Carbon and Oxygen Isotope Compositions of Calcite and Rhodochrosite from Geothermal Exploratory Drills TH‐4 and TH‐6 near the Toyoha Deposit,Hokkaido, Japan

We studied calcite and rhodochrosite from exploratory drill cores (TH‐4 and TH‐6) near the Toyoha deposit, southwestern Hokkaido, Japan, from the aspect of stable isotope geochemistry, together with measuring the homogenization temperatures of fluid inclusions. The alteration observed in the drill cores is classified into four zones: ore mineralized zone, mixed‐layer minerals zone, kaolin minerals zone, and propylitic zone. Calcite is widespread in all the zones except for the kaolin minerals zone. The occurrence of rhodochrosite is restricted in the ore mineralized zone associated with Fe, Mn‐rich chlorite and sulfides, the mineral assemblage of which is basically equivalent to that in the Toyoha veins. The measured δ¹⁸O_SMOW and δ¹³C_PDB values of calcite scatter in the relatively narrow ranges from ?2 to 5‰ and from ?9 to ?5‰, respectively; those of rhodochrosite from 3 to 9‰ and from ?9 to ?5‰, excluding some data with large deviations. The variation of the isotopic compositions with temperature and depth could be explained by a mixing process between a heated surface meteoric water (100°C δ¹⁸O =?12‰, δ¹³C =?10‰) and a deep high temperature water (300°C, δ¹⁸O =?5‰, δ¹³C =?4‰). Boiling was less effective in isotopic fractionation than that of mixing. The plots of δ¹⁸O and δ¹³C indicate that the carbonates precipitated from H₂CO₃‐dominated fluids under the conditions of pH = 6–7 and T = 200–300°C. The sequential precipitation from calcite to rhodochrosite in a vein brought about the disequilibrium isotopic fractionation between the two minerals. The hydrothermal fluids circulated during the precipitation of carbonates in TH‐4 and TH‐6 are similar in origin to the ore‐forming fluids pertaining to the formation of veins in the Toyoha deposit.     

Fluid flow in the Sicilian accretionary wedge: Primary geochemical signatures or recrystallization mask

Veins in the Sicilian accretionary wedge were studied petrographically and geochemically with the aim to investigate the relation between fluid flow in a décollement horizon and in overlying Mesozoic basinal sediments. Fluids expelled along the décollement horizon precipitated calcite cements that show a broad spread in stable isotope signatures and that generally have rather high Fe and Mn content. The fluids most likely originated from mixing of hot deep metamorphic fluids and dewatering of the clay unit along which the principal overthrusting occurred.Synkinematic veins in the overlying basinal units are cemented with calcite. The trace element content and δ¹³C signatures of these veins are host-rock dependent, pointing to a host-rock buffering effect. Petrographic observations indicate that calcite cements have been recrystallized. Thus the cements could have inherited their geochemical signatures from the host-rock during recrystallization. This is also supported by their δ¹⁸O signature, which is controlled by temperature fractionation.     

Paragenesis of Cretaceous to Eocene carbonate reservoirs in the Ionian fold and thrust belt (Albania): relation between tectonism and fluid flow

ABSTRACT This paper examines the diagenetic history of dual (i.e. matrix and fracture) porosity reservoir lithologies in Cretaceous to Eocene carbonate turbidites of the Ionian fold and thrust belt, close to the oil‐producing centre of Fier–Ballsh (central Albania). The first major diagenetic event controlling reservoir quality was early cementation by isopachous and syntaxial low‐Mg calcite. These cements formed primarily around crinoid and rudist fragments, which acted as nucleation sites. In sediments in which these bioclasts are the major rock constituent, this cement can make up 30% of the rock volume, resulting in low effective porosity. In strata in which these bioclasts are mixed with reworkedmicrite, isopachous/syntaxial cements stabilized the framework, and matrixporosity is around 15%. The volumetric importance of these cements, their optical and luminescence character (distribution and dull orange luminescence) and stable isotopic signal (δ¹⁸O and δ¹³C averaging respectively; ?0·5‰ VPDB and +2‰ VPDB) all support a marine phreatic origin. Within these turbidites and debris flows, several generations of fractures alternated with episodes of cementation. A detailed reconstruction of this history was based on cross‐cutting relationships of fractures and compactional and layer‐parallel shortening (LPS) stylolites. The prefolding calcite veins possess orange cathodoluminescence similar to that of the host rock. Their stable isotope signatures (δ¹⁸O of ?3·86 to ?0·85‰ VPDB and δ¹³C of – 0·14 to + 2·98‰ VPDB) support a closed diagenetic rock‐buffered system. A similar closed system accounts for the selectively reopened and subsequently calcite‐cemented LPS stylolites (δ¹⁸O of ?1·81 to ?1·14‰ VPDB and δ¹³C of +1·52 to +2·56‰ VPDB). Within the prefolding veins, brecciated host rock fragments and complex textures such as crack and seal features resulted from hydraulic fracturing. They reflect expulsion of overpressured fluids within the footwall of the frontal thrusts. After folding and thrust sheet emplacement, some calcite veins are still rock buffered (δ¹⁸O of ?0·96 to +0·2‰ VPDB and δ¹³C of +0·79 to +1·37‰ VPDB), whereas others reflect external (i.e. extraformational) and thus large‐scale fluid fluxes. Some of these veins are linked to basement‐derived fluid circulation or originated from fluid flow along evaporitic décollement horizons (δ¹⁸O around +3·0‰ VPDB and δ¹³C around +1·5‰ VPDB). Others are related to the maturation of hydrocarbons in the system (δ¹⁸O around ?7·1‰ VPDB and δ¹³C around +9·3‰ VPDB). An open joint system reflecting an extensional stress regime developed during or after the final folding stage. This joint system enhanced vertical connectivity. This open joint network can be explained by the high palaeotopographical position and the folding of the reservoir analogue within the deformational front. The joint system is pre‐Burdigalian in age based upon a dated karstified discordance contact. Sediment‐filled karst cavity development is linked to meteoric water infiltration during emergence of some of the structures. Despite its sediment fill, the karst network is locally an important contributor to reservoir matrix porosity in otherwise tight lithologies. Development of secondary porosity along bed‐parallel and bed‐perpendicular (i.e. layer‐parallel shortening) stylolites is interpreted as a late‐stage diagenetic event associated with migration of acidic fluids during hydrocarbon maturation. Development of porosity along the LPS system enhanced the vertical reservoir connectivity.     

