Composition Of Fluid Inclusions Research Articles

A combined fluid inclusion and S–H–O–He–Ar isotope study of the Devonian Ashele VMS-type copper–zinc deposit in the Altay orogenic belt, northwest China

The Altay orogenic belt of Kazakhstan and China incorporates one of the world-class volcanogenic massive sulfide (VMS) polymetallic metallogenic belt. More than 12 large and superlarge VMS deposits have been found in this belt. The Ashele Basin is located at the western end of the Chinese Altay bordering Kazakhstan and hosts the large Ashele copper–zinc deposit, which is a typical VMS deposit and the largest one in this basin. The principal orebodies are stratabound and located between basalt and tuff units in the Ashele Formation. The mineralization has a two-layered structure that consists of an upper stratiform, concordant, massive Cu–Zn (or barite) orebody, and a lower veinlet–disseminated and stockwork Cu (or Cu–Pb–Zn–Ag) orebody associated with silicic alteration. Several exhalative rocks, such as barite, hematitic jasper, pyrite and silicified units also occur.Here we investigate the ore-forming fluids of the exhalative–sedimentary units including jaspilte, stratiform barite and Cu–Zn orebodies which carry fluid inclusions that show homogenization temperatures of 100–410 °C, with two peaks around 230 and 150 °C, and low salinity (clustering between 2 and 8 wt% NaCl equiv), corresponding to NaCl–H2O fluids. The ore-forming fluids of the vein orebody and silicified zones are characterized by low to medium temperature (peak homogenization temperatures between 120 and 280 °C), low to medium salinity (0.7–12.3 wt% NaCl equiv), and H2O–CO2 (±CH4/N2)–NaCl fluids. The δ34S values of barite associated with the stratiform barite orebody range from 20.4‰ to 21.4‰, indicating that the sulfur was derived from the seawater. The sulfur isotope values of sulfide (−3.7‰ to 7.7‰ with a mean of 3.1‰) are similar to those of VMS deposits from other parts of the world. The host volcanic rocks are inferred to be the major source from which the mineralizing fluid leached the ore-forming elements. The 3He/4He ratios of fluid inclusions in pyrite are in the range of 0.136–0.260 (R/Ra), broadly similar to the helium ratios of the crust. The 40Ar/36Ar ratios range from 394 to 9515, and are higher than those of atmospheric argon. The 40Ar/4He ratios of the ore fluids range from 0.002 to 0.064 with a mean of 0.034. The helium and argon isotope compositions of fluid inclusions suggest that the ore fluids of the Ashele deposit were mainly derived from the crust and were mixed with a minor amount of mantle component. The δ18OSMOW values of quartz from the silicified zones and vein orebody range from 8.3‰ to 11.1‰, with corresponding δ18Ofluid values of −4.45‰ to 2.24‰, whereas the δD values of fluid inclusions are between −140‰ and −90‰. The δ18OSMOW values of barite from the stratiform barite orebody range from 7.7‰ to 9.1‰, with corresponding δ18Ofluid values of –3.03‰ to 1.79‰, with δD values of fluid inclusions showing a range of –162‰ and –135‰. The combined isotopic data (H–O and He–Ar) suggest that the ore-forming fluids of the Ashele deposit were mainly derived from deep circulation of seawater and mixed with magmatic fluids. The decrease in temperature and pressure, water–rock exchange, and changes in the composition of ore fluids played important roles in the ore-forming processes of the Ashele Cu–Zn deposit.

Composition and source of fluids in high-temperature graphite-bearing granitoids associated with granulites: Examples from the Southern Marginal Zone, Limpopo Complex, South Africa

P-T conditions, fluid regime and carbon isotope composition of graphite and fluid inclusions from garnet-sillimanite-bearing leucocratic tonalites, trondhjemites and granites associated with orthopyroxene-bearing granulite metapelites in the Southern Marginal Zone (SMZ) of the Limpopo Complex, South Africa, are presented in the paper. Re-integrated compositions of perthitic alkali feldspars and antiperthitic plagioclase, as well as P-T and T-XCO2 phase equilibria modeling using PERPLE_X software indicate that the granitoids began to crystallize at temperatures of 900–940 °C and pressures of 7–9 kbar, and were equilibrated with a fluid phase with XCO2 > 0.5–0.6 as is recorded in dense fluid inclusions in quartz. A small fraction of a saline fluid accumulated during cooling only. Average δ13CPDB values for graphite (−6.52 to −8.65‰) and fluid inclusions (−2.50 to −5.58‰) from the granitoids differ substantially from the values, which have been obtained in previous studies for graphite from the surrounding SMZ metapelites. Isotope data thus indicate that fluids associated with the granitoid magmas of the SMZ originated from a source unrelated to the host metapelites. In terms of the “heavy” isotope signatures of carbon, the granitoids might carry fluids, which have been produced during devolatilization of mafic rocks (amphibolites) interlayered with hydrothermal carbonate veins in the adjacent granite-greenstone successions of the Kaapvaal craton that have been buried underneath the SMZ granulites during their exhumation. The cratonic rock could serve as a source for the trondhjemite magmas intruding the SMZ granulites. In this scenario, the studied granitoids crystallized from these magmas variously contaminated by metapelitic material. Graphite precipitated via reduction of CO2-rich fluid as the result of dissolution of pyrrhotite-rich metapelites in the magmas.

