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.     

A preliminary stable isotope study on Mogok Ruby, Myanmar

The primary occurrence of ruby in the Mogok area, northern Myanmar is exclusively found in marble along with spinel–forsterite-bearing marble and phlogopite–graphite marble. These marble units are enclosed within banded biotite–garnet–sillimanite–oligoclase gneisses. Samples of these marbles collected for C–O stable isotope analysis show two trends of δ¹³C–δ¹⁸O variation resulting most likely from fluid–rock interactions. Ruby-bearing marble and phlogopite–graphite marble follow a trend with coupled C–O depletion, whereas spinel–forsterite-bearing marble follows a δ¹⁸O depletion trend with relatively constant δ¹³C values. Ruby formation might have resulted from CO₂-rich fluid–rock interaction, while spinel–forsterite-bearing marble was genetically related to CO₂-poor fluid–rock interaction. Both fluids may have arisen from external sources. Based on graphite Raman spectral thermometry, the estimated temperature for phlogopite–graphite marble, and probably ruby-bearing marble, was lower than 607 °C, and for spinel–forsterite-bearing marble, lower than 710 °C. Contrasting C/O diffusion between graphite/ruby/spinel/forsterite and calcite, local variations of isotopic compositions of newly formed minerals as a result of non-pervasive fluid infiltration, and open-system isotopic disturbance during cooling may have affected C-/O-isotopic fractionations between minerals. The estimated high formation temperatures for ruby and spinel/forsterite imply that the parental fluids may have been related to nearby igneous intrusions and/or metamorphic processes. Whether these two types of fluid were genetically related is unclear based on the present data.     

“Cretaceous black flysch” in the Pieniny Klippen Belt, West Carpathians: a case of geological misinterpretation

This is a critical assessment of the paper by Oszczypko et al. (2004: Cretaceous Research 25, 89–113), in which they tried to prove a mid-Cretaceous age for the Szlachtowa (“black flysch”) and Opaleniec Formations, in the Pieniny Klippen Belt, West Carpathians, both of which had previously been shown to be of Jurassic age. We argue that the mid-Cretaceous age assignment is a misinterpretation, primarily resulting from their field samples having been collected from some Cretaceous lithostratigraphic units, tectonically associated with the Jurassic formations, and/or from tectonic contact-breccias involving Jurassic and Cretaceous strata. In addition, we suggest that they have overlooked a number of significant palaeontological papers, published since 1962, which record the presence of in situ ammonites, aptychi, belemnites, thin-shelled bivalves (Bositra), gryphaeids, foraminifera, and ostracod assemblages, all indicating a Jurassic (mainly Aalenian), and not a Cretaceous, age for the Szlachtowa Formation, and also the in situ Jurassic (Bajocian) ammonites and thin-shelled bivalves (Bositra), Bositra-microfacies, and age-diagnostic foraminiferal assemblages of the Opaleniec Formation.Our presentation here of recently published dinocyst data from well-preserved assemblages further supports the Jurassic ages for the Szlachtowa (“black flysch”) and Opaleniec Formations.     

流体包裹体成分测定的低温相变和显微拉曼光谱分析技术研究进展

论述了包裹体低温分析技术的原理以及进展。传统的流体包裹体低温分析技术是以显微冷冻测温测定无机盐体系为主,目前已发展到应用低温原位拉曼光谱技术对包裹体中的阳离子和阴离子进行定量-半定量分析。油气包裹体原位低温分析技术也取得了较大的突破,对不同成分油气包裹体低温下的相变过程取得了一定的认识,据此对油气包裹体进行分类,推测其主要成分,为油气包裹体计算提供基础参数。     

气相色谱法测定地下水中六六六结果的不确定度评定

依照《测量不确定度评定与表示》,对气相色谱法测定地下水中六六六(HCH)四种单体结果进行了不确定度评定。分析了测量过程中引入的不确定度来源,包括提取液体积的量取、样品提取溶液的定容体积、分析仪器的进样量、标准系列溶液的测量以及仪器重复测定等分量引入不确定度及其各参数的采集和计算方法,最后合成标准不确定度,通过乘以95%概率下的扩展因子2,获得测量结果的扩展不确定度。     

碱消解-高效液相色谱-电感耦合等离子体质谱法测定生物样品中的甲基汞和乙基汞

建立了碱消解-高效液相色谱-电感耦合等离子体质谱联用系统测定生物样品中甲基汞(MeHg)与乙基汞(EtHg)的分析方法。为提高灵敏度,选用微流量的PFA雾化器,在优化的检测条件下,MeHg及EtHg检出限可达到0.036μg/L和0.03μg/L;线性范围达到4个数量级,两条工作曲线线性相关系数为1。对1.78μg/L MeHg、1.65μg/L EtHg的混合标准溶液重复测定7次,色谱峰面积的相对标准偏差(RSD)分别为1.79%和1.44%。对标准物质BCR 464(金枪鱼)的分析结果表明,测定值与标准值基本吻合,但略低于标准值;甲基汞和乙基汞的加标回收率分别为85.9%和84.5%。高效液相色谱与质谱联用技术的高灵敏度和低检出限能够满足生物样品中汞形态定量分析的要求。     

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。     

激光拉曼光谱法分析多种显微组分荧光变化及其应用

利用激发488 nm激光的氩离子激光器作为RENISHAW inVia型激光拉曼光谱仪的光源,建立了多种显微组分荧光变化(FAMM)分析方法,并对镜质体反射率明显抑制的东营凹陷有效烃源岩进行了测定。结果表明,东营凹陷有效烃源岩的有机质类型越好,镜质体反射率抑制程度越高,有效烃源岩的真实成熟度应主要处于0.64%~1.30%,而不是实测镜质体反射率所反映的0.37%~1.10%。