Graphite morphologies from the Borrowdale deposit (NW England,UK): Raman and SIMS data

Graphite in the Borrowdale (Cumbria, UK) deposit occurs as large masses within mineralized pipe-like bodies, in late graphite–chlorite veins, and disseminated through the volcanic host rocks. This occurrence shows the greatest variety of crystalline graphite morphologies recognized to date from a single deposit. These morphologies described herein include flakes, cryptocrystalline and spherulitic aggregates, and dish-like forms. Colloform textures, displayed by many of the cryptocrystalline aggregates, are reported here for the first time from any graphite deposit worldwide. Textural relationships indicate that spherulitic aggregates and colloform graphite formed earlier than flaky crystals. This sequence of crystallization is in agreement with the precipitation of graphite from fluids with progressively decreasing supersaturation. The structural characterization carried out by means of Raman spectroscopy shows that, with the exception of colloform graphite around silicate grains and pyrite within the host rocks, all graphite morphologies display very high crystallinity. The microscale SIMS study reveals light stable carbon isotope ratios for graphite (δ ¹³C = −34.5 to −30.2‰), which are compatible with the assimilation of carbon-bearing metapelites in the Borrowdale Volcanic Group magmas. Within the main mineralized breccia pipe-like bodies, the isotopic signatures (with cryptocrystalline graphite being lighter than flaky graphite) are consistent with the composition and evolution of the mineralizing fluids inferred from fluid inclusion data which indicate a progressive loss of CO₂. Late graphite–chlorite veins contain isotopically heavier spherulitic graphite than flaky graphite. This agrees with CH₄-enriched fluids at this stage of the mineralizing event, resulting in the successive precipitation of isotopically heavier graphite morphologies. The isotopic variations of the different graphite morphologies can be attributed therefore, to changes in the speciation of carbon in the fluids coupled with concomitant changes in the XH₂O during precipitation of graphite and associated hydrous minerals (mainly epidote and chlorite).     

Fluid inclusion and stable isotopic constraints on fluid sources and evolution of the Luojiahe Cu deposit in the southern margin of the North China Craton

The Luojiahe Cu deposit in the Zhongtiaoshan region is located in the southern margin of the North China Craton. The orebodies are hosted in the mafic volcanic-sedimentary sequences of the metamorphosed (greenschist-facies) Neoarchean Songjiashan Group. The Luojiahe Cu mineralization can be divided into the primary volcanogenic massive sulfide (VMS) mineralization stage (Stage I, banded or stockwork ores) and the subsequent metamorphic remobilization stage (Stage II, coarse-vein ores).Three types of quartz selected for fluid inclusion (FI) studies were collected from the Stage I banded (Q1) and stockwork (Q2) ores and Stage II coarse-vein (Q3) ores. Four types of FIs were identified: (1) liquid-rich FIs (L-type), (2) pure vapor and vapor-rich FIs (V-type), (3) daughter mineral-bearing FIs (S-type), and (4) CH₄-H₂O FIs (C-type). Systematical microthermometric and H-O isotopic studies show that the Stage I ore-forming fluids consist predominantly of high salinity evolved seawater (125–220 °C; 23.9–27.9 wt.% NaCl equiv.) and some magmatic-hydrothermal fluids (249–339 °C; 34.5–42.2 wt.% NaCl equiv.). The two fluid end-members are represented by the L-type FIs in Q1 and the S- and V-type FIs in Q2. The temperature- and salinity variation trends of the L-type FIs in Q1 indicate a mixing process between the hot evolved seawater and cold seawater at Stage I. Furthermore, the V- and S-type FI coexistence in Q2 and their microthermometric data suggest that fluid unmixing has occurred in original magmatic fluids at Stage I. In contrast, the Stage II ore-forming fluids consist of CH₄-rich metamorphic fluids (192–350 °C; 10.6–43.2 wt.% NaCl equiv.). Carbon isotopic analysis of the Stage II calcite (− 4.58 to − 10.83‰) and graphite (− 32.01 to − 39.16‰) in the ore-hosting chlorite schist indicates that the metamorphic ore-forming fluids had exchanged carbon isotope with graphite. The generation of CH₄ may have resulted from the interaction between H₂O (released by metamorphic devolatilization) and graphite. The continuous consumption of H₂O in the hydrothermal fluid system may have increased the fluid salinity and triggered fluid unmixing in the CH₄-NaCl-H₂O system. In addition, the VMS metallogenic environment is generally favorable for microbial communities. It is considered that the graphite at Luojiahe may have been derived from sedimentary organic matter formed in seafloor hydrothermal vent systems, as also supported by carbon isotopic data.We propose that at Stage I, the main mineralization may have been resulted from 1) fluid mixing of hot evolved seawater and cold seawater in the near-surface environment; and 2) fluid unmixing caused by the percolation of magmatic fluids into syn-volcanic faults, forming the stockwork ores. At Stage II, the interaction between H₂O and graphite may have resulted in the reduction of ore-forming fluids and Cu precipitation, and fluid unmixing in the CH₄-NaCl-H₂O system may have further promoted the Cu mineralization.     