Formation of epithermal Sn-Ag-(Zn) vein-type mineralization at the Pirquitas deposit, NW Argentina: Fluid inclusion and noble gas isotopic constraints

The Pirquitas Sn-Ag-(Zn) deposit in northwestern Argentina is thought to be an analogue to the Miocene polymetallic epithermal Sn-Ag deposits of the southern Bolivian Tin Belt, but little is known in detail about the origin and evolution of ore-forming fluids at Pirquitas. This paper reports on a microthermometric study of fluid inclusions in quartz, sphalerite, Ag-Sn sulfides, and Ag-rich sulfosalts using transmitted near infrared and visible light, combined with noble gas isotope analyses of fluids released from mineral separates. The study focused on the vein-hosted mineralization, which formed during two major mineralization events, whereby the first event I comprises two stages (I-1 and I-2). All studied minerals exclusively contain aqueous two-phase inclusions, indicating that the ore-forming fluids did not undergo two-phase phase separation (boiling). Salinity of fluid inclusions in I-1 quartz that precipitated along with pyrite and pyrrhotite ranges between 0 and 7.5 wt% NaCl equiv. and homogenization temperatures (Th) are between 233 and 370 °C. Stage I-2 is characterized by abundant Sn-Ag-Pb-Zn-sulfides and a variety of Ag-rich sulfosalts. Fluid inclusions in stage I-2 Ag-Sn sulfides have salinities up to 10.6 wt% NaCl equiv. and Th between 213 and 274 °C. The deposition of stage I-2 ore is likely related to a new pulse of saline magmatic fluids to the hydrothermal system. The mineralization event II deposited the richest Ag ores at Pirquitas. Colloform sphalerite and pyrargyrite deposited during event II contain two-phase aqueous fluid inclusions with homogenization temperatures between 190 and 252 °C and salinities between 0.9 and 4.3 wt% NaCl equiv.Noble gas concentrations and isotopic compositions of ore-hosted fluid inclusions were determined from crushing hand-picked ore minerals from both mineralization events. With one exception, all samples yielded 3He/4He ratios between 1.9 and 4.1 Ra, which is within the range of published data from the volcanic arc and somewhat higher than typical values of meteoric water-derived hot-springs in the region. This demonstrates a significant contribution of magmatic fluids to the Pirquitas mineralization although no intrusive rocks are exposed in the mine region. Taking the noble gas evidence for a magmatic fluid source, we interpret the trends of decreasing Th and salinity values in fluid inclusions from events I and II to represent waning of the magmatic-hydrothermal system and/or increased admixing of meteoric water to the magmatic fluids.

Genesis of giant Early Proterozoic magnesite and related talc deposits in the Mafeng area, Liaoning Province, NE China

This study aims to understand the origin of giant magnesite and talc deposits in the Liaohe Group (Liaoning Province, NE China). Magnesite stromatolites and the composition of fluid inclusions suggest that magnesite or high-Mg calcite precipitated directly from strongly restricted seawater pools with meteoric influx. A primary evaporitic origin is also indicated for parts of the investigated dolomites by comparably heavy δ18O values. Later, intense metasomatic activity led to the formation of a magnesite/dolomite succession with irregular contacts and a lighter isotopic signature of oxygen. A slight shift in δ18O to more positive values was observed for talc-hosting magnesite, which can be explained by the incorporation of isotopically light oxygen into talc. This highlights that the hydrothermal processes that led to talc formation influenced the hosting carbonates as well, which is also documented by a tendency to smaller crystal sizes, a higher whiteness and lower trace element concentrations in samples from locations nearby large talc bodies. Although δ13C is suggested to be less sensitive to hydrothermal activity, comparably light δ13C values were determined for magnesite sinters, as well as for remobilized magnesites. In general, the δ13C signature of the investigated magnesites is lighter than expected for Proterozoic carbonates. A single-stage generation of the giant talc deposit in the study area is suggested based on elemental and isotopic data. Later deformation led to a (iso-chemical) re-location of talc at least once. During this process, irregularly distributed, cloudy/massive talc bodies acted as weak zones and were incorporated into shear bands up to several meters in thickness, which form the actually present, structurally controlled deposit. The original ore type is preserved only in areas with minor deformation. Lamprophyre dykes prove Jurassic volcanism and are clearly younger than the main phase of talc generation. A younger (post-Jurassic?), intense tectonic event is indicated by strongly tectonized dyke material that is re-worked into strike-slip faults and shows siliceous contact zones to the surrounding magnesite. These faults occasionally cross-cut the older, deposit-forming talc shear bands, indicating that the event that led to the deformation of lamprophyre dykes was younger than the main phase of talc re-location. However, this younger event did not lead to a second phase of major talc generation or affect the quality of the initial deposit to a large extent.

