地球化学景观吸引子的发现及其意义

勘查地球化学对异常评价的最大不确定性源于对地球化学景观特性的认识不够。我们应用构造相空间的方法分析了浙江儒岙幅（1:5万）水系沉积物测量的Ag含量数据，揭示了地球化学景观是具有低维吸引子（DZ≈2．9）的混饨系统。这一发现将对勘查地球化学中采样密度的选择、地球化学场模拟、异常评价等根本性问题产生重大影响。     

Fluid geochemistry in the Ivigtut cryolite deposit, South Greenland

The 1.27 Ga old Ivigtut (Ivittuut) intrusion in South Greenland is world-famous for its hydrothermal cryolite deposit [Na₃AlF₆] situated within a strongly metasomatised A-type granite stock. This detailed fluid inclusion study characterises the fluid present during the formation of the cryolite deposit and thermodynamic modelling allows to constrain its formation conditions.Microthermometry revealed three different types of inclusions: (1) pure CO₂, (2) aqueous-carbonic and (3) saline-aqueous inclusions. Melting temperatures range between − 23 and − 15 °C for type 2 and from − 15 to − 10 °C for type 3 inclusions. Most inclusions homogenise between 110 and 150 °C into the liquid.Stable isotope compositions of CO₂ and H₂O were measured from crushed inclusions in quartz, cryolite, fluorite and siderite. The δ¹³C values of about − 5‰ PDB are typical of mantle-derived magmas. The differences between δ¹⁸O of CO₂ (+ 21 to + 42‰ VSMOW) and δ¹⁸O of H₂O (− 1 to − 21.7‰ VSMOW) suggest low-temperature isotope exchange. δD (H₂O) ranges from − 19 to − 144‰ VSMOW. The isotopic composition of inclusion water closely follows the meteoric water line and is comparable to Canadian Shield brines. Ion chromatography revealed the fluid's predominance in Na, Cl and F. Cl/Br ratios range between 56 and 110 and may imply intensive fluid–rock interaction with the host granite.Isochores deduced from microthermometry in conjunction with estimates for the solidification of the Ivigtut granite suggest a formation pressure of approximately 1–1.5 kbar for the fluid inclusions. Formation temperatures of different types of fluid inclusions vary between 100 and 400 °C. Thermodynamic modelling of phase assemblages and the extraordinary high concentration in F (and Na) may indicate that the cryolite body and its associated fluid inclusions could have formed during the continuous transition from a volatile-rich melt to a solute-rich fluid.     

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.     

Fluid and source magma evolution of the Questa porphyry Mo deposit,New Mexico,USA

Combined fluid inclusion microthermometry and microanalysis by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) are used to constrain the hydrothermal processes forming a typical Climax-type porphyry Mo deposit. Molybdenum mineralisation at Questa occurred in two superimposed hydrothermal stages, a magmatic-hydrothermal breccia and later stockwork veining. In both stages, texturally earliest fluids were single-phase, of low salinity (~7 wt.% NaCl_equiv.) and intermediate-density. Upon decompression to ~300 bar, they boiled off a vapour phase, leaving behind a residual brine (up to 45 wt.% NaCl_equiv) at temperatures of ~420°C. The highest average Mo concentrations in this hot brine were ~500 μg/g, exceeding the Mo content of the intermediate-density input fluid by about an order of magnitude and reflecting pre-concentration of Mo by fluid phase separation prior to MoS₂ deposition from the brine. Molybdenum concentrations in brine inclusions, then, decrease down to 5 μg/g, recording Mo precipitation in response to cooling of the saline liquid to ~360°C. Molybdenite precipitation from a dense, residual and probably sulphide-depleted brine is proposed to explain the tabular shape of the ore body and the absence of Cu-Fe sulphides in contrast to the more common Cu-Mo deposits related to porphyry stocks. Cesium and Rb concentrations in the single-phase fluids of the breccia range from 2 to 8 and from 40 to 65 μg/g, respectively. In the stockwork veins, Cs and Rb concentrations are significantly higher (45–90 and 110–230 μg/g, respectively). Because Cs and Rb are incompatible and hydrothermally non-reactive elements, the systematic increase in their concentration requires two distinct pulses of fluid exsolution from a progressively more fractionated magma. By contrast, major element and ore metal concentrations of these two fluid pulses remain essentially constant. Mass balance calculations using fluid chemical data from LA-ICPMS suggest that at least 25 km³ of melt and 7 Gt of deep input fluid were necessary to provide the amount of Mo contained in the stockwork vein stage alone. While the absolute amounts of fluid and melt are uncertain, the well-constrained element ratios in the fluids together with empirical fluid/melt partition coefficients derived from the inclusion analyses suggest a high water content of the source melt of ~10%. In line with other circumstantial evidence, these results suggest that initial fluid exsolution may have occurred at a confining pressure exceeding 5 kbar. The source of the molybdenum-mineralising fluids probably was a particularly large magma chamber that crystallised and fractionated in the lower crust or at mid-crustal level, well below the shallow intrusions immediately underlying Questa and other porphyry molybdenum deposits. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Anhydrite pseudomorphs and the origin of stratiform Cu–Co ores in the Katangan Copperbelt (Democratic Republic of Congo)