Speciation of reduced C-O-H volatiles in coexisting fluids and silicate melts determined in-situ to ∼1.4 GPa and 800 °C

The structure of silicate melts in the system Na₂O·4SiO₂ saturated with reduced C-O-H volatile components and of coexisting silicate-saturated C-O-H solutions has been determined in a hydrothermal diamond anvil cell (HDAC) by using confocal microRaman and FTIR spectroscopy as structural probes. The experiments were conducted in-situ with the melt and fluid at high temperature (up to 800 °C) and pressure (up to 1435 MPa). Redox conditions in the HDAC were controlled with the reaction, Mo + H₂O = MoO₂ + H₂, which is slightly more reducing than the Fe + H₂O = FeO + H₂ buffer at 800 °C and less.The dominant species in the fluid are CH₄ + H₂O together with minor amounts of molecular H₂ and an undersaturated hydrocarbon species. In coexisting melt, CH₃ - groups linked to the silicate melt structure via Si-O-CH₃ bonding may dominate and possibly coexists with molecular CH₄. The abundance ratio of CH₃ - groups in melts relative to CH₄ in fluids increases from 0.01 to 0.07 between 500 and 800 °C. Carbon-bearing species in melts were not detected at temperatures and pressures below 400 °C and 730 MPa, respectively. A schematic solution mechanism is, Si-O-Si + CH₄?Si-O-CH₃+H-O-Si. This mechanism causes depolymerization of silicate melts. Solution of reduced (C-O-H) components will, therefore, affect melt properties in a manner resembling dissolved H₂O.     

Metamorphic fluid flow in the northeastern part of the 3.8-3.7 Ga Isua Greenstone Belt (SW Greenland): A re-evalution of fluid inclusion evidence for early Archean seafloor-hydrothermal systems

Fluid inclusions in quartz globules and quartz veins of a 3.8-3.7 Ga old, well-preserved pillow lava breccia in the northeastern Isua Greenstone Belt (IGB) were studied using microthermometry, Raman spectrometry and SEM Cathodoluminescence Imaging. Petrographic study of the different quartz segregations showed that they were affected by variable recrystallization which controlled their fluid inclusion content. The oldest unaltered fluid inclusions found are present in vein crystals that survived dynamic and static recrystallization. These crystals contain a cogenetic, immiscible assemblage of CO₂-rich (+H₂O, +graphite) and brine-rich (+CO₂, +halite, +carbonate) inclusions. The gas-rich inclusions have molar volumes between 44.8 and 47.5 cm³/mol, while the brine inclusions have a salinity of ∼33 eq. wt% NaCl. Modeling equilibrium immiscibility using volumetric and compositional properties of the endmember fluids indicates that fluid unmixing occurred at or near peak-metamorphic conditions of ∼460 °C and ∼4 kbar. Carbonate and graphite were precipitated cogenetically from the physically separated endmember fluids and were trapped in fluid inclusions.In most quartz crystals, however, recrystallization obliterated such early fluid inclusion assemblages and left graphite and carbonate as solid inclusions in recrystallized grains. Intragranular fluid inclusion trails in the recrystallized grains of breccia cementing and crosscutting quartz veins have CO₂-rich assemblages, with distinctly different molar volumes (either between 43.7 and 47.5 cm³/mol or between 53.5 and 74.1 cm³/mol), and immiscible, halite-saturated H₂O-CO₂-NaCl(-other salt) inclusions. Later intergranular trails have CH₄-H₂ (X_H2 up to ∼0.3) inclusions of variable density (ranging from 48.0 to >105.3 cm³/mol) and metastable H₂O-NaCl(-other salt?) brines (∼28 eq. wt% NaCl). Finally, the youngest fluid inclusion assemblages are found in non-luminescent secondary quartz and contain low-density CH₄ (molar volume > 105.33 cm³/mol) and low-salinity H₂O-NaCl (0.2-3.7 eq. wt% NaCl). These successive fluid inclusion assemblages record a retrograde P-T evolution close to a geothermal gradient of ∼30 °C/km, but also indicate fluid pressure variations and the introduction of highly reducing fluids at ∼200-300 °C and 0.5-2 kbar. The quartz globules in the pillow fragments only contain sporadic CH₄(+H₂) and brine inclusions, corresponding with the late generations present in the cementing and crosscutting veins. We argue that due to the large extent of static recrystallization in quartz globules in the pillow breccia fragments, only these relatively late fluid inclusions have been preserved, and that they do not represent remnants of an early, seafloor-hydrothermal system as was previously proposed.Modeling the oxidation state of the fluids indicates a rock buffered system at peak-metamorphic conditions, but suggests a change towards fluid-graphite disequilibrium and a logf_H2/f_H2O above the Quartz-Fayalite-Magnetite buffer during retrograde evolution. Most likely, this indicates a control on redox conditions and on fluid speciation by ultramafic rocks in the IGB.Finally, this study shows that microscopic solid graphite in recrystallized metamorphic rocks from Isua can be deposited inorganically from a fluid phase, adding to the complexity of processes that formed reduced carbon in the oldest, well-preserved supracrustal rocks on Earth.     