Genetic implications for the Damajianshan W‐Cu‐As polymetallic deposit in Lvchun, Southwest China: Constraints from H–O, He–Ar, S, and Pb isotopes

The Sanjiang Tethyan domain in SE Asia is one of the most important mineral belts in China. The Damajianshan (DMJS) W‐Cu‐As polymetallic deposit is located in the southern part of Sanjiang Tethyan domain, related to Triassic quartz porphyry. Detailed exploration thereafter shows that the reserves of W, Cu, and As are 0.09, 0.42, and 0.12 Mt, respectively. The W is a typical oxyphile element and always coexisted with Sn–Li–Be–Nb–Ta. The Cu–As are typical sulphophile elements and always coexisted with Au–Ag–Pb–Zn–Sb–Hg. It is rarely reported that a deposit preserves tungsten and copper–arsenic simultaneously in the southern Sanjiang region. In this study, the S–Pb isotopic ratios of sulphides, the H–O isotopic compositions of fluid inclusions in hydrothermal quartz, and the He–Ar isotopic ratios of fluid inclusions in sulphides were analysed to constrain the origin of the DMJS deposit. Studies have shown that the δ34S values of sulphides from ores are mainly between −6.17‰ and +0.02‰; the sulphur isotope compositions indicate that the ore‐forming materials might originate from deep sources. The Pb isotope characteristics indicate that the ore metals might originate from deep sources and be closely related to the quartz porphyry. The δ18Ofluid values of ore‐forming fluids calculated from hydrothermal quartz range from −5.5‰ to +7.5‰, and the δD values of the fluid inclusions in quartz are from −81.7‰ to −50.2‰. The H–O isotope systematics indicate that the ore fluids in the DMJS deposit were probably initially sourced from magmatic water and later gradually mixed with Mesozoic meteoric water. Fluid inclusions in pyrite, chalcopyrite, arsenopyrite, and pyrrhotite possess 3He/4He ratios of 0.02–0.05 Ra, and their 40Ar/36Ar ratios range from 562.47 to 4159.15, indicating a complete crustal fluids and with higher radiogenic 40Ar. The noble gas isotopic data, along with the stable isotopic data, suggest that the ore‐forming fluids have a deep source. The unique geologic structure of the Sanjiang Tethys tectonic metallogenic region and the evolution of ore‐forming fluids both promoted the formation of this rare DMJS deposit.

Reconstruction of a >200 Ma multi-stage “five element” Bi-Co-Ni-Fe-As-S system in the Penninic Alps, Switzerland

Hydrothermal five-element veins (Ag-Co-Ni-Bi-As) are mineral successions of native metals, encapsulated by Fe-Co-Ni arsenides and carbonates. Recent studies focused on the evolution from ordinary base-metal systems (sulfide-rich) to five-element veins (sulfide-poor) and revealed the importance of hydrocarbon-dominated fluids as essential redox agent in these systems. Although mineral successions reveal the natural subdivision into native As-, native Ag/Bi- or arsenide-dominated vein types and suggested processes explain the mineralogical variation to a certain degree, the Ni-Co-Fe-variations among the arsenides are not well understood yet.This is the first case study explaining compositional, mineralogical, and textural features of five-element veins by changing metal contents, arsenic/sulfur activities, pH and temperatures, applied to a multi-stage vein mineralization in the Penninic Alps, Switzerland. Textural relationships, mineral chemistry, fluid inclusion compositions (microthermometry and Raman spectroscopy), stable S-isotopes and in-situ U-Pb age dating of carbonates, magnetite and multi-mineral isochrons were investigated.U-Pb ages of paragenetic mineral fractions constrain a primary formation of löllingite-skutterudite-dolomite-dominated ores at 233 ± 10 Ma and niccolite-gersdorffite-skutterudite-ankerite-dominated ores at 188 ± 32 Ma, which links their formation to crustal thinning caused by the breakup of the Meliata ocean and Alpine Tethys. As secondary processes during the Alpine Orogeny, a in-situ remobilization of the ores occurred as mostly ternary Fe-Co-Ni sulfarsenides at ∼73–24 Ma due to continent-continent collision and neoformations of safflorite-cobaltite-skutterudite-dominated ores at ∼29–16 Ma due to transtensional strike-slip tectonics.Ore textures indicate that the dissolution of primary siderite, oxidation of ferrous iron and its precipitation as magnetite was the redox couple to precipitate native Bi, arsenides and sulfarsenides (Bi0, As3− and As−1) from their oxidized aqueous species Bi3+Cl4−, and As3+(OH)3 at temperatures between 200 and 300 °C. Ni and Co signatures of the arsenides/sulfarsenides show increasing mobilization from the host rocks during the successive evolution of the hydrothermal system in the Triassic, Jurassic and during the Alpine Orogeny. Stable S-isotopes and As/S signatures of the sulfarsenides indicate an increasing mobilization of host rock sulfides (i.e. fahlbands) from the primary to the secondary ores. Fluid inclusions and stable S-isotopes suggest involvement of fluid modification by water-rock interactions (i.e. cover rocks: carbonate, sulfate and halite dissolution; basement rocks: albitisation of plagioclase) during fluid descent.