Fluid generation, vein formation and the degree of fluid–rock interaction during decompression of high-pressure terranes: the Schistes Lustrés, Alpine Corsica, France

Centimetre‐ to decimetre‐wide quartz+calcite veins in schistes lustrés from Alpine Corsica were formed during exhumation at 30–40 Ma following blueschist facies metamorphism. The δ¹⁸O and δ¹³C values of the veins overlap those of the host schistes lustrés, and the δ¹⁸O values of the veins are much higher than those of other rocks on Corsica. These data suggest that the vein‐forming fluids were derived from the schistes lustrés. Fluids were probably generated by reactions that broke down carpholite, lawsonite, chlorite and white mica at 300–350 °C during decompression between c. 1400 and 800 MPa. However, the δ¹⁸O values of the veins are locally several per mil higher than expected given those of their host rocks. The magnitude of oxygen isotope disequilibrium between the veins and the host rock is inversely proportional to the δ¹⁸O value of the host rock. Additionally, calcite in some schists is in isotopic equilibrium with calcite in adjacent veins, but not with the silicate fraction of the schists. Locally, the schists are calcite bearing only within 1–20 cm of the veins. The vein‐forming fluids may have been preferentially derived from calcite‐bearing, high‐δ¹⁸O rocks that are common within the schistes lustrés and that locally contain abundant (>15%) veins. If the fluids were unable to completely isotopically equilibrate with the rocks, due to relatively rapid flow at moderate temperatures or being confined to fractures, they could form veins with higher δ¹⁸O values than those of the surrounding rocks. Alteration of the host rocks was probably inhibited by isolation of the fluid in ‘quartz‐armoured’ veins. Overall, the veins represent a metre‐ to hectometre‐scale fluid‐flow system confined to within the schistes lustrés unit, with little input from external sources. This fluid‐flow system is one of several that operated in the western Alps during exhumation following high‐pressure metamorphism.     

Post-Variscan hydrothermal vein mineralization,Taunus, Rhenish Massif (Germany): Constraints from stable and radiogenic isotope data

Post-Variscan hydrothermal base-metal mineralization of the Taunus ore district, SE Rhenish Massif (Germany), has been studied through combination of stable (S, C, O) and radiogenic (Pb) isotope geochemistry. Based on field and textural observations, five hydrothermal mineralization types can be distinguished. These are (1) tetrahedrite–tennantite bearing quartz–ankerite veins, (2) quartz veins with Pb–Zn–Cu ores, (3) giant quartz veins, (4) metasomatic dolomite in Devonian reef complexes, and (5) calcite–(quartz) mineralization in Devonian reefs. The δ¹⁸O_V-SMOW quartz values of base-metal veins are in the range of 18.0–21.5‰, whereas those of giant quartz veins have lower values of 15.9–18.6‰. This difference reflects the higher fluid fluxes and smaller extent of rock-buffering for the giant quartz veins. Hydrothermal carbonates from the tetrahedrite and Pb–Zn–Cu veins have variable but distinctly negative δ¹³C_V-PDB values. They can be explained by contributions from fluids that had picked up low δ¹³C_V-PDB carbon via oxidation of organic matter and from fluids that interacted with Devonian reef carbonate having positive δ¹³C_V-PDB. Metasomatic dolomite has positive δ¹³C_V-PDB values that closely reflect those of the precursor limestone. By contrast, carbonates of calcite–(quartz) mineralization have negative δ¹³C_V-PDB values which are negatively correlated with the δ¹⁸O values. This pattern is explained by fluid mixing processes where contributions from descending cooler fluids with rather low salinity were dominant. The isotope data suggest that tetrahedrite veins, Pb–Zn–Cu veins, and giant quartz veins formed from fluid mixing involving two end-members with contrasting chemical features. This is supported by fluid inclusion data (Adeyemi, 1982) that show repeated alternation between two different types of fluid inclusions, which are hotter intermediate- to high-salinity NaCl–CaCl₂ fluids and cooler low-salinity NaCl-dominated fluids. The metal-rich saline fluids were likely generated at the boundary between the pre-Devonian basement and the overlying Devonian–Carboniferous nappe pile. Fault activation resulted in strong fluid focusing and upward migration of large volumes of hot Na–Ca brines, which mixed with cooler and more dilute fluids at shallower crustal levels. Variable contributions from both fluid types, local fluid fluxes, temperature variations, and variations in pH and oxidation state have then controlled the vein mineralogy and metal inventory.     