Molecular dynamics simulation of the CH4 and CH4-H2O systems up to 10 GPa and 2573 K

Based on our previous study of the intermolecular potential for pure H₂O and the strict evaluation of the competitive potential models for pure CH₄ and the ab initio fitting potential surface across CH₄-H₂O molecules in this study, we carried out more than two thousand molecular dynamics simulations for the PVTx properties of pure CH₄ and the CH₄-H₂O mixtures up to 2573 K and 10 GPa. Comparison of 1941 simulations with experimental PVT data for pure CH₄ shows an average deviation of 0.96% and a maximum deviation of 2.82%. The comparison of the results of 519 simulations of the mixtures with the experimental measurements reveals that the PVTx properties of the CH₄-H₂O mixtures generally agree with the extensive experimental data with an average deviation of 0.83% and 4% in maximum, which is equivalent to the experimental uncertainty. Moreover, the maximum deviation between the experimental data and the simulation results decreases to about 2% as temperature and pressure increase, indicating that the high accuracy of the simulation is well retained in the high temperature and pressure region.After the validation of the simulation method and the intermolecular potential models, we systematically simulated the PVTx properties of this binary system from 673 K and 0.05 GPa to 2573 K and 10 GPa. In order to integrate all the simulation results and the experimental data for the calculation of thermodynamic properties, an equation of state (EOS) is developed for the CH₄-H₂O system covering 673-2573 K and 0.01-10 GPa. Isochores for compositions <4 mol% CH₄ up to 773 K and 600 MPa are also determined in this paper. The program for the EOS can be downloaded from www.geochem-model.org/programs.htm.     

Thermodynamic modeling of binary CH4-H2O fluid inclusions

This work reports the application of thermodynamic models, including equations of state, to binary (salt-free) CH₄-H₂O fluid inclusions. A general method is presented to calculate the compositions of CH₄-H₂O inclusions using the phase volume fractions and dissolution temperatures of CH₄ hydrate. To calculate the homogenization pressures and isolines of the CH₄-H₂O inclusions, an improved activity-fugacity model is developed to predict the vapor-liquid phase equilibrium. The phase equilibrium model can predict methane solubility in the liquid phase and water content in the vapor phase from 273 to 623 K and from 1 to 1000 bar (up to 2000 bar for the liquid phase), within or close to experimental uncertainties. Compared to reliable experimental phase equilibrium data, the average deviation of the water content in the vapor phase and methane solubility in the liquid phase is 4.29% and 3.63%, respectively. In the near-critical region, the predicted composition deviations increase to over 10%. The vapor-liquid phase equilibrium model together with the updated volumetric model of homogenous (single-phase) CH₄-H₂O fluid mixtures (Mao S., Duan Z., Hu J. and Zhang D. (2010) A model for single-phase PVTx properties of CO₂-CH₄-C₂H₆-N₂-H₂O-NaCl fluid mixtures from 273 to 1273 K and from 1 to 5000 bar. Chem. Geol.275, 148-160), is applied to calculate the isolines, homogenization pressures, homogenization volumes, and isochores at specified homogenization temperatures and compositions. Online calculation is on the website: http://www.geochem-model.org/.     

Experimental investigation of single carbon compounds under hydrothermal conditions

The speciation of carbon in subseafloor hydrothermal systems has direct implications for the maintenance of life in present-day vent ecosystems and possibly the origin of life on early Earth. Carbon monoxide is of particular interest because it represents a key reactant during the abiotic synthesis of reduced carbon compounds via Fischer-Tropsch-type processes. Laboratory experiments were conducted to constrain reactions that regulate the speciation of aqueous single carbon species under hydrothermal conditions and determine kinetic parameters for the oxidation of CO according to the water water-gas shift reaction (CO₂ + H₂ = CO + H₂O). Aqueous fluids containing added CO₂, CO, HCOOH, NaHCO₃, NaHCOO, and H₂ were heated at 150, 200, and 300 °C and 350 bar in flexible-cell hydrothermal apparatus, and the abundances of carbon compounds was monitored as a function of time. Variations in fluid chemistry suggest that the reduction of CO₂ to CH₃OH under aqueous conditions occurs via a stepwise process that involves the formation of HCOOH, CO, and possibly CH₂O, as reaction intermediaries. Kinetic barriers that inhibit the reduction of CH₃OH to CH₄ allow the accumulation of reaction intermediaries in solution at high concentrations regulated by metastable thermodynamic equilibrium. Reaction of CO₂ to CO involves a two-step process in which CO₂ initially undergoes a reduction step to HCOOH which subsequently dehydrates to form CO. Both reactions proceed readily in either direction. A preexponential factor of 1.35 × 10⁶ s⁻¹ and an activation energy of 102 kJ/mol were retrieved from the experimental results for the oxidation of CO to CO₂. Reaction rates amongst single carbon compounds during the experiments suggest that ΣCO₂ (CO₂ + HCO₃⁻ + CO₃²⁻), CO, ΣHCOOH (HCOOH + HCOO⁻), and CH₃OH may reach states of redox-dependent metastable thermodynamic equilibrium in subseafloor and other hydrothermal systems. The abundance of CO under equilibrium conditions is strongly dependent on temperature, the total carbon content of the fluid, and host-rock lithology. If crustal residence times following the mixing of high-temperature hydrothermal fluids with cool seawater are sufficiently long, reequilibration of aqueous carbon can result in the generation of additional reduced carbon species such as HCOOH and CH₃OH, and the consumption of H₂. The present study suggests that abiotic reactions involving aqueous carbon compounds in hydrothermal systems are sufficiently rapid to influence metabolic pathways utilized by organisms that inhabit vent environments.     