N-δ13C-inclusion profiles of cloudy diamonds from Koffiefontein: Evidence for formation by continuous Rayleigh fractionation and multiple fluids

Abstract Six diamonds with a fibrous core, intermediate zone and monocrystalline outer zone (“cloudy diamonds”) from the Koffiefontein mine, South Africa, were investigated for N concentrations, carbon isotope compositions and micro-inclusion compositions along core to rim traverses. This study evaluates the nature of the change from fibrous to gem diamond growth and the relation between major element composition of high density fluid inclusions and N − δ13C in fibrous growth zones. Three diamonds contain saline to carbonatitic fluid micro-inclusions with constant or increasing carbon isotope values which are inferred to have formed by varying amounts of Rayleigh fractionation in a closed system of a carbonate-bearing fluid. Continuous N − δ13C fractionation trends from the fibrous to gem growth zone in two of the diamonds and equally low nitrogen aggregation states indicate formation of diamond shortly before kimberlite eruption from a single fluid without a time gap between fibrous and gem diamond growth. High major element/CO32– ratios in the growth media resulted in a constant major element composition of the fluid inclusions found in the studied fibrous diamonds. The transition from fibrous to gem diamond growth is likely caused by the precipitation of diamond reducing the degree of oversaturation of carbon in the fluid and hence decreasing the rate of diamond growth. Two other diamonds have inclusions that change from silicate minerals in the inner fibrous growth zones towards pure saline fluid compositions in the outer fibrous growth zones. This decrease in Si, Mg and Ca and increase in K and Cl in the inclusions is accompanied by a decrease in δ13C values and N contents. These trends are suggested to be the result from gradually mixing in more saline fluids with lower δ13C values. One diamond with silicic inclusions has significant N aggregation into B-centres, suggesting this fluid is different and that diamond formation occurred significantly (e.g. 1250 °C gives ≥10 Ma) before the kimberlite eruption.

Genesis of the Xishadegai Mo deposit in Inner Mongolia, North China: Constraints from geology, geochronology, fluid inclusion, and isotopic compositions

The Xishadegai Mo deposit is a medium‐sized deposit located in the northern margin of the North China Craton. The Mo mineralization is structurally controlled, and spatially and temporally related to the Xishadegai felsic intrusive rocks. Ore bodies mainly occur as quartz veins/veinlets in altered granitic rocks associated with potassic, phyllic, argillic, and fluorite alterations. The ore‐forming process can be divided into 3 stages: Stage I K‐feldspar‐quartz ± molybdenite, Stage II quartz‐pyrite‐molybdenite‐muscovite ± fluorite, and Stage III quartz‐fluorite ± muscovite. Four types of fluid inclusions were distinguished in smoky grey and dark grey quartz of the main‐ore stage (II), including two‐phase aqueous inclusions, CO2‐H2O inclusions, daughter mineral‐bearing multiphase inclusions, and minor vapour aqueous inclusions. The fluid inclusions in smoky grey and dark grey quartz are homogenized at temperatures of 195–350 °C and 191–291 °C, respectively, with calculated salinities of 3.9–11.1% NaCleq and 31.5–33.0% NaCleq, respectively. The ore‐forming fluids belong to a H2O‐CO2‐NaCl system characterized by abundant CO2, moderate to high temperature, and low to high salinity. The δ18OH2O and δD values of ore‐stage quartz vary from −0.2‰ to 0.9‰ and from −120‰ to −104‰, respectively, indicating that the ore‐forming fluids were evolved from magmatic water and gradually mixed with significant amounts of meteoric water. Sulphur and lead isotopic compositions indicate that the ore materials were mainly derived from magmatic sources. Zircon LA‐ICP‐MS U–Pb dating on the mineralized porphyritic moyite yielded a weighted mean age of 235.1 ± 2.0 Ma, corresponding to the Triassic postcollisional setting following the closure of the Paleo‐Asian Ocean between the Siberian Plate and the North China Craton. The εHf(t) values and TDM2 ages range from −15.0 to −12.8 and from 2.2 to 2.1 Ga, respectively, suggesting that the Xishadegai granite was mainly generated by melting of Paleoproterozoic crustal components. Collectively, evidence from geology, fluid inclusion, H‐O‐S‐Pb isotopes, and geochronology suggests that the Xishadegai deposit could be classified as a magmatic–hydrothermal vein Mo deposit. Phase separation (immiscibility and boiling) was the most likely mechanism for ore deposition.

Evidence of high-temperature rock salt transformations in areas of occurrence of borate minerals (Zechstein, Kłodawa salt dome, Poland)

Occurrences of borate minerals in the Zechstein salt-bearing deposits of the Klodawa salt dome (central Poland), and the manner of their development, suggest that the minerals were formed at high temperatures, that considerably exceed the temperature estimated from the thermal gradient (~180°C). Research on rock salt and potassium-magnesium salts containing congolite and boracite, respectively, are consistent with high-temperature processes of transformations affecting the salt rocks in certain sections of the salt dome. The chemical composition of, and daughter minerals occurring in, primary fluid inclusions in halite, originating from the congolite zone, indicated a very high proportion of potassium and magnesium in the brines from which the halite crystallised. The thermal transformations observed in inclusions indicate a halite crystallisation temperature exceeding 420°C. Anhydrite crystals, co-occurring with borate minerals, represent unique features as to the distribution and composition of solid and fluid inclusions. These features indicate crystallisation or recrystallisation in conditions that differed considerably from those typical of the salt dome, with the involvement of solutions of changing chemical compositions. The crystals contain multiple solid inclusions of transparent and non-transparent minerals, among which we have focused on carnallite. The relationships of carnallite with liquid and gaseous phases indicate, as in the congolite zone, migration of very highly concentrated brines with respect to potassium and magnesium, or even transport of carnallite in the form of melt (liquid). Measurements of fluid inclusion homogenization temperatures, within the range from 197.8 to 473.8°C, supported a high-temperature origin for these minerals in hydrothermal conditions.