A study of oxygen isotopic fractionation during bio-induced calcite precipitation in eutrophic Baldeggersee,Switzerland

In order to better understand environmental factors controlling oxygen isotope shifts in autochthonous lacustrine carbonate sequences, we undertook an extensive one-year study (March, 1995 to February, 1996) of water-column chemistry and daily sediment trap material from a small lake in Central Switzerland. Comparisons between calculated equilibrium isotope values, using the fractionation equation of Friedman and O’Neil, (1977) and measured oxygen isotope ratios of calcite in the sediment-traps reveal that oxygen isotopic values of autochthonous calcite (δ¹⁸O) are in isotopic equilibrium with ambient water during most of the spring and summer, when the majority of the calcite precipitates. In contrast, small amounts of calcite precipitated in early-spring and again in late-autumn are isotopically depleted in ¹⁸O relative to the calculated equilibrium values, by as much as 0.8‰. This seasonally occurring apparent isotopic nonequilibrium is associated with times of high phosphorous concentrations, elevated pH (∼8.6) and increased [CO₃²⁻] (∼50 μmol/l) in the surface waters. The resulting weighted average δ¹⁸O value for the studied period is −9.6‰, compared with a calculated equilibrium δ¹⁸O value of −9.4‰. These data convincingly demonstrate that δ¹⁸O of calcite are, for the most part, a very reliable proxy for temperature and δ¹⁸O of the water.     

A-type granites induced by a breaking-off and delamination of the subducted Junggar oceanic plate,West Junggar,Northwest China

The A-type granites with highly positive ε_Nd(t) values in the West Junggar, Central Asian Orogenic Belt (CAOB), have long been perceived as a group formed under the same tectonic and geodynamic setting, magmatic sourceq and petrogenetic model. Geological evidence shows that these granites occurred at two different tectonic units related to the southeastern subduction of Junggar oceanic plate: the Hongshan and Karamay granites emplaced in the southeast of West Junggar in the Baogutu continental arc; whereas the Akebasitao and Miaoergou granites formed in the accretionary prism. Here the authors present new bulk-rock geochemistry and Sr-Nd isotopes, zircon U-Pb ages and Hf-O isotopes data on these granites. The granites in the Baogutu continental arc and accretionary prism contain similar zircon ε_Hf(t) values (+10.9 to +16.2) and bulk-rock geochemical characteristics (high SiO₂ and K₂O contents, enriched LILEs (except Sr), depleted Sr, Ta and Ti, and negative anomalies in Ce and Eu). The Hongshan and Karamay granites in the Baogutu continental arc have older zircon U-Pb ages (315–305 Ma) and moderate ¹⁸O enrichments (δ¹⁸O_zircon=+6.41‰–+7.96‰); whereas the Akebasitao and Miaoergou granites in the accretionary prism have younger zircon U-Pb ages (305–301 Ma) with higher ¹⁸O enrichments (δ¹⁸O_zircon=+8.72‰–+9.89‰). The authors deduce that the elevated ¹⁸O enrichments of the Akebasitao and Miaoergou granites were probably inherited from low-temperature altered oceanic crusts. The Akebasitao and Miaoergou granites were originated from partial melting of low-temperature altered oceanic crusts with juvenile oceanic sediments below the accretionary prism. The Hongshan and Karamay granites were mainly derived from partial melting of basaltic juvenile lower crust with mixtures of potentially chemical weathered ancient crustal residues and mantle basaltic melt (induced by hot intruding mantle basaltic magma at the bottom of the Baogutu continental arc). On the other hand, the Miaoergou charnockite might be sourced from a deeper partial melting reservoir under the accretionary prism, consisting of the low-temperature altered oceanic crust, juvenile oceanic sediments, and mantle basaltic melt. These granites could be related to the asthenosphere’s counterflow and upwelling, caused by the break-off and delamination of the subducted oceanic plate beneath the accretionary prism Baogutu continental arc in a post-collisional tectonic setting.©2022 China Geology Editorial Office.     