江西大吉山钨多金属矿床流体包裹体研究

大吉山钨矿床是赣南地区的一个大型钨多金属矿床,由石英脉型钨矿体和花岗岩浸染型钨、钽、铌、铍矿体构成.在详细的岩相学观察的基础上,文章采用“流体包裹体组合”法,对石英脉型矿体和花岗岩浸染型矿体石英中的流体包裹体进行了显微测温和拉曼探针分析.研究表明,与石英脉型矿体成矿相关的流体为中-高温、中-低盐度的NaCl-H2O-CO2-CH4±N2体系,与花岗岩浸染型矿体成矿相关的流体为高温、中-低盐度的NaCl-H2O±CO2±CH4体系,两者流体的性质不同.笔者认为,在流体体系冷却过程中,所发生的以CO2逸失为特征的流体不混溶作用是石英脉型矿体的主要形成机制,而花岗岩浸染型矿体中金属元素的沉淀则主要由流体体系的冷却作用所致,这两类矿体的成矿流体的来源可能不同.     

Ancient graphite in the Eoarchean quartz-pyroxene rocks from Akilia in southern West Greenland II: Isotopic and chemical compositions and comparison with Paleoproterozoic banded iron formations

We present detailed petrographic surveys of apatite grains in association with carbonaceous material (CM) in two banded iron formations (BIFs) from the Paleoproterozoic of Uruguay and Michigan for comparison with similar mineral associations in the highly debated Akilia Quartz-pyroxene (Qp) rock. Petrographic and Raman spectroscopic surveys of these Paleoproterozoic BIFs show that apatite grains typically occur in bands parallel to bedding and are more often associated with CM when concentrations of organic matter are high. Carbonaceous material in the Vichadero BIF from Uruguay is generally well-crystallized graphite and occurs in concentrations around 0.01 wt% with an average δ¹³C_gra value of −28.6 ± 4.4‰ (1σ). In this BIF, only about 5% of apatite grains are associated with graphite. In comparison, CM in the Bijiki BIF from Michigan is also graphitic, but occurs in concentrations around 2.4 wt% with δ¹³C_gra values around −24.0 ± 0.3‰ (1σ). In the Bijiki BIF, more than 78% of apatite grains are associated with CM. Given the geologic context and high levels of CM in the Bijiki BIF, the significantly higher proportion of apatite grains associated with CM in this rock is interpreted to represent diagenetically altered biomass and shows that such diagenetic mineral associations can survive metamorphism up to the amphibolite facies.Isotope compositions of CM in muffled acidified whole-rock powders from the Akilia Qp rock have average δ¹³C_gra values of −17.5 ± 2.5‰ (1σ), while δ¹³C_carb values in whole-rock powders average −4.0 ± 1.0‰ (1σ). Carbon isotope compositions of graphite associated with apatite and other minerals in the Akilia Qp rock were also measured with the NanoSIMS to have similar ranges of δ¹³C_gra values averaging −13.8 ± 5.6‰ (1σ). The NanoSIMS was also used to semi-quantitatively map the distributions of H, N, O, P, and S in graphite from the Akilia Qp rock, and relative abundances were found to be similar for graphite associated with apatite or with hornblende, calcite, and sulfides. These analyses revealed generally lower abundances of trace elements in the Akilia graphite compared to graphite associated with apatite from Paleoproterozoic BIFs.Graphite associated with hornblende, calcite, and sulfides in the Akilia Qp rock was fluid-deposited at high-temperature from carbon-bearing fluids, and since this graphite has similar ranges of δ¹³C_gra values and of trace elements compared to graphite associated with apatite, we conclude that the Akilia graphite in different mineral associations formed from the same source(s) of CM. Collectively our results do not exclude a biogenic origin of the carbon in the Akilia graphite, but because some observations can not exclude graphitization of abiogenic carbon from CO₂- and CH₄-bearing mantle fluids, there remain ambiguities with respect to the exact origin of carbon in this ancient metasedimentary rock. Accordingly, there may have been several generations of graphite formation along with possibly varying mixtures of CO₂- and CH₄-bearing fluids that may have resulted in large ranges of δ¹³C_gra values. The possibility of fluid-deposited graphite associated with apatite should be a focus of future investigations as this may prove to be an alternative pathway of graphitization from phosphate-bearing fluids. Correlated micro-analytical approaches tested on terrestrial rocks in this work provide insights into the origin of carbon in ancient graphite and will pave the way for the search for life on other ancient planetary surfaces.     