Origin of ore-forming fluids of the Zn-Pb-(Cu) deposits in the Jinbao mine district of eastern Guizhou Province, China: Evidence from chemical compositions of fluid inclusions and their lithium isotopes

Origin of ore-forming fluids of the Zn-Pb-(Cu) deposits in the Jinbao mine district of eastern Guizhou Province, China: Evidence from chemical compositions of fluid inclusions and their lithium isotopes

Origins of ore-forming fluid and material of the quartz–vein type Mo deposits in the East Qinling–Dabie molybdenum belt: A case study of the Qianfanling Mo deposit

The Qianfanling quartz–vein type molybdenum deposit is located in the East Qinling–Dabie Mo belt. The Mo mineralization in the deposit is mainly present as structurally controlled Mo-bearing quartz veins. Based on chromatography analysis of the Qianfanling Mo deposit, the gas compositions of fluid inclusions in quartz dominantly contain H2O and relatively high concentrations of CO2 (11.019 to 18.554mol%). Cations and anions of liquid compositions of fluid inclusions are mainly Na+ and Ca2+, and SO42− and Cl−, respectively. The characteristics of gas and liquid compositions of fluid inclusions in quartz indicate that the Qianfanling Mo deposit formed under conditions of high oxygen fugacity. Analytical results of He-Ar isotopes of fluid inclusions in pyrite from the Qianfanling Mo deposit show that 3He/4He ratios vary from 0.02438 to 0.0796 Ra (Ra is the 3He/4He ratio of air=1.40×10−6), with F4He values of 252,509–885,224. The calculated Hemantle values range from 0.18 to 0.87%, with an average of 0.39%. 40Ar/36Ar ratios are 694.4–1473.4, with the estimated 40Ar* (radiogenic 40Ar) proportion of 79.9%. These He-Ar isotopic data indicate that most of the He in the fluid inclusions was derived from the crust, with negligible atmospheric He and only a very small input from the mantle probably. Furthermore, the Ar in the ore-forming fluid was mainly derived from the crustal source, with minor atmospheric Ar involved. 17 Re–Os model ages of 15 molybdenite samples from the 4 quartz-vein type Mo deposits (Qianfanling, Daxigou, Maogou, and Zhifang) range from 215.0 to 248.2Ma, with a mean value of 235.6Ma, which is close to the age of peak collision between the North China and Yangtze Cratons. The Re contents in molybdenite from the 4 deposits range from 0.19 to 39.16ppm, with an average of 17.41ppm, indicating a crust-dominated source. Re contents in molybdenite from Mesozoic Mo deposits in different ages and types in the East Qinling–Dabie Mo belt show different characteristics of ore sources. Combined with gas and liquid compositions and He-Ar isotopic characteristics of fluid inclusions, as well as Re contents in molybdenite of this paper and previous studies, we suggest that the ore-forming fluid and material of the Qianfanling Mo deposit were mainly derived from crustal magmatic source. This magmatic source could have formed by partial melting of deep crustal rocks under a certain condition during the collision between the North China and Yangtze Cratons.

Evidence for large scale fractionation of carbon isotopes and of nitrogen impurity during crystallization of gem quality cubic diamonds from placers of North Yakutia

The spatial distribution of carbon and nitrogen isotopes and of nitrogen concentrations is studied in detail in three gem quality cubic diamonds of variety II according to Orlov’s classification. Combined with the data on composition of fluid inclusions our results point to the crystallization of the diamonds from a presumably oxidized carbonate fluid. It is shown that in the growth direction δ13C of the diamond becomes systematically lighter by 2–3‰ (from –13.7 to –15.6‰ for one profile and from –11.7 to –14.1‰ for a second profile). Simultaneously, we observe substantial decrease in the nitrogen concentration (from 400–1000 to 10–30 at ppm) and a previously unrecognized enrichment of nitrogen in light isotope, exceeding 30‰. The systematic and substantial changes of the chemical and isotopic composition can be explained using the Burton-Prim-Slichter model, which relates partition coefficients of an impurity with the crystal growth rate. It is shown that changes in effective partition coefficients due to a gradual decrease in crystal growth rate describes fairly well the observed scale of the chemical and isotopic variations if the diamond-fluid partition coefficient for nitrogen is significantly smaller than unity. This model shows that nitrogen isotopic composition in diamond may result from isotopic fractionation during growth and not reflect isotopic composition of the mantle fluid. Furthermore, it is shown that the infra-red absorption at 1332 сm-1 is an integral part of the Y-defect spectrum. In the studied natural diamonds the 1290 сm-1 IR absorption band does not correlate with boron concentration.