Constraints on the application of carbon isotope thermometry in high- to ultrahigh-temperature metamorphic terranes

Nine marble horizons from the granulite facies terrane of southern India were examined in detail for stable carbon and oxygen isotopes in calcite and carbon isotopes in graphite. The marbles in Trivandrum Block show coupled lowering of δ¹³C and δ¹⁸O values in calcite and heterogeneous single crystal δ¹³C values (? 1 to ? 10‰) for graphite indicating varying carbon isotope fractionation between calcite and graphite, despite the granulite facies regional metamorphic conditions. The stable isotope patterns suggest alteration of δ¹³C and δ¹⁸O values in marbles by infiltration of low δ¹³C–δ¹⁸O‐bearing fluids, the extent of alteration being a direct function of the fluid‐rock ratio. The carbon isotope zonation preserved in graphite suggests that the graphite crystals precipitated/recrystallized in the presence of an externally derived CO₂‐rich fluid, and that the infiltration had occurred under high temperature and low f_O2 conditions during metamorphism. The onset of graphite precipitation resulted in a depletion of the carbon isotope values of the remaining fluid+calcite carbon reservoir, following a Rayleigh‐type distillation process within fluid‐rich pockets/pathways in marbles resulting in the observed zonation. The results suggest that calcite–graphite thermometry cannot be applied in marbles that are affected by external carbonic fluid infiltration. However, marble horizons in the Madurai Block, where the effect of fluid infiltration is not detected, record clear imprints of ultrahigh temperature metamorphism (800–1000 °C), with fractionations reaching <2‰. Zonation studies on graphite show a nominal rimward lowering δ¹³C on the order of 1 to 2‰. The zonation carries the imprint of fluid deficient/absent UHT metamorphism. Commonly, calculated core temperatures are > 1000 °C and would be consistent with UHT metamorphism.     

Nature of the Ore-Forming Fluid at the Quaternary Noya Gold Deposit in Kyushu,Japan

We discuss the nature of the ore-forming hydrothermal fluid in the Noya gold-bearing calcite-quartz-adularia veins of central Kyushu, Japan on the basis of oxygen, carbon, and strontium isotope ratios, and aqueous speciation calculations for the present-day geothermal fluid. The isotopic values of the Noya ore-forming fluid were estimated to be −6.5‰ for δ¹³C and −7.5‰ for δ¹⁸O. The oxygen isotopic equilibrium temperatures for vein calcite are more than 180°C at the bottom of the Noya mineralization zone, and decrease with increasing elevation. As the temperature decreased, the dominant carbon species in the fluid changed from H₂CO₃ to HCO₃^- at about 120°C. The equilibrium temperatures for vein quartz are consistent with the calcite calculations. The carbon and oxygen isotope trends of the Noya vein calcite and the isotope ratios of strontium suggest that the fluids that precipitated the Noya veins were controlled by an andesite-dominated geology. Chondrite-normalized REE patterns for the white-colored veins from wells 51-WT-1 and 51-WT-2 displayed a light REE-rich pattern with positive Eu anomalies, suggesting the existence of a reducing environment for the fluid. The pyrite-rich gray-colored veins and a silicified rock from well 51-WT-2 showed higher REE concentrations than did the white veins. Altered host andesitic rocks have similar REE patterns to that of the silicified rock, and have higher REE contents than the others in the drill cores. Aqueous speciation calculations showed that the fluid in the hydrothermal reservoir is currently in muscovite stability. The fluid at the ore-mineralization stage may have contained more potassium or have had a higher pH, so that adularia precipitated with calcite and quartz, as well as gold. Fluid boiling at depth in the system produced the gold-bearing calcite-quartz-adularia veins.     

江西德兴铜厂铜矿水－岩体系氢氧同位素演化

 江西铜厂铜矿床露天采场岩石76个全岩氧同位素组成表明,该超大型铜矿的形成与具有5个水-岩交换成矿体系汇集在一起有关。水-岩体系计算表明,成矿流体储库形成是大气降水与千枚岩和花岗闪长斑岩在300℃以及W/R比值为0.5左右条件下形成,而后上升进入矿化沉积体系时温度降低,W/R比值超过10.0,计算的最少水量达1.9×10¹⁰t以上。     

Genesis of the Gold Deposit in the Indus-Yarlung Tsangpo Suture Zone, Southern Tibet: Evidence from Geological and Geochemical Data