The stratiform Cu–Co ore mineralisation in the Katangan Copperbelt consists of dispersed sulphides and sulphides in nodules and lenses, which are often pseudomorphs after evaporites. Two types of pseudomorphs can be distinguished in the nodules and lenses. In type 1 examples, dolomite precipitated first and was subsequently replaced by Cu–Co sulphides and authigenic quartz, whereas in type 2 examples, authigenic quartz and Cu–Co sulphides precipitated prior to dolomite and are coarse-grained. The sulphur isotopic composition of the copper–cobalt sulphides in the type 1 pseudomorphs is between −10.3 and 3.1‰ relative to the Vienna Canyon Diablo Troilite, indicating that the sulphide component was derived from bacterial sulphate reduction (BSR). The generation of during this process caused the precipitation and replacement of anhydrite by dolomite. A second product of BSR is the generation of H₂S, resulting in the precipitation of Cu–Co sulphides from the mineralising fluids. Initial sulphide precipitation occurred along the rim of the pseudomorphs and continued towards the core. Precipitation of authigenic quartz was most likely induced by a pH decrease during sulphide precipitation. Fluid inclusion data from quartz indicate the presence of a high-salinity (8–18 eq. wt.% NaCl) fluid, possibly derived from evaporated seawater which migrated through the deep subsurface. ⁸⁷Sr/⁸⁶Sr ratios of dolomite in type 1 nodules range between 0.71012 and 0.73576, significantly more radiogenic than the strontium isotopic composition of Neoproterozoic marine carbonates (⁸⁷Sr/⁸⁶Sr = 0.7056–0.7087). This suggests intense interaction with siliciclastic sedimentary rocks and/or the granitic basement. The low carbon isotopic composition of the dolomite in the pseudomorphs (−7.02 and −9.93‰ relative to the Vienna Pee Dee Belemnite, V-PDB) compared to the host rock dolomite (−4.90 and +1.31‰ V-PDB) resulted from the oxidation of organic matter during BSR.     

The sandstone-hosted stratiform copper mineralization at Mwitapile and its relation to the mineralization at Lufukwe, Lufilian foreland, Democratic Republic of Congo