Lithium isotopes in fluid inclusions as tracers of crustal fluids: An exploratory study

Lithium isotopes are extensively used to trace fluid migration and fluid-rock interactions in the shallow Earth's crust. Although, Li isotope systematics might give important information about deep crustal fluids, this stable isotope system remains surprisingly under exploited in fluid inclusions. Here, twenty-three samples from a variety of deep environments, from diagenetic, metamorphic to magmatic-hydrothermal conditions (~150 to 600°C), have been investigated in order to provide the first exploratory overview of the range in Li isotopic composition of fluid inclusions. From 1 to 2g of hydrothermal quartz or dolomite, cation analysis (Na, K, Ca, Mg, Sr, Li), Li fraction recovery and Li isotopic analysis of bulk fluid inclusion leachates were carried out by using an innovative approach coupling crush-leach extraction, high performance ion chromatography and MC-ICPMS analysis. Reconstructed Li concentrations and δ7Li values of these fluid inclusions (respectively 12 to 653mg/l and −1.4±0.2‰ to +41.3±0.8‰) are compatible with previously proposed models for the origin of the fluids and fluid-rock interactions. δ7Li values are independent from other tracers (Br/Cl, I/Cl) and parameters such as temperature, salinity, and cation content. The results show that, in conjunction with other parameters, the Li isotopic compositions of fluid inclusions are potentially powerful source and process tracers of deep crustal fluids within a wide range of geological environments and related ore-forming systems, for example in from sedimentary basins, seafloor hydrothermal systems and subduction zones.

Fluid evolution in the southern part of the Proterozoic Vazante Group, Brazil: Implications for exploration of sedimentary-hosted base metal deposits

The Proterozoic Vazante Group carbonate rocks were submitted to multiple stages of fluid circulation from diagenesis to orogenesis as documented by detailed mineralogical, fluid inclusion and isotopic studies of the Upper Morro do Pinheiro and Lower Pamplona members from the Serra do Poço Verde Formation in the southern part of the paleo-basin. These units are the main hosts for the hypogene, structurally-controlled zinc silicate deposits in the Vazante Zinc District, including the Vazante mine, which is considered to be the largest willemitic (Zn2SiO4) deposit in the world, with estimated total resources of 40–60Mt at 20% Zn. Five hydrothermal alteration types were identified in the Southern Extension of the Vazante Group. (I) Early stage alteration comprises dolomite substitution bands and nodules, associated with moderate salinity H2O-NaCl-CaCl2 fluids, with temperatures around 90°C, interpreted as late-diagenetic. The calculated C and O isotopic compositions of the fluids suggest meteoric and/or connate origin and interaction with organic carbon. (II) Pre-ore stage alteration is evidenced by dog-tooth dolomite and quartz with minor Fe-oxi/hydroxides which fills dissolution voids formed by H2O-NaCl-CaCl2±MgCl2 fluids at temperatures around 100° to 150°C. The C isotopic data also indicate interaction with organic carbon. The two first stages are poor in ore-related elements. (III) Ore stage encompasses four phases of mineral precipitation. The first is distal and characterized by red stained dolostones due to disseminated hematite and red dolomite. The second is the main phase of the ore stage, composed of massive red dolomite, massive hematite and willemite with enrichment mainly in Fe2O3, SiO2, Ag, As, Cd, Cu, Ni, Pb, Se and Zn. The third phase comprises white dolomite, hematite and traces of willemite with enrichment in MnO, Cd, Ni and Pb. The calculated C and O isotopic compositions of the fluids (at 180°C) associated with pervasive alteration yielded values heavier than the diagenetic stage and lower than the host rock. The fourth phase corresponds to Zn-chlorite and quartz which are associated with H2O-NaCl fluids of variable salinities and distinct temperatures (90–140°C and 170–190°C). (IV) Pyrite-bearing vein characterized by pyrite, sphalerite, white dolomite, fine hematite and late quartz, with C and O isotopic and fluid inclusion compositions that are similar to the three phases of dolomite of the ore stage. These data suggest a co-genetic relationship of these two alteration styles. (V) The late sulfide stage characterized by rare galena-bearing stringers with sphalerite, chalcocite, greenockite, covellite and white dolomite that cross-cut the main ore stage phases. The ore-related fluid compositions associated with the silicate zinc mineralization in the southern part of the Vazante Group are also similar to the fluids reported in previous work for the sulfide zinc-lead deposits in the northern part, indicating favorable conditions for metal transport during the Brasiliano Orogeny. Sulfide ore would have precipitated in zones where sulfur was available and silicate zinc in structures where mineralizing fluids interacted with evolved meteoric water. This finding implies that carbonate sequences in other districts with sulfide lead-zinc deposits may also host hypogene silicate zinc deposits.

Composition and Evolution of Fluids Forming the Baiyinnuo’er Zn-Pb Skarn Deposit, Northeastern China: Insights from Laser Ablation ICP-MS Study of Fluid Inclusions*