The Nianzha gold deposit,located in the central section of the Indus-Yarlung Tsangpo suture(IYS) zone in southern Tibet,is a large gold deposit(Au reserves of 25 tons with average grade of 3.08 g/t) controlled by a E-W striking fault that developed during the main stage of Indo-Asian collision(~65-41 Ma).The main orebody is 1760 m long and 5.15 m thick,and occurs in a fracture zone bordered by Cretaceous diorite in the hanging wall to the north and the Renbu tectonic melange in the footwall to the south.High-grade mineralization occurs in a fracture zone between diorite and ultramafic rock in the Renbu tectonic melange.The wall-rock alteration is characterized by silicification in the fracture zone,serpentinization and the formation of talc and magnesite in the ultramafic unit,and chloritization and the formation of epidote and calcite in diorite.Quartz veins associated with Au mineralization can be divided into three stages.Fluid inclusion data indicate that the deposit formed from H_2O-NaCl-organic gas fluids that homogenize at temperatures of 203℃-347℃ and have salinities of 0.35wt%-17.17wt%NaCl equivalent.The quartz veins yield δ~(18)O_(fluid) values of 0.15‰-10.45‰,low δD_(V-SMOW)values(-173‰ to-96‰),and the δ~(13)C values of-17.6‰ to-4.7‰,indicating the ore-forming fluids were a mix of metamorphic and sedimentary orogenic fluids with the addition of some meteoric and mantle-derived fluids.The pyrite within the diorite has δ~(34)S_(V-CDT) values of-2.9‰-1.9‰(average-1.1‰),~(206)Pb/~(204)Pb values of 18.47-18.64,~(207)Pb/~(204)Pb values of 15.64-15.74,and ~(208)Pb/~(204)Pb values of 38.71-39.27,all of which are indicative of the derivation of S and other ore-forming elements from deep in the mantle.The presence of the Nianzha,Bangbu,and Mayum gold deposits within the IYS zone indicates that this area is highly prospective for large orogenic gold deposits.We identified three types of mineralization within the IYS,namely Bangbu-type accretionary,Mayum-type microcontinent,and Nianzha-type ophiolite-associated orogenic Au deposits.The three types formed at different depths in an accretionary orogenic tectonic setting.The Bangbu type was formed at the deepest level and the Nianzha type at the shallowest.     

Fluid flow and mass transport at the Valentine wollastonite deposit, Adirondack Mountains, New York State

The Valentine wollastonite skarn in the north-west Adirondack Mountains, New York, is a seven million ton deposit which resulted from channellized infiltration of H₂O-rich, silica-bearing fluids. The wollastonite formed by reaction of these fluids with non-siliceous calcite marble. The skarn formed at the contact of the syenitic Diana Complex and was subsequently overprinted by Grenville-age granulite facies metamorphism and retrograde hydrothermal alteration during uplift. Calcite marbles adjacent to the deposit have generally high δ¹⁸O values (c. 21‰), typical of Grenville marbles which have not exchanged extensively with externally derived fluids. Carbon isotopic fractiona-tions between coexisting calcite and graphite in the marbles indicate equilibration at 675d? C, consistent with the conditions of regional metamorphism. Oxygen isotopic ratios from wollastonite skarn are lower than in the marbles and show a 14‰ variation (-1‰ to 13‰). Some isotopic heterogeneity is preserved from skarn formation, and some represents localized exchange with low-δ¹⁸O retrograde fluids. Detailed millimetre- to centimetre-scale isotopic profiles taken across skarn/marble contacts reveal steep δ¹⁸O gradients in the skarn, with values increasing towards the marble. The gradients reflect isotopic evolution of the fluid as it reacted with high δ¹⁸O calcite to form wollastonite. Calcite in the marble preserves high δ¹⁸O values to within <5 mm of the skarn contact. The preservation of high δ¹⁸O values in marbles at skarn contacts and the disequilibrium fractionation between wollastonite skarn and calcite marble across these contacts indicate that the marbles were not infiltrated with significant quantities of the fluid. Thus, the marbles were relatively impermeable during both the skarn formation and retrograde alteration. Skarn formation may have been episodic and fluid flow was either chaotic or dominantly parallel to lithological contacts. Although these steep isotope gradients resemble fluid infiltration fronts, they actually represent the sides of the major flow system. Because chromatographic infiltration models of mass transport require the assumption of pervasive fluid flow through a permeable rock, such models are not applicable to this hydrothermal system and, by extension, to many other metamorphic systems where low-permeability rocks restrict fluid migration pathways. Minimum time-integrated fluid fluxes have been calculated at the Valentine deposit using oxygen isotopic mass balance, reaction progress of fluid buffering reactions, and silica mass balance. All three approaches show that large volumes of fluid were necessary to produce the skarn, but silica mass balance calculations yield the largest minimum flux and are hence the most realistic.     

俯冲带流体作用的地球化学示踪

俯冲带流体包括俯冲带岩石脱水形成的水流体和熔融作用产生的熔体。俯冲带流体循环及伴随的化学作用是壳幔演化和物质交换的重要机制。岛弧火山岩地球化学研究可以示踪流体的性质、成分。造山带变质岩内高压脉是俯冲带流体活动的直接记录。通过高压脉及其主岩地球化学研究 ,可以示踪流体成分和来源。俯冲带水流体成分与流体释放深度有关 ,俯冲带深处 ( >5 0km)形成的水流体内溶质相当可观。水流体流动方式有大规模沟道式和小规模弥散式 ,与其相应的流体来源分别为外来的和内部的。俯冲带流体组分、流动方式、物质交换机制与俯冲带深度、热状态、物质结构的定量关系 ,以及矿物 /水流体间元素分配系数的高压实验可能将是俯冲带流体今后研究的重要课题。中国西天山高压变质带榴辉岩及蓝片岩中广泛发育高压脉 ,根据脉的矿物组合 ,高压脉可分成 4种类型。高压脉氧同位素研究表明 ,脉体与流体间氧同位素交换宏观与局部平衡 ,流体活动为大规模的 ;流体活动方式既有沟道式 ,又有渗透式 ;流体的δ18O值为 + 10 .8‰左右 ,流体来源于主岩经过海水低温蚀变的大洋玄武岩。西天山广泛发育的高压脉 (尤其是蓝片岩中的高压脉的发现目前在世界范围尚属首例 ) ,是研究古俯冲带流体作用良好的野外天然实验室。     