The use of vein fluorite as probe for paleofluid REE and Sr-Nd isotope geochemistry: The Santa Catarina Fluorite District, Southern Brazil

Fluorite can be used as a probe for the source of Sr and REE, as well as for the Sr and Nd isotope systematics of mineralizing solutions, allowing characterization of the composition, oxidation state and sources of the fluids. The ⁸⁷Sr / ⁸⁶Sr ratios in vein fluorite from the Santa Catarina Fluorite District, southern Brazil, are low (0.720 to 0.745) relative to those of the majority of host granites at the time of mineralization (90 Ma), but are similar to those of less abundant and less evolved Sr- and Ca-rich granites and plagioclases of the heterogeneous Pedras Grandes granite association. Major contributions of Sr from the unradiogenic Parana Basin rocks (⁸⁷Sr / ⁸⁶Sr_{90 Ma} = 0.705 to 0.718) are unlikely, considering the radiogenic character of the lower ⁸⁷Sr / ⁸⁶Sr end-member in fluorite mixing lines. Estimated fluorite fluid partition coefficients (K_d^Sr-Ca = 0.019 and D^Sr ≈ 600) indicate a Sr / Ca ratio in the fluorite-forming solution of 0.012, and Sr contents of 0.05 to 0.25 ppm, which are similar to those of present-day granitic geothermal waters. Initial Nd isotopic compositions of the vein fluorites (0.5120 to 0.512) are similar to those of the Pedras Grandes granites. The ¹⁴³Nd / ¹⁴⁴Nd_{90 Ma} of the evolved granites of the Tabuleiro granite association, their accessory fluorites and the Parana Basin rocks are considerably more radiogenic (0.5120 to 0.5127) and these are thus considered to be unlikely sources of the fluids. The REE patterns of vein fluorites, normalized to upper continental crust, show a range of LREE-depleted patterns, with highly variable positive and negative Eu anomalies. The host Pedras Grandes granites show flat to slightly depleted UCC normalized LREE patterns with strong negative Eu anomalies. Depletion of the LREE in fluorites resulted from the mobility of HREE fluoride complexes during fluid migration. A REE fractionation model based on ionic potential ratios indicates that Eu³⁺ was stable during fluid migration and fluorite precipitation. The coexistence of pyrite and Eu³⁺ in the mineralizing fluids is consistent with low pH and oxygen fugacities near the hematite-magnetite buffer.     

A unified equation for calculating methane vapor pressures in the CH4-H2O system with measured Raman shifts

A unified equation has been derived by using all available data for calculating methane vapor pressures with measured Raman shifts of C-H symmetric stretching band (υ₁) in the vapor phase of sample fluids near room temperature. This equation eliminates discrepancies among the existing data sets and can be applied at any Raman laboratory. Raman shifts of C-H symmetric stretching band of methane in the vapor phase of CH₄-H₂O mixtures prepared in a high-pressure optical cell were also measured at temperatures between room temperature and 200 °C, and pressures up to 37 MPa. The results show that the CH₄υ₁ band position shifts to higher wavenumber as temperature increases. We also demonstrated that this Raman band shift is a simple function of methane vapor density, and, therefore, when combined with equation of state of methane, methane vapor pressures in the sample fluids at elevated temperatures can be calculated from measured Raman peak positions. This method can be applied to determine the pressure of CH₄-bearing systems, such as methane-rich fluid inclusions from sedimentary basins or experimental fluids in hydrothermal diamond-anvil cell or other types of optical cell.     

Fluid sources for the La Guitarra epithermal deposit (Temascaltepec district, Mexico): Volatile and helium isotope analyses in fluid inclusions