The Lufilian foreland is a triangular-shaped area located in the SE of the Democratic Republic of Congo and to the NE of the Lufilian arc, which hosts the well-known Central African Copperbelt. The Lufilian foreland recently became an interesting area with several vein-type (e.g., Dikulushi) and stratiform (e.g., Lufukwe and Mwitapile) copper occurrences. The Lufilian foreland stratiform Cu mineralization is, to date, observed in sandstone rock units belonging to the Nguba and Kundelungu Groups (Katanga Supergroup).The Mwitapile sandstone-hosted stratiform Cu prospect is located in the north eastern part of the Lufilian foreland. The host rock for the Cu mineralization is the Sonta Sandstone of the Ngule Subgroup (Kundelungu Group). A combined remote sensing, petrographic and fluid inclusion microthermometric analysis was performed at Mwitapile and compared with similar analysis previously carried out at Lufukwe to present a metallogenic model for the Mwitapile- and Lufukwe-type stratiform copper deposits. Interpretation of ETM+ satellite images for the Mwitapile prospect and the surrounding areas indicate the absence of NE–SW or ENE–WSW faults, similar to those observed controlling the mineralization at Lufukwe. Faults with these orientations are, however, present to the NW, W, SW and E of the Mwitapile prospect. At Mwitapile, the Sonta Sandstone host rock is intensely compacted, arkosic to calcareous with high silica cementation (first generation of authigenic quartz overgrowths). In the Sonta Sandstone, feldspar and calcite are present in disseminated, banded and nodular forms. Intense dissolution of these minerals caused the presence of disseminated rectangular, pipe-like and nodular dissolution cavities. Sulfide mineralization is mainly concentrated in these cavities. The hypogene sulfide minerals consist of two generations of pyrite, chalcopyrite, bornite and chalcocite, separated by a second generation of authigenic quartz overgrowth. The hypogene sulfide minerals are replaced by supergene digenite and covellite. Fluid inclusion microthermometry on the first authigenic quartz phase indicates silica precipitation from an H₂O–NaCl–CaCl₂ fluid with a minimum temperature between 111 and 182 °C and a salinity between 22.0 and 25.5 wt.% CaCl₂ equiv. Microthermometry on the second authigenic quartz overgrowths and in secondary trails related to the mineralization indicate that the mineralizing fluid is characterized by variable temperatures (Th = 120 to 280 °C) and salinities (2.4 to 19.8 wt.% NaCl equiv.) and by a general trend of increasing temperatures with increasing salinities.Comparison between Mwitapile and Lufukwe indicates that the stratiform Cu mineralization in the two deposits is controlled by similar sedimentary, diagenetic and structural factors and likely formed from a similar mineralizing fluid. A post-orogenic timing is proposed for the mineralization in both deposits. The main mineralization controlling factors are grain size, clay and pyrobitumen content, the amount and degree of feldspar and/or calcite dissolution and the presence of NE–SW to ENE–WSW faults. The data support a post-orogenic fluid-mixing model for the Mwitapile- and Lufukwe-type sandstone-hosted stratiform Cu deposits, in which the mineralization is related to the mixing between a Cu-rich hydrothermal fluid, with a temperature up to 280 °C and a maximum salinity of 19.8 wt.% NaCl equiv., with a colder low salinity reducing fluid present in the sandstone host rock. The mineralizing fluid likely migrated upwards to the sandstone source rocks along NE–SW to ENE–WSW orientated faults. At Lufukwe, the highest copper grades at surface outcrops and boreholes were found along and near to these faults. At Mwitapile, where such faults are 2 to 3 km away, the Cu grades are much lower than at Lufukwe. Copper precipitation was possibly promoted by reduction from pre-existing hydrocarbons and non-copper sulfides and by the decrease in fluid salinity and temperature during mixing. Based on this research, new Cu prospects were proposed at Lufukwe and Mwitapile and a set of recommendations for further Cu exploration in the Lufilian foreland is presented.     

Calcareous nannoplankton, planktonic foraminiferal, and carbonate carbon isotope stratigraphy of the Cenomanian–Turonian boundary section in the Ultrahelvetic Zone (Eastern Alps, Upper Austria)