Hydrothermal Alteration and Mineralization of Middle Jurassic Dexing Porphyry Cu-Mo Deposit, Southeast China

The Dexing deposit is located in a NE‐trending magmatic belt along the southeastern margin of the Yangtze Craton. It is the largest porphyry copper deposit in China, consisting of three porphyry copper orebodies of Zhushahong, Tongchang and Fujiawu from northwest to southeast. It contains 1168 Mt of ores with 0.5% Cu and 0.01% Mo. The Dexing deposit is hosted by Middle Jurassic granodiorite porphyries and pelitic schist of Proterozoic age. The Tongchang granodiorite porphyry has a medium K cal‐alkaline series, with medium K₂O content (1.94–2.07 wt%), and low K₂O/(Na₂O + K₂O) (0.33–0.84) ratios. They have high large‐ion lithophile elements, high light rare‐earth elements, and low high‐field‐strength elements. The hydrothermal alteration at Tongchang is divided into four alteration mineral assemblages and related vein systems. They are early K‐feldspar alteration and A vein; transitional (chlorite + illite) alteration and B vein; late phyllic (quartz + muscovite) alteration and D vein; and latest carbonate, sulfate and oxide alteration and hematite veins. Primary fluid inclusions in quartz from phyllic alteration assemblage include liquid‐rich (type 1), vapor‐rich (type 2) and halite‐bearing ones (type 3). These provide trapping pressures of 20–400 ´ 10⁵ Pa of fluids responsible for the formation of D veins. Igneous biotite from least altered granochiorite porphyry and hydrothermal muscovite in mineralized granodiorite porphyry possess δ¹⁸O and δD values of 4.6‰ and ?87‰ for biotite and 7.1–8.9‰, ?71 to ?73‰ for muscovite. Stable isotopic composition of the hydrothermal water suggests a magmatic origin. The carbon and oxygen isotope for hydrothermal calcite are ?4.8 to ?6.2‰ and 6.8–18.8‰, respectively. The δ³⁴S of pyrite in quartz vein ranges from ?0.1 to 3‰, whereas δ³⁴S for chalcopyrite in calcite veins ranges from 4 to 5‰. These are similar to the results of previous studies, and suggest a magmatic origin for sulfur. Results from alteration assemblages and vein system observation, as well as geochemical, fluid inclusion, stable isotope studies indicate that the involvement of hydrothermal fluids exsolved from a crystallizing melt are responsible for the formation of Tongchang porphyry Cu‐Mo orebodies in Dexing porphyry deposit.     

Speleothem preservation and diagenesis in South African hominin sites implications for paleoenvironments and geochronology

Plio‐Pleistocene speleothems from australopithecine‐bearing caves of South Africa have the potential to yield paleoenvironmental and geochronological information using isotope geochemistry. Prior to such studies it is important to assess the preservation of geochemical signals within the calcitic and aragonitic speleothems, given the tendency of aragonitic speleothems to recrystallize to calcite. This study documents the geochemical suitability of speleothems from the principal hominin‐bearing deposits of South Africa. We use petrography, together with stable isotope and trace element analysis, to identify the occurrence of primary aragonite, primary calcite, and secondary calcite. This study highlights the presence of diagenetic alteration at many of the sites, often observed as interbedded primary and secondary fabrics. Trace element and stable isotopic values distinguish primary calcite from secondary calcite and offer insights into geochemical aspects of the past cave environment. δ¹³C values of the primary and secondary calcites range from +6 to −9‰ and δ¹⁸O values range from −4 to −6‰. The data are thus typical of meteoric calcites with highly variable δ¹³C and relatively invariant δ¹⁸O. High carbon isotope values in these deposits are associated with the effects of recrystallization and rapid outgassing of CO₂ during precipitation. Mg/Ca and Sr/Ca ratios differ between primary and secondary calcite speleothems, aiding their identification. Carbon and oxygen isotope values in primary calcite reflect the proportion of C₃ and C₄ vegetation in the local environment and the oxygen isotope composition of rainfall. Primary calcite speleothems preserve the pristine geochemical signals vital for ongoing paleoenvironmental and geochronological research. © 2009 Wiley Periodicals, Inc.     