The La Guitarra deposit (Temascaltepec district, South-Central Mexico), belongs to the low/intermediate sulfidation epithermal type, has a polymetallic character although it is currently being mined for Ag and Au. The mineralization shows a polyphasic character and formed through several stages and sub-stages (named I, IIA, IIB, IIC, IID, and III). The previous structural, mineralogical, fluid inclusion and stable isotope studies were used to constrain the selection of samples for volatile and helium isotope analyses portrayed in this study. The N₂/Ar overall range obtained from analytical runs on fluid inclusion volatiles, by means of Quadrupole Mass Spectrometry (QMS), is 0 to 2526, and it ranges 0 to 2526 for stage I, 0 to 1264 for stage IIA, 0 to 1369 for stage IIB, 11 to 2401 for stage IIC, 19 to 324 for stage IID, and 0 to 2526 for stage III. These values, combined with the CO₂/CH₄ ratios, and N₂-He-Ar and N₂-CH₄-Ar relationships, suggest the occurrence of fluids from magmatic, crustal, and shallow meteoric sources in the forming epithermal vein deposit. The helium isotope analyses, obtained by means of Noble Gas Mass Spectrometry, display R/Ra average values between 0.5 and 2, pointing to the occurrence of mantle-derived helium that was relatively diluted or “contaminated” by crustal helium. These volatile analyses, when correlated with the stable isotope data from previous works and He isotope data, show the same distribution of data concerning sources for mineralizing fluids, especially those corresponding to magmatic and crustal sources. Thus, the overall geochemical data from mineralizing fluids are revealed as intrinsically consistent when compared to each other.The three main sources for mineralizing fluids (magmatic, and both deep and shallow meteoric fluids) are accountable at any scale, from stages of mineralization down to specific mineral associations. The volatile and helium isotope data obtained in this paper suggest that the precious metal-bearing mineral associations formed after hydrothermal pulses of predominantly oxidized magmatic fluids, and thus it is likely that precious metals were carried by fluids with such origin. Minerals from base-metal sulfide associations record both crustal and magmatic sources for mineralizing fluids, thus suggesting that base metals could be derived from deep leaching of crustal rocks. At the La Guitarra epithermal deposit there is no evidence for an evolution of mineralizing fluids towards any dominant source. Rather than that, volatile analyses in fluid inclusions suggest that this deposit formed as a pulsing hydrothermal system where each pulse or set of pulses accounts for different compositions of mineralizing fluids.The positive correlation between the relative content of magmatic fluids (high N₂/Ar ratios) and H₂S suggests that the necessary sulfur to carry mostly gold as bisulfide complexes came essentially from magmatic sources. Chlorine necessary to carry silver and base metals was found to be abundant in inclusion fluids and although there is no evidence about its source, it is plausible that it may come from magmatic sources as well.     

The genesis of the west shropshire orefield: Evidence from fluid inclusions,sphalerite chemistry,and sulphur isotopic ratios

The Pb + Zn + Ba veins of West Shropshire, England, occupy fractures in Ordovician and Precambrian rocks of the Shelve Inlier. Precipitation of sphaleritic ores was succeeded by galena + baryte mineralization, with chalcopyrite also occurring late in the mineralizing episode. Three generations of sphalerite are recognized, and second being chemically zoned with distinct Fe + Cd-rich growth zones. Associated with these iron-rich bands are smaller (∼ 10 μm) zones rich in indium (>1.0 wt%) and copper, electron electron probe microanalyses suggesting coupled substitution of Cu⁺ + In⁺³ in the ZnS. Based on the sequence of growth zones and their chemistry a sphalerite stratigraphy can be recognized within the orefield. Fluid inclusions studies reveal the mineralizing fluids to be highly saline (18–30 wt% CaCl₂ equivalent) Na + Ca-richbrines, with mineralizing temperatures in the range 200–120°C. A trend from higher temperature-low salinity to low temperature-high salinity fluids with time is recognized. Sulphide sulphur isotopic ratios are consistent and suggest a ΔS³⁴S_H2S of the mineralizing fluid of 10%, while ³⁴S_baryte values are in the range + 14 to + 19%, indicating separate sulphate and sulphide sulphur sources. The mineralogical, fluid inclusion, and isotopic data suggest the saline fluids rose into an open plumbing system where mineral precipitation was mainly controlled by fluid cooling. The baryte however, formed due to mixing with oan overlying sulphate-bearing reservioir. Theree possible fluid sources are considered, namely: Lower Carboniferous seawater, basinal brines, and metamorphic fluids. However, the information available does not allow the source to be positively identified.     

Decrepitation Thermometry and Compositions of Fluid Inclusions of the Damoqujia Gold Deposit,Jiaodong Gold Province,China:Implications for Metallogeny and Exploration

The recently discovered Damoqujia (大磨曲家) gold deposit is a large shear zone-hosted gold deposit of disseminated sulphides located in the north of the Zhaoping (招平) fault zone, Jiaodong (胶东) gold province, China. In order to distinguish the temperature range of cluster inclusions from different mineralization stages and measure their compositions, 16 fluid inclusions and 5 isotopic geochemistry samples were collected for this study. Corresponding to different mineralization stages, the multirange peaks of quartz decrepitation temperature (250-270, 310-360 and 380-430℃(2) indicate that the activity of ore-forming fluids is characterized by multistage. The ore-forming fluids were predominantly of high-temperature fluid system (HTFS) by CO2-rich, and SO2-4-K type magmatic fluid during the early stage of mineralization and were subsequently affected by low-temperature fluid system (LTFS) of CH4-rich, and Cl--Na /Ca2 type meteoric fluid during the late stage of mineralization. Gold is transferred by Au-HS- complex in the HTFS, and Au-Cl- complex can be more important in the LTFS. The transition of fluids from deeper to shallow environments results in mixing between the HTFS and LTFS, which might be one of the most key reasons for gold precipitation and large-scale mineralization. The ore-forming fluids are characterized by high-temperature, strong-activity, and superimposed mineralization, so that there is a great probability of forming large and rich ore deposit in the Damoqujia gold deposit. The main bodies are preserved and extend toward deeper parts, thereby suggesting a great potential in future.     