Ultrahelvetic units of the Eastern Alps were deposited on the distal European continental margin of the (Alpine) Tethys. The Rehkogelgraben section (“Buntmergelserie”, Ultrahelvetic unit, Upper Austria) comprises a 5 m thick succession of upper Cenomanian marl-limestone cycles overlain by a black shale interval composed of three black shale layers and carbonate-free claystones, followed by lower Turonian white to light grey marly limestones with thin marl layers. The main biostratigraphic events in the section are the last occurrence of Rotalipora and the first occurrences of Helvetoglobotruncana helvetica and Quadrum gartneri. The thickest black shale horizon has a TOC content of about 5%, with predominantly marine organic matter of kerogen type II. Vitrinite reflectance and Rock-Eval parameter T_max (<424 °C) indicate low maturity. HI values range from 261 to 362 mg HC/g TOC. δ¹³C values of bulk rock carbonates display the well documented positive shift around the black shale interval, allowing correlation of the Rehkogelgraben section with other sections such as the Global Boundary Stratotype Section and Point (GSSP) succession at Pueblo, USA, and reference sections at Eastbourne, UK, and Gubbio, Italy. Sediment accumulation rates at Rehkogelgraben (average 2.5 mm/ka) are significantly lower than those at Pueblo and Eastbourne.     

徐州土壤多环芳烃的环境地球化学迁移特征

选择江苏徐州黄棕壤进行不同深度层位多环芳烃含量的定量分析,研究并探讨了多环芳烃在土壤深度剖面中的地球化学迁移特征。研究结果显示,多环芳烃在徐州土壤剖面中主要集中在地表0~20 cm内。其中低环多环芳烃化合物的迁移能力较强,4~6环等高环化合物相对较难迁移,主要残留于地表生态系统环境中。     

滇西北保山核桃坪铅锌矿床成矿流体来源的同位素地球化学证据

滇西北核桃坪铅锌矿是保山地块内沿澜沧江断裂带发育的一个大型铅锌多金属矿床,矿体严格受近SN向的断裂带及层间破碎带控制,赋存于上寒武统核桃坪组和沙河厂组大理岩化灰岩及矽卡岩中。文章在分析矿床地质特征的基础上,通过对V1矿体的氢、氧、碳、硫、硅和铅同位素地球化学的示踪研究,探讨了成矿溶液中水、碳、硅、硫和铅的来源以及成矿流体的演化问题。研究表明,V1矿体中矿石的石英δ18O水值变化范围为6·1‰~7·6‰,平均为6·7‰,其δDV-SMOW值变化范围为-100‰~-108‰,平均为-104‰,说明成矿流体主要来自深部岩浆分异水,并在后期成矿作用过程中有地层建造水和大气降水的加入;矿石中方解石的δ13CV-PDB和δ18O水值分别为-6·6‰~-5·9‰和5·0‰~5·2‰,反映成矿流体的碳、氧具有深部流体与围岩发生交代反应的特征。硅、硫和铅同位素具深部岩浆或地幔来源的特点,但遭受后期壳源物质的混染。据此提出该矿床是与深部岩浆热液或幔源流体贯入有关的构造热液脉型矿床,其成矿作用受控于深部过程的驱动和控制,可为指导地质找矿提供依据。     

内蒙古正蓝旗羊蹄子山-磨石山钛矿区硅质岩地球化学特征及沉积环境意义

文章通过详细的野外地质调查和系统的岩石化学、稀土元素、微量元素及硅、氧同位素等研究,探讨了羊蹄子山-磨石山钛矿区无矿白色硅质岩和富钛硅质岩的成因及形成地质构造环境。研究结果表明,呈厚层状产出的无矿白色硅质岩具较高的SiO2、Al2O3含量及Al/(Al Fe Mn)、Al2O3/(Al2O3 Fe2O3)比值,稀土元素总量很低,其北美页岩标准化配分模式为向右倾的曲线,无明显铈异常和铕异常,表明其形成于受陆源影响的大陆边缘构造环境;赋矿岩系中薄层状富钛硅质岩的TiO2、Fe2O3、Cu、V含量较高,但Al/(Al Fe Mn)、Al2O3/(Al2O3 Fe2O3)比值较低,稀土元素总量较高,北美页岩标准化曲线为明显左倾型-平坦型,具弱的负铈异常,表明其形成于洋脊及附近环境。两种硅质岩的δ30Si值为变化较小的负值,与热水沉积和某些生物成因硅质岩的硅同位素组成相似,两者的δ18O值范围和平均值均相似。两类硅质岩的成因及形成构造环境不同,富钛硅质岩的地球化学特征表明,该矿床的形成与本区元古宙海底火山热液喷流作用有关。