg), from the same lens from the polymetamorphic complex of the Brossasco-Isasca Unit (BIU) (southern Dora-Maira Massif) have been petrologically investigated and modelled by calculating P – T phase-diagram projections for H₂O–CO₂ mixed-volatile systems. Thermobarometric data obtained from the calcite marble suggest Alpine peak conditions in the diamond stability field (4.0 GPa at 730 °C), and allow reconstruction of the earlier portion of the Alpine retrograde P – T path, which is characterized by a significant decompression coupled with a moderate and continuous cooling to 650 °C at 2.50 GPa. The modelled fluid compositions at peak conditions point to 0.025 ≤  X (CO₂) ≤ 0.10 and X (CO₂) ≤ 0.0012 in the calcite marble and dolomite marble, respectively, suggesting fluid heterogeneity at the local scale and an internally buffered fluid evolution of the studied impure marbles. The lack of micro-diamond in the BIU marbles is explained by the very-low X (CO₂) values, which favoured relatively high f O₂-conditions, preventing the formation of diamond at the UHP peak metamorphic conditions.