Potential of microbial methane formation in a high-temperature hydrocarbon seep

Hydrocarbon seepage is a surface expression where fluids mixed with sediments and hydrocarbons are expelled through fracture systems that potentially tap into gas–petroleum reservoirs. Hydrocarbons released from most seeps appear to be thermogenic on the basis of their relative abundance and isotopic composition. The potential for subsurface microbial processes modifying these geochemical fingerprints remains poorly constrained. In this study, microcosm incubations were conducted on mud slurries supplied with/without various methanogenic precursors at temperatures ranging from ambient conditions to 90 °C, in order to assess microbial CH₄ formation in the subsurface beneath hydrocarbon seeps. The analyses indicated that CH₄ production was positive at ?80 °C, regardless of whether or not or which precursors were added. However, the pattern of CH₄ production rates varied with the precursor and temperature. In general, the optimum CH₄ production from H₂/CO₂ and formate occurred over a wide range of temperatures (?40 °C), whereas that from acetate, methanol and methylamine was restricted to relatively lower temperatures (40–50 °C). The CH₄ recoveries, together with the C isotopic compositions of CH₄, further indicated that the quantities of CH₄ produced could not completely account for the quantities of precursor consumed, suggesting that a complex metabolic network was involved in the transformation of the added precursor and organic C inherited from inoculated sediments. Microbial CH₄ was estimated to constitute 7–61% of the CH₄ observed using experimentally-derived apparent isotope fractionations as the end member compositions. This illustrates the possibility that microbial CH₄ produced at shallower depths could quantitatively and isotopically alter deeply-sourced thermogenic CH₄ in hydrocarbon seep environments.     

The solubility of FeS

The solubility of FeS_m, synthetic nanoparticulate mackinawite, in aqueous solution was measured at 23 °C from pH 3-10 using an in situ precipitation and dissolution procedure and the solution species was investigated voltammetrically. The solubility is described by a pH-dependent reaction and a pH-independent reaction. The pH-dependent dissolution reaction can be described by

FeS_m+2H⁺→Fe²⁺+H₂S     

The Mari Rosa late Hercynian Sb-Au deposit, western Spain

The central Iberian zone of the Hesperian Massif hosts a series of late Hercynian vein-type Sb deposits. One of them is the Mari Rosa mineralization, hosted by metagreywackes and slates of the Schist-Greywacke Complex (Upper Precambrian). The mineralization is characterized by a complex paragenesis comprising three hydrothermal stages: stage H1 arsenopyrite-(pyrite); stage H2 stibnite-gold; and stage H3 pyrite-pyrrhotite-galena-sphalerite-chalcopyrite-tetrahedrite-boul-angerite-stibnite. Of these only the second episode was of importance and gave rise to the main mineralized bodies of the deposit. Hydrothermal alteration consists of a mild sericitization, chloritization and carbonatization of the metasedimentary rocks around the veins. Chemical changes in the hydrothermal halos include a remarkable increase in the ratio K₂O/Na₂O, and a decrease in the ratio SiO₂/volatiles, together with a sharp increase in Sb, Mo, Au and N. Fluids associated with ore deposition lie in the H₂O-NaCl-CO₂-CH₄-N₂ compositional system. These fluids evolved, progressively cooling, from initial circulaion temperatures close to 400 °C in the early stage (H1) to temperatures of approximately 150 °C in the late one (H3). Fluid composition evolution was characterized by a progressive increase in the bulk water content of the fluids and with an increase in the relative proportion of N₂ with respect to CH₄ and CO₂ in the volatile fraction. Massive stibnite deposition resulted from a boiling process developed at 300 °C and 0.9–1 Kb at a depth of 4–5 km. Geological, geochemical and fluid inclusion evidence suggest that the intrusion of the Alburquerque batholith (late Hercynian S-type granitoids) triggered hydrothermal activity leading to the transport and deposition of Sb and Au in Mari Rosa.     

Evidence of magmatic CO2-rich fluids in peraluminous graphite-bearing leucogranites from Deep Freeze Range (northern Victoria Land,Antarctica)

Fine-grained peraluminous synkinematic leuco-monzogranites (SKG), of Cambro-Ordovician age, occur as veins and sills (up to 20–30 m thick) in the Deep Freeze Range, within the medium to high-grade metamorphics of the Wilson Terrane. Secondary fibrolite + graphite intergrowths occur in feldspars and subordinately in quartz. Four main solid and fluid inclusion populations are observed: primary mixed CO₂+H₂O inclusions + Al₂SiO₅ ± brines in garnet (type 1); early CO₂-rich inclusions (± brines) in quartz (type 2); early CO₂+CH₄ (up to 4 mol%)±H₂O inclusions + graphite + fibrolite in quartz (type 3); late CH₄+CO₂+N₂ inclusions and H₂O inclusions in quartz (type 4). Densities of type 1 inclusions are consistent with the crystallization conditions of SKG (750°C and 3 kbar). The other types are post-magmatic: densities of type 2 and 3 inclusions suggest isobaric cooling at high temperature (700–550°C). Type 4 inclusions were trapped below 500°C. The SKG crystallized from a magma that was at some stage vapour-saturated; fluids were CO₂-rich, possibly with immiscible brines. CO₂-rich fluids (±brines) characterize the transition from magmatic to post-magmatic stages; progressive isobaric cooling (T<670°C) led to a continuous decrease off _{O 2} can entering in the graphite stability field; at the same time, the feldspars reacted with CO₂-rich fluids to give secondary fibrolite + graphite. Decrease ofT andf _{O 2} can explain the progressive variation in the fluid composition from CO₂-rich to CH₄ and water dominated in a closed system (in situ evolution). The presence of N₂ the late stages indicates interaction with external metamorphic fluids.Contribution within the network Hydrothermal/metamorphic water-rock interactions in crystalline rocks: a multidisciplinary approach on paleofluid analysis. CEC program: Human Capital and Mobility     

