A fluid inclusion and stable isotope study of 200 Ma of fluid evolution in the Galway Granite, Connemara, Ireland

Fluid inclusions in granite quartz and three generations of veins indicate that three fluids have affected the Caledonian Galway Granite. These fluids were examined by petrography, microthermometry, chlorite thermometry, fluid chemistry and stable isotope studies. The earliest fluid was a H₂O-CO₂-NaCl fluid of moderate salinity (4–10 wt% NaCl eq.) that deposited late-magmatic molybdenite mineralised quartz veins (V₁) and formed the earliest secondary inclusions in granite quartz. This fluid is more abundant in the west of the batholith, corresponding to a decrease in emplacement depth. Within veins, and to the east, this fluid was trapped homogeneously, but in granite quartz in the west it unmixed at 305–390 °C and 0.7–1.8 kbar. Homogeneous quartz δ¹⁸O across the batholith (9.5 ± 0.4‰n = 12) suggests V₁ precipitation at high temperatures (perhaps 600 °C) and pressures (1–3 kbar) from magmatic fluids. Microthermometric data for V₁ indicate lower temperatures, suggesting inclusion volumes re-equilibrated during cooling. The second fluid was a H₂O-NaCl-KCl, low-moderate salinity (0–10 wt% NaCl eq.), moderate temperature (270–340 °C), high δD (−18 ± 2‰), low δ¹⁸O (0.5–2.0‰) fluid of meteoric origin. This fluid penetrated the batholith via quartz veins (V₂) which infill faults active during post-consolidation uplift of the batholith. It forms the most common inclusion type in granite quartz throughout the batholith and is responsible for widespread retrograde alteration involving chloritization of biotite and hornblende, sericitization and saussuritization of plagioclase, and reddening of K-feldspar. The salinity was generated by fluid-rock interactions within the granite. Within granite quartz this fluid was trapped at 0.5–2.3 kbar, having become overpressured. This fluid probably infiltrated the Granite in a meteoric-convection system during cooling after intrusion, but a later age cannot be ruled out. The final fluid to enter the Granite and its host rocks was a H₂O-NaCl-CaCl₂-KCl fluid with variable salinity (8–28 wt% NaCl eq.), temperature (125–205 °C), δD (−17 to −45‰), δ¹⁸O (−3 to + 1.2‰), δ¹³C_CO2 (−19 to 0‰) and δ³⁴S_sulphate (13–23‰) that deposited veins containing quartz, fluorite, calcite, barite, galena, chalcopyrite sphalerite and pyrite (V₃). Correlations of salinity, temperature, δD and δ¹⁸O are interpreted as the result of mixing of two fluid end-members, one a high-δD (−17 to −8‰), moderate-δ¹⁸O (1.2–2.5‰), high-δ¹³C_CO2 (> −4‰), low-δ³⁴S_sulphate (13‰), high-temperature (205–230 °C), moderate-salinity (8–12 wt% NaCl eq.) fluid, the other a low-δD (−61 to −45‰), low-δ¹⁸O (−5.4 to −3‰), low-δ¹³C (<−10‰), high-δ³⁴S_sulphate (20–23‰) low-temperature (80–125 °C), high-salinity (21–28 wt% NaCl eq.) fluid. Geochronological evidence suggests V₃ veins are late Triassic; the high-δD end-member is interpreted as a contemporaneous surface fluid, probably mixed meteoric water and evaporated seawater and/or dissolved evaporites, whereas the low-δD end-member is interpreted as a basinal brine derived from the adjacent Carboniferous sequence. This study demonstrates that the Galway Granite was a locus for repeated fluid events for a variety of reasons; from expulsion of magmatic fluids during the final stages of crystallisation, through a meteoric convection system, probably driven by waning magmatic heat, to much later mineralisation, concentrated in its vicinity due to thermal, tectonic and compositional properties of granite batholiths which encourage mineralisation long after magmatic heat has abated. Received: 3 April 1996 / Accepted: 5 May 1997     

Fluid evolution at the Variscan front in the vicinity of the Aachen thrust

Quartz–carbonate–chlorite veins were studied in borehole samples of the RWTH-1 well in Aachen. Veins formed in Devonian rocks in the footwall of the Aachen thrust during Variscan deformation and associated fluid flