Fluid evolution in the W–Cu–Zn–Pb San Cristobal vein, Peru: fluid inclusion and stable isotope evidence

The Zn–Pb±Ag±Cu San Cristobal district is located 100 km east of Lima in the western cordillera of Peru. It is centred around the Chumpe intrusion and is composed of vein and carbonate replacement ore types. The main San Cristobal vein presents a paragenesis that can be divided into three stages: (a) an early wolframite–quartz–pyrite stage, (b) a quartz–base metal stage, and (c) a late quartz–carbonate–barite stage.

Fluid inclusions in quartz from the tungsten stage are biphase (LV) at room temperature and homogenise to the liquid phase between 146 and 257 °C. Their salinities range between 2.1 and 5.1 wt.% NaCl equiv. Rare inclusions contain an additional crystal of halite and have salinities of 46–54 wt.% NaCl equiv. Data of the first two stages show a decrease in homogenisation temperatures concomitant with a salinity decline. Fluid inclusions in quartz from the late stage homogenise at higher temperatures, between 252 and 323 °C, with salinities ranging between 4.6 and 6.7 wt.% NaCl equiv.

Hydrogen and oxygen isotope data indicate a two-stage evolution. Isotopic compositions of the fluid associated with the first two stages define a trend with constant δ¹⁸O values and decreasing δD values (δ¹⁸O=3.2‰ to 5.0‰ V-SMOW and δD=−60‰ to −112‰ V-SMOW), which is interpreted as mixing of a dominantly magmatic component with minor meteoric water that had equilibrated with the host rocks. This interpretation is supported by sulphur and lead isotopic data from previous studies. By contrast, the quartz–carbonate–barite stage bears isotopic characteristics defining a trend with a coupled decrease of δ¹⁸O and δD (δ¹⁸O=−8.1‰ to 2.5‰ V-SMOW and δD=−57‰ to −91‰ V-SMOW) and is explained by addition of meteoric water to the system and subsequent mixing with a less important magmatic component.

Different fluid origins are confirmed by laser ablation ICP-MS analyses of the triphase (LVH) and biphase (LV) primary inclusions. The concentrations of the major ore elements, i.e., W, Cu, Zn and Pb, decrease throughout the paragenesis; W, and to a lesser extent Cu, show significant variations, associated with a steep decrease in their concentration. The decreasing concentrations can be explained by mineral deposition and dilution by the meteoric fluid; differences in the rate of decrease indicate selective precipitation of W. Fluid inclusions of the quartz–carbonate stages show an abrupt increase in Ba and Sr concentrations. This is interpreted to reflect a higher volume of host rock silicate alteration, probably due to the increasing size of the fluid flow cell and is explained by the input of a third fluid of unknown origin. LA-ICP-MS analyses show that the fluids were already depleted in W and Cu before reaching the emplacement of carbonate replacement ore type, whereas Zn and Pb were still present in considerable amounts. This is again due to selective precipitation and is consistent with the interpretation that the economically interesting metals were dominantly introduced by magmatic fluids.     

Hydrothermal Fluid Sources of the Fengjia Barite–fluorite Deposit in Southeast Sichuan,China: Evidence from Fluid Inclusions and Hydrogen and Oxygen Isotopes

The Fengjia barite–fluorite deposit in southeast Sichuan is a stratabound ore deposit which occurs mainly in Lower Ordovician carbonate rocks. Here we present results from fluid inclusion and oxygen and hydrogen isotope studies to determine the nature and origin of the hydrothermal fluids that generated the deposit. The temperature of the ore‐forming fluid shows a range of 86 to 302 °C. Our detailed microthermometric data show that the temperature during mineralization of the fluorite and barite in the early ore‐forming stage was higher than that during the formation of the calcite in the late ore‐forming stage. The salinity varied substantially from 0.18% to 21.19% NaCl eqv., whereas the density was around 1.00 g/cm³. The fluid composition was mainly H₂O (>91.33%), followed by CO₂, CH₄ and traces of C₂H₆, CO, Ar, and H₂S. The dominant cation was Na⁺ and the dominant anion Cl^‐, followed by Ca²⁺, SO₄^2‐, K⁺, and Mg²⁺, indicating a mid–low‐temperature, mid‐low‐salinity, low‐density NaCl–H₂O system. Our results demonstrate that the temperature decreased during the ore‐forming process and the fluid system changed from a closed reducing environment to an open oxidizing environment. The hydrogen and oxygen isotope data demonstrate that the hydrothermal fluids in the study area had multiple sources, primarily formation water, as well as meteoric water and metamorphic water. Combined with the geological setting and mineralization features we infer that the stratabound barite–fluorite deposits originated from mid–low‐temperature hydrothermal fluids and formed vein filling in the fault zone.     

Altitudinal shift in stable hydrogen isotopes and microbial tetraether distribution in soils from the Southern Alps,NZ: Implications for paleoclimatology and paleoaltimetry

The Southern Alps are an ideal locality for studying patterns of isotopic fractionation associated with orographic precipitation. We have evaluated whether altitudinal change is reflected in the stable hydrogen isotopic composition (δ²H) of stream water, plant stem water and leaf wax lipids (n-alkanes) from living plants and soils, as well as in soil temperature. Samples were collected along an altitudinal transect from the windward side of the Southern Alps to Lake Hawea in the rain shadow. The results indicate that δ²H values of stem water overlap with stream water, demonstrating a gradual decrease with elevation that complied with modeled Rayleigh distillation, reflecting an isotopic lapse rate of −18.0 (± 1.1, 1σ)‰/km. Leaf and soil n-alkanes shared similar δ²H values and were ²H depleted relative to stem/stream waters. The values for soil n-alkanes indicated an isotopic lapse rate of −21.8 (± 2.0, 1σ)‰/km, consistent with precipitation data and long term observations. MBT/CBT derived soil temperature values based on the relative distribution of microbial tetraether lipids were similar to midsummer temperature observations, displaying an elevational decrease rate of −5.6 (± 1.5, 1σ) °C/km, consistent with regional and global observations.The results indicate that sedimentary lipid δ²H and microbial tetraether temperature estimates captured altitudinal trends in the isotopic composition of precipitation and mean temperature and further support their application in the reconstruction of past climate and surface uplift histories. However, notable differences in isotopic composition and temperature estimates between in situ soils and those with downslope transport of material emphasize the importance of facies analysis when interpreting past systems.     

藏南羊卓雍错近代沉积物碳酸盐氧同位素特征及其环境意义

20世纪80年代以来气候变暖加剧,青藏高原冰川物质负平衡趋势增强,导致众多湖泊水位上升,但位于藏南地区的羊卓雍错,湖泊水位近年来却呈现出显著的波动下降趋势。本研究通过对羊卓雍错YZYC2沉积岩芯(长23 cm)进行²¹⁰Pb活度测定,建立沉积物的年代序列;分析公元1989年以来沉积物全样碳酸盐含量及其氧同位素组成,并结合现代气象及水文观测数据,揭示羊卓雍错沉积物碳酸盐氧同位素(δ¹⁸O)的环境意义及其对气候变化的响应过程与机制。结果表明,YZYC2岩芯碳酸盐矿物以自生成因的文石为主,其含量变化范围为23.3 % ~39.7 %,δ¹⁸O值变化范围为-4.7 ‰ ~-3.2 ‰。沉积物碳酸盐δ¹⁸O值总体呈波动上升趋势,较好地记录了近30年来羊卓雍错湖泊水位变化。1989~2019年羊卓雍错水位变化总体由降水与蒸发共同作用下的湖区有效湿度变化主导,同时也可能受到羊湖电站运行的影响。

     

基于共生金属硫化物硫同位素分馏程度约束热液活动温度：以川中下寒武统龙王庙组为例

硫循环及硫同位素(δ³⁴S)分馏研究对地表圈层的成岩作用具有重要意义,其中多种金属硫化物中硫同位素的分馏程度可以约束成矿热流体温度,进而作为地温计证据约束热液活动。四川盆地龙王庙组储集层内的热液改造影响着该储集层的非均质性,本研究着重讨论目的层中与热液成因白云石所伴生的黄铁矿(FeS₂)-黄铜矿(CuFeS₂)成矿现象：基于详尽的岩石学证据,应用纳米二次离子探针(NanoSIMS)对金属硫化物内部硫同位素分布进行测定,并基于热力学驱动下的硫化物间平衡分馏程度计算其成矿温度,进而约束层段内热液活动过程。研究发现：(1)微区硫同位素分布显示黄铁矿(FeS₂)与黄铜矿(CuFeS₂)沉淀过程中不仅存在热力学分馏,还存在动力学分馏现象,其中动力学分馏程度可以达到40.1‰,应用NanoSIMS微区测定手段可以有效剔除动力学分馏数据影响,获取热力学平衡分馏数据;(2)黄铁矿(FeS₂)与黄铜矿(CuFeS₂)成矿过程或利用不同的硫源,其中黄铁矿...     

Role of fluid mixing and wallrock sulfidation in gold mineralization at the Semna mine area, central Eastern Desert of Egypt: Evidence from hydrothermal alteration, fluid inclusions and stable isotope data

The Semna gold deposit is one of several vein-type gold occurrences in the central Eastern Desert of Egypt, where gold-bearing quartz veins are confined to shear zones close to the boundaries of small granitoid stocks. The Semna gold deposit is related to a series of sub-parallel quartz veins along steeply dipping WNW-trending shear zones, which cut through tectonized metagabbro and granodiorite rocks. The orebodies exhibit a complex structure of massive and brecciated quartz consistent with a change of the paleostress field from tensional to simple shear regimes along the pre-existing fault segments. Textural, structural and mineralogical evidence, including open space structures, quartz stockwork and alteration assemblages, constrain on vein development during an active fault system. The ore mineral assemblage includes pyrite, chalcopyrite, subordinate arsenopyrite, galena, sphalerite and gold. Hydrothermal chlorite, carbonate, pyrite, chalcopyrite and kaolinite are dominant in the altered metaggabro; whereas, quartz, sericite, pyrite, kaolinite and alunite characterize the granodiorite rocks in the alteration zones. Mixtures of alunite, vuggy silica and disseminated sulfides occupy the interstitial open spaces, common at fracture intersections. Partial recrystallization has rendered the brecciation and open space textures suggesting that the auriferous quartz veins were formed at moderately shallow depths in the transition zone between mesothermal and epithermal veins.Petrographic and microthermometric studies aided recognition of CO₂-rich, H₂O-rich and mixed H₂O–CO₂ fluid inclusions in the gold-bearing quartz veins. The H₂O–CO₂ inclusions are dominant over the other two types and are characterized by variable vapor: liquid ratios. These inclusions are interpreted as products of partial mixing of two immiscible carbonic and aqueous fluids. The generally light δ³⁴S of pyrite and chalcopyrite may suggest a magmatic source of sulfur. Spread in the final homogenization temperatures and bulk inclusion densities are likely due to trapping under pressure fluctuation through repeated fracture opening and sealing. Conditions of gold deposition are estimated on basis of the fluid inclusions and sulfur isotope data as 226–267 °C and 350–1100 bar, under conditions transitional between mesothermal and epithermal systems.The Semna gold deposit can be attributed to interplay of protracted volcanic activity (Dokhan Volcanics?), fluid mixing, wallrock sulfidation and a structural setting favoring gold deposition. Gold was transported as Au-bisulfide complexes under weak acid conditions concomitant with quartz–sericite–pyrite alteration, and precipitated through a decrease in gold solubility due to fluid cooling, mixing with meteoric waters and variations in pH and fO₂.     

Carbonate stromatolites from a Messinian hypersaline setting in the Caltanissetta Basin, Sicily: petrographic evidence of microbial activity and related stable isotope and rare earth element signatures

Lower Messinian stromatolites of the Calcare di Base Formation at Sutera in Sicily record periods of low sea‐level, strong evaporation and elevated salinity, thought to be associated with the onset of the Messinian Salinity Crisis. Overlying aragonitic limestones were precipitated in normal to slightly evaporative conditions, occasionally influenced by an influx of meteoric water. Evidence of bacterial involvement in carbonate formation is recorded in three dolomite‐rich stromatolite beds in the lower portion of the section that contain low domes with irregular crinkly millimetre‐scale lamination and small fenestrae. The dominant microfabrics are: (i) peloidal and clotted dolomicrite with calcite‐filled fenestrae; (ii) dolomicrite with bacterium‐like filaments and pores partially filled by calcite or black amorphous matter; and (iii) micrite in which fenestrae alternate with dark thin wispy micrite. The filaments resemble Beggiatoa‐like sulphur bacteria. Under scanning electron microscopy, the filaments consist of spherical aggregates of dolomite, interpreted to result from calcification of bacterial microcolonies. The dolomite crystals are commonly arranged as rounded grains that appear to be incorporated or absorbed into developing crystal faces. Biofilm‐like remains occur in voids between the filaments. The dolomite consistently shows negative δ¹³C values (down to ?11·3‰) and very positive δ¹⁸O (mean value 7·9‰) that suggest formation as primary precipitate with a substantial contribution of organic CO₂. Very negative δ¹³C values (down to ?31·6‰) of early diagenetic calcite associated with the dolomite suggest contribution of CO₂ originating by anaerobic methane oxidation. The shale‐normalized rare earth element patterns of Sutera stromatolites show features similar to those in present‐day microbial mats with enrichment in light rare earth elements, and M‐type tetrad effects (enrichment around Pr coupled to a decline around Nd and a peak around Sm and Eu). Taken together, the petrography and geochemistry of the Sutera stromatolites provide diverse and compelling evidence for microbial influence on carbonate precipitation.