Deep‐burial alteration of early‐diagenetic carbonate concretions formed in Palaeozoic deep‐marine greywackes and mudstones (Bardo Unit,Sudetes Mountains,Poland)

Carbonate concretions formed in bathyal and deeper settings have been studied less frequently than those formed in shallow‐marine deposits. Similarly, concretions affected by catagenetic conditions have rarely been reported. Calcite concretions in deep‐marine mudstones and greywackes of the Bardo Unit (Sudetes Mountains, Poland) formed during early diagenesis and were buried to significant depths. Petrographic and geochemical (elemental and stable C and O isotopic) analyses document their formation close to the sediment–water interface, prior to mechanical compaction within the sulphate reduction zone and their later burial below the oil window. Although the concretions were fully formed during early diagenesis, the effects of increased temperature and interaction with late‐diagenetic interstitial fluids can be discerned. During maximum burial, the concretions underwent thorough recrystallization that caused alteration of fabric and elemental and O isotope composition. The initial finely crystalline cement was replaced by more coarsely crystalline, sheaf‐like, poikilotopic calcite in the concretions. These large calcite crystals engulf and partially replace unstable detrital constituents. The extremely low δ¹⁸O values (down to ?21·2‰ Vienna Pee Dee Belemnite) in the concretions are the result of the increased temperature in combination with alteration of volcanic glass, both causing a significant ¹⁸O‐depletion of bicarbonate dissolved in the interstitial fluids. Recrystallization led to uniform O isotope ratios in the concretions, but did not affect the C isotope signature. The δ¹³C values of the late‐diagenetic cements precipitated in the greywacke and in cracks cutting through concretions imply crystallization in the catagenetic zone and decarboxylation as a source of the bicarbonate. These late‐diagenetic processes took place in a supposedly overpressured setting, as suggested by clastic dykes and hydrofractures that cut through both concretions and host rock. All of these features show how the effects of early and late diagenesis can be distinguished in such rocks.     

Evinosponges in the Triassic Esino Limestone (Southern Alps): documentation of early lithification and late diagenetic overprint

A carbonate buildup of Middle Triassic age, the Esino Limestone, outcrops in the Southern Calcareous Alps of Lombardy (N Italy). Along its margin and within the open subtidal facies, the Esino Limestone contains calcite cement-filled cavities of cm to m size. These features, known as evinosponges, may form pervasive networks within the host rock. The filling consists of concentric, isopachous layers of fibrous low-Mg calcite crystals characterized by strong undulose extinction and bent cleavages. The cement crusts are non-luminescent under cathodoluminescence, but both cements and host rock are cross-cut by micro-fractures filled with bright-luminescent calcite, related to late void-filling sparite. Mixing of different carbonates is reflected in stable isotope data. On the hand specimen scale, the oxygen and carbon isotope compositions of cements and host rock show little variation. When compared on a regional scale, the values cover a broad range from δ¹⁸O(PDB)=?5‰ to ?12‰ and from δ¹³O =0‰ to +3‰. The linear covariant trends defined by the oxygen and carbon isotope data for different sampling regions reflect the admixture of late, isotopically depleted calcite with an isotopically enriched non-luminescent calcite of early diagenetic origin. The Esino Limestone fibrous cements, which were probably precipitated in the marine or marine-meteoric phreatic environment, were affected by late diagenetic processes that caused mineral deformation and isotopic depletion through recrystallization and the admixture of a later calcite. These later calcites precipitated from penetrative fluids possibly related to Late Triassic volcanic activity and/or to the Late Cretaceous/Early Palaeogene alpine orogeny.     

Ordovician low- to intermediate-Mg calcite marine cements from Sweden: marine alteration and implications for oxygen isotopes in Ordovician seawater

Petrography demonstrates the presence of three types of fibrous calcite cement in buildup deposits of the Kullsberg Limestone (middle Caradoc), central Sweden. Translucent fibrous calcite has intrinsic blue luminescence (CL) indicative of pure calcite. This cement has 2–5 mol% MgCO₃, low Mn and Fe (≤ 100 p.p.m.), and is considered to be slightly altered to unaltered, primary low- to intermediate-Mg calcite. Grey turbid fibrous calcite has variable but generally low MgCO₃ content (most analyses <2 mol%) and variable CL response, with Mn and Fe concentrations up to 1200 and 500 p.p.m., respectively. The heterogeneous characteristics of this variety of fibrous calcite are caused by diagenetic alteration of a translucent fibrous calcite precursor. Light-brown turbid fibrous calcite has low MgCO₃ (near 1 mol%) and variable Mn (up to 800 p.p.m.) and Fe (up to 500 p.p.m.) concentrations, with an abundance of bright luminescent patches, which formed during alteration caused by reducing diagenetic fluids. The δ¹³C and δ¹⁸O values of all fibrous calcite form a tight field (δ¹³C=1·7 to 3·1‰ PDB, δ¹⁸O= ? 2·6 to ? 4·1‰ PDB) compared with fibrous calcite isotope values from other units. Fibrous calcite δ¹⁸O values are larger than adjacent meteoric or burial cements, which have δ¹⁸O δ ? 8‰ PDB. Consequently, most diagenetic alteration of Kullsberg fibrous calcite is interpreted to have occurred in the marine diagenetic realm. First-generation equant and bladed calcite cements, which pre-date fibrous calcite, are interpreted as unaltered, low-Mg calcite marine cements based on δ¹³C and δ¹⁸O data (δ¹³C = 2·3 to 2·7‰ PDB, δ¹⁸O= ? 2·8 to ? 3·5‰ PDB). Unlike fibrous cement, which reflects global sea water chemistry, first-generation equant and bladed calcite are indicators of localized modification of seawater chemistry in restricted settings. Kullsberg abiotic marine cements have larger δ¹⁸O values than most Caradoc marine precipitates from equatorial Laurentia. Positive Kullsberg δ¹⁸O values are attributed to lower seawater temperatures and/or slightly elevated salinity on the Baltic platform relative to seawater from which other marine precipitates formed.     