The La Unión Au ± Cu prospect,Camagüey District,Cuba: fluid inclusion and stable isotope evidence for ore-forming processes

The Camagüey district, Cuba, is known for its epithermal precious metal deposits in a Cretaceous volcanic arc setting. Recently, the La Unión prospect was discovered in the southern part of the district, containing gold and minor copper mineralization interpreted as porphyry type. Mineralization is hosted in a 73.0 ± 1.5 Ma calc–alkaline I-type oxidized porphyry quartz diorite intrusive within volcanic and volcaniclastic rocks of the early Cretaceous Guáimaro Formation. The porphyry is affected by propylitic alteration and crosscut by a network of quartz and carbonate veinlets and veins. Chlorite, epidote, sericite, quartz, and pyrite are the main minerals in the early veins which are cut by late carbonate and zeolite veins. Late barite pseudomorphously replaces pyrite. Gold is associated with pyrite as disseminations in the altered quartz diorite and in the veins, occurring as inclusions or filling fractures in pyrite with 4 g/t Au in bulk samples, and up to 900 ppm Au in in pyrite. Fluid inclusion and oxygen isotope data are consistent with a H₂O–NaCl–(KCl) mineralizing fluid, derived from the quartz diorite magma, and trapped at least at 425°C and 1.2 kbar. This primary fluid unmixed into two fluid phases, a hypersaline aqueous fluid and a low-salinity vapor-rich fluid. Boiling during cooling may have played an important role in metal precipitation. Pyrite δ³⁴S values for the La Unión prospect range between 0.71‰ and 1.31‰, consistent with a homogeneous magmatic sulfur source. The fluids in equilibrium with the mineralized rocks have estimated δ¹⁸O values from 8‰ to 11.8‰, calculated for a temperature range of 480–505°C. The tectonic environment of the La Unión prospect, its high gold and low copper contents, the physical–chemical characteristics of the mineralizing fluids and the isotopic signature of the alteration minerals and fluids indicate that the La Unión gold mineralization is similar to the porphyry gold type, even though the ore-related epidote–chlorite alteration can be classified as propylitic and not the classic potassic and/or phyllic alteration. The low copper contents in the prospect could be due to a mineralizing fluid previously saturated in copper, which is indicated by trapped chalcopyrite crystals in high-temperature fluid inclusions. The low-temperature paragenesis, represented by carbonate, zeolite and barite, indicates epithermal overprint. The study shows the potential for other gold porphyry-type deposits in the Cretaceous volcanoplutonic arc of Cuba.     

Fluid evolution,wallrock alteration,and ore mineralization associated with the Rodalquilar epithermal gold-deposit in southeast Spain

At Rodalquilar gold mineralization is found in Late Tertiary volcanic rocks of the Sierra del Cabo de Gata and is related to a caldera collapse. Radial and concentric faults were preferred sites for gold deposition. Hydrothermal activity produced a specific alteration zoning around gold-bearing vein structures, grading from an innermost advanced argillic via an argillic into a more regionally developed propylitic zone. Advanced argillic alteration with silica, pyrophyllite, alunite, and kaolinite extends down to several hundred m indicating a hypogene origin. High-grade gold mineralization in vein structures is confined to the near-surface part of the advanced argillic alteration. Fine-grained gold is associated with hematite, jarosite, limonite, or silica. At a depth of about 120 m, the oxidic ore assemblage grades into sulfide mineralization with pyrite and minor chalcopyrite, covellite, bornite, enargite, and tennantite. Two types of fluids from different sources were involved in the hydrothermal system. Overpressured and hypersaline fluids of presumably magmatic origin initiated the hydrothermal system. Subsequent hydrothermal processes were characterized by the influx of low-salinity solutions of probable marine origin and by interactions between both fluids. Deep-reaching, advanced argillic alteration formed from high-salinity fluids with 20–30 equiv. wt% NaCl at about 225°C. Near-surface gold precipitation and silification are related to fluids with temperatures of about 175°C and 3–4 equiv. wt% NaCl. Gold was transported as Au(HS) ₂ ^– , and precipitation resulted from boiling with a concomitant decrease in temperature, pressure, and pH and an increase in fO₂. All features of the Rodalquilar gold deposit reveal a close relationship to acid-sulfate-type epithermal gold mineralization.