The Baiyinnuo'er skarn deposit is one of the largest Zn-Pb deposits in northeastern China, with 32.74 million metric tons (Mt) resources averaging 5.44% Zn, 2.02% Pb, and 31.36 g/t Ag. The deposit formed in three stages: the preore stage (prograde skarn minerals with minor magnetite), the synore stage (sulfides and retrograde skarn minerals including calcite and minor quartz), and the postore stage (late veins composed of calcite, quartz, fluorite, and chlorite; cutting the above mineral assemblages). In this study we analyzed the composition of single fluid inclusions using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to (1) determine the composition of the fluids and the evolution through the stages, (2) infer the fluid and metal sources, and (3) explore the metal deposition mechanisms. The preore fluids trapped in pyroxene have higher homogenization temperatures (432°–504°C), higher salinity (36.5–46.1 wt % NaCl equiv), and higher concentrations of Zn (~0.9 wt %), Pb (~1.4 wt %), and other elements (e.g., Na, K, Li, As, Rb, Sr, Cs, Ba, Cl, and Br) than synore mineralizing fluids (<370°C, <10 wt % NaCl equiv, ~450 ppm Zn, and ~290 ppm Pb). The postore fluids show lower temperatures (<250°C) and a rather dilute composition (<4 wt % NaCl equiv, ~33 ppm Zn, and ~24 ppm Pb). Geochemically, the fluids of all paragenetic stages in Baiyinnuo'er have magmatic signatures based on the element mass ratios, including elevated K/Na, Zn/Na, and Rb/Na ratios, lower Ca/K ratios, and combined Cl/Br-Na/K ratios, which are distinctively different from basinal brines. Inclusion fluids in preore stage show little variation in composition between ~510° and ~430°C, indicative of a closed cooling system. In contrast, the major components of the syn- and postore fluids, including Cl, Na, and K, decrease and correlate with a drop of homogenization temperatures from ~370° to ~200°C, indicating a dilution by mixing with groundwater. The Baiyinnuo'er mineralizing fluids (trapped in sphalerite) have higher Ca/K mass ratios (avg ~0.78) than other proximal magmatic hydrothermal systems (0.06–0.52) but lower than that of the distal El Mochito skarn (avg ~6.4), probably reflecting a gradually weakened magmatic signal away from the causative intrusions. The metal contents in preore fluids are significantly higher than those in synore fluids, but no mineralization occurred. This confirms that the early fluids were, although enriched in metals, not responsible for ore precipitation, most likely due to their high temperature and high salinities. One important factor controlling Zn-Pb mineralization was mixing with groundwater, which resulted in temperature decrease and dilution that significantly reduced the metal solubility, thereby promoting metal deposition. Another main driving force was the interaction with carbonate wall rock that buffered the acidity generated during the breakdown of Zn and (Pb)-Cl complexes and the precipitation of sulfides. Phase separation occurred in both the preore and the early part of the synore stages, but no evidence indicated that it caused metal deposition. The prograde minerals and retrograde minerals (including ore minerals) coexisting in the same samples could have been caused by two (or more) successive pulses of hydrothermal fluids released from residual melts of a progressively downward crystallizing magma. Each fluid produced a series of proximal high-temperature prograde to distal low-temperature assemblages, with the lower temperature assemblages of later fluids overprinting the higher temperature assemblages at most locations.

Noble gas data from Goldfield and Tonopah epithermal Au-Ag deposits, ancestral Cascades Arc, USA: Evidence for a primitive mantle volatile source

The He, Ne, and Ar isotopic composition of fluid inclusions in ore and gangue minerals were analyzed to determine the source of volatiles in the high-grade Goldfield and Tonopah epithermal Au-Ag deposits in southwestern Nevada, USA. Ar and Ne are mainly atmospheric, whereas He has only a minor atmospheric component. Corrected 3He/4He ratios (with atmospheric He removed) range widely from 0.05 to 35.8 times the air 3He/4He ratio (RA), with a median of 1.43 RA. Forty-one percent of measured 3He/4He ratios are ≥4 RA, corresponding to ≥50% mantle He assuming a mantle ratio of 8 RA. These results suggest that mafic magmas were part of the magmatic-hydrothermal system underlying Goldfield and Tonopah, and that associated mantle-sourced volatiles may have played a role in ore formation. The three highest corrected 3He/4He ratios of 17.0, 23.7, and 35.8 RA indicate a primitive mantle He source and are the highest yet reported for any epithermal-porphyry system and for the Cascades arc region. Compiled 3He/4He measurements from epithermal-porphyry systems in subduction-related magmatic arcs around the world (n=209) display a statistically significant correlation between 3He/4He and Au-Ag grade. The correlation suggests that conditions which promote higher fluid inclusion 3He/4He ratios (abundance of mantle volatiles and focused upward volatile transport) have some relation to conditions that promote higher Au-Ag grades (focused flow of metal-bearing fluids and efficient chemical traps). Results of this and previous investigations of He isotopes in epithermal-porphyry systems are consistent with the hypothesis posed in recent studies that mafic magmas serve an important function in the formation of these deposits.

The Sources of Ore‐forming Fluids from the Jinchang Gold Deposit, Heilongjiang Province, NE China: Constraints from the He–Ar Isotopic Evidence

AbstractThe Jinchang gold deposit (more than 40 tons of gold) is located in the easternmost portion of the Central Asian Orogenic Belt. The gold mineralization types include mainly breccia, quartz vein and alteration rock types. Geological and geochemical characteristics suggest that the Jinchang gold deposit formed by the superposition of epithermal gold deposits and porphyry gold deposits. In this study, the helium and argon isotopic compositions of fluid inclusions in pyrites from the different ores are analyzed. The results show that 3He/4He ratios of fluid inclusions in pyrites range from 0.13 to 2.42 Ra, 40Ar/36Ar ratios are within 308.9–336.7, indicating that the ore‐forming fluids of the Jinchang gold deposit were a mixture of crustal‐derived fluids and partial mantle‐derived fluids, and were contaminated by circum‐flow meteoric water. From the early to the late mineralization stages, Jinchang gold deposit had a fluid evolution trend from more mantle fluid in the central area to crustal fluid in the outer area. Jinchang gold deposit is the result of superimposition of mineralization of magmatic fluids at different phases and nature.