Origin and evolution of fluids from mud volcanoes in the Barbados accretionary complex

A large collection of fluids (54 interstitial fluids and four expelled fluids) were sampled at the Manon site, at the outer edge of the Barbados accretionary complex. These warm fluids (up to 20°C) are expelled by sub-marine (5000 mbsl) mud volcanoes consisting of diapirs (unchanneled flow) and diatremes (channeled).Chlorine stable isotope ratios of these fluids were measured by IRMS with a reproducibility of ± 0.05‰ (1σ) versus SMOC (Standard Mean Ocean Chloride).A large range of δ³⁷Cl between −5.3‰ and +0.1‰ is observed. Data from each volcanic structure describe a mixing between seawater and a low-δ³⁷Cl fluid. The whole set of data is interpreted as the result of a mixing between two deep components and seawater. The two deep fluids are chemically distinct (e.g., in Ca, Mg, K, Li, Sr and Br contents and Br/Cl ratio). They display low and significantly different ⁸⁷Sr/⁸⁶Sr ratios (0.707790 and 0.707892, respectively) and δ³⁷Cl values (−4.51 and −5.24‰, respectively).Physicochemical processes such as mineralogical transformation, diffusion, compaction or ion filtration are known to fractionate chlorine stable isotopes and can produce fluids with negative δ³⁷Cl values. Ion filtration due to sediment compaction appears to be the more likely process to explain the negative δ³⁷Cl values observed at the Manon site. A model for the generation of these signatures is proposed where a residual negative δ³⁷Cl fluid reservoir is created at the bottom of the prism or the sediment pile. Further compaction/fracturing and/or dewatering of the slab may flush out these fluids and focus them towards the décollement zone. Mixing between the fluids and ultimately with seawater and water released during gas hydrate destabilizations may explain the data set within the individual cores and between the different structures.     

Channelized fluids in subducted continental crust: constraints from δD–δ18O of quartz and fluid inclusions in quartz veins from the Chinese Continental Scientific Drilling Project

Fluid inclusions hosted by quartz veins in high-pressure to ultrahigh-pressure (HP-UHP) metamorphic rocks from the Chinese Continental Scientific Drilling (CCSD) Project main drillhole have low, varied hydrogen isotopic compositions (δD?=??97‰ to??69‰). Quartz δ¹⁸O values range from??2.5‰ to 9.6‰; fluid inclusions hosted in quartz have correspondingly low δ¹⁸O values of??11.66‰ to 0.93‰ (T _h?=?171.2～318.8°C). The low δD and δ¹⁸O isotopic data indicate that protoliths of some CCSD HP-UHP metamorphic rocks reacted with meteoric water at high latitude near the surface before being subducted to great depth. In addition, the δ¹⁸O of the quartz veins and fluid inclusions vary greatly with the drillhole depth. Lower δ¹⁸O values occur at depths of ～900–1000 m and ～2700 m, whereas higher values characterize rocks at depths of about 1770 m and 4000 m, correlating roughly with those of wall-rock minerals. Given that the peak metamorphic temperature of the Dabie-Sulu UHP metamorphic rocks was about 800°C or higher, much higher than the closure temperature of oxygen isotopes in quartz under wet conditions, such synchronous variations can be explained by re-equilibration. In contrast, δD values of fluid inclusions show a different relationship with depth. This is probably because oxygen is a major element of both fluids and silicates and is much more abundant in the quartz veins and silicate minerals than is hydrogen. The oxygen isotope composition of fluid inclusions is evidently more susceptible to late-stage re-equilibration with silicate minerals than is the hydrogen isotope composition. Therefore, different δD and δ¹⁸O patterns imply that dramatic fluid migration occurred, whereas the co-variation of oxygen isotopes in fluid inclusions, quartz veins, and wall-rock minerals can be better interpreted by re-equilibration during exhumation.

Quartz veins in the Dabie-Sulu UHP metamorphic terrane are the product of high-Si fluids. Given that channelized fluid migration is much faster than pervasive flow, and that the veins formed through precipitation of quartz from high-Si fluids, the abundant veins indicate significant fluid mobilization and migration within this subducted continental slab. Many mineral reactions can produce high-Si fluids. For UHP metamorphic rocks, major dehydration during subduction occurred when pressure–temperature conditions exceeded the stability of lawsonite. In contrast, for low-temperature eclogites and other HP metamorphic rocks with peak metamorphic P–T conditions within the stability field of lawsonite, dehydration and associated high-Si fluid release may have occurred as hydrous minerals were destabilized at lower pressure during exhumation. Because subduction is a continuous process whereas only a minor fraction of the subducted slabs returns to the surface, dehydration during underflow is more prevalent than exhumation even in subducted continental crust, which is considerably drier than altered oceanic crust.