Chemical Compositions of Fluid Inclusions in the Jalal –Abad iron oxide deposit, North West of Zarand, Using LA-ICP-MS Microanalysis

روش میکروآنالیز LA-ICP-MS برای آنالیز ترکیب سیال‌های درگیر واقع در کانسار آهن جلال‌آباد استفاده شد. نمونه های مورد بررسی از گمانه های حفاری شده و پیت معدن که با کانی سازی ارتباط داشتند، برداشت شده است. سیالات درگیر چند فازی (L+V+S) در کوارتز فراوان است و دمای همگن شدن آنها 260 تا 440 درجه سانتی‌گراد است. شوری سیالات بین 30 تا 52 درصد معادل وزنی نمک طعام است. نتایج LA-ICP-MS روی سیالات درگیر نشان داد که مقدار Fe و Cu به‌ترتیب تا 16076 و 3204 گرم بر تن و میانگین 6914 و 792 گرم بر تن هستند. مقدار Na در سیالات درگیر بین 26906 تا 140716 گرم بر تن و K در محدوده 2372 تا 70484 گرم بر تن اندازه‌گیری شد. نسبت Ca/K بین 53/0 تا 68/8 و با میانگین 75/1 است که نشان‌دهنده اختلاط سیالات ماگمایی و غیر ماگمایی است. نسبت Mn/Fe در سیالات درگیر در محدوده 21/0 تا 87/1 است که نشان‌دهنده حضور دو نوع سیال اکسیدی و احیایی است. نتایج به‌دست آمده از بررسی‌های کانی شناسی، میکروترمومتری و شیمی سیالات درگیر نشان می دهد سیالات ماگمایی- گرمابی حاوی فلزات، سیالات گرمابی- غیر ماگمایی و اختلاط آنها با یکدیگر علت کانی سازی اکسید آهن- مس- طلا در کانسار جلال آباد بوده است.

Organic compounds in fluid inclusions of Archean quartz-Analogues of prebiotic chemistry on early Earth.

The origin of life is still an unsolved mystery in science. Hypothetically, prebiotic chemistry and the formation of protocells may have evolved in the hydrothermal environment of tectonic fault zones in the upper continental crust, an environment where sensitive molecules are protected against degradation induced e.g. by UV radiation. The composition of fluid inclusions in minerals such as quartz crystals which have grown in this environment during the Archean period might provide important information about the first organic molecules formed by hydrothermal synthesis. Here we present evidence for organic compounds which were preserved in fluid inclusions of Archean quartz minerals from Western Australia. We found a variety of organic compounds such as alkanes, halocarbons, alcohols and aldehydes which unambiguously show that simple and even more complex prebiotic organic molecules have been formed by hydrothermal processes. Stable-isotope analysis confirms that the methane found in the inclusions has most likely been formed from abiotic sources by hydrothermal chemistry. Obviously, the liquid phase in the continental Archean crust provided an interesting choice of functional organic molecules. We conclude that organic substances such as these could have made an important contribution to prebiotic chemistry which might eventually have led to the formation of living cells.

Fluid Inclusion, H-O, S, Pb and noble gas isotope studies of the Aerhada Pb-Zn-Ag deposit, Inner Mongolia, NE China

The Aerhada Pb-Zn-Ag deposit is located in the western segment of the Great Hinggan Range Ag-Pb-Zn-Cu-Mo-Au-Fe metallogenic belt in NE China. Orebodies occur mainly as vein type and are hosted by sandstone and siliceous slate. Three stages of primary mineralization, including an early arsenopyrite-pyrite-quartz, a middle polymetallic and silver sulfides-quartz and a late sphalerite-pyrite-calcite-fluorite are recognized. Four types of fluid inclusions have been identified in the ore-bearing quartz and fluorite veins, i.e., liquid-rich, gas-rich, three-phase CO2 aqueous inclusions, and pure gas or liquid aqueous inclusions. Microthermometric studies on fluid inclusions reveal that homogenization temperatures from early to late stages range from 253° to 430°C, 195° to 394°C and 133° to 207°C, respectively. Fluid salinities range from 2.9 to 14.0wt.% NaCl equiv. The vapor composition of the ore fluid is dominated by H2O, CO2 and CH4, with minor proportions of N2. The fluid δ18OH2O and δDH2O values vary from +1.6 to +9.3‰ and −122 to −56‰, respectively, and reflect a magmatic fluid and a meteoric fluid dominant hydrothermal system for the early and late stages of mineralization, respectively. The calculated δ34SH2S values of hydrothermal fluids in equilibrium with sulfides range from +5.2 to +7.1‰, suggesting a mixed source for sulfur, i.e., the local magmatic and sedimentary rocks. The Pb isotope compositions of sulfides are similar to those of the local magmatic and sedimentary rocks, implying that lead and possibly silver relate to these sources. The noble gas isotope compositions of fluid inclusions hosted in ore minerals suggest that the ore-forming fluids were dominantly derived from a deep mantle source. Fluid mixing and dilution are inferred as the dominant mechanisms for ore deposition. The Aerhada Pb-Zn-Ag deposit can be classified as a medium to low temperature hydrothermal vein type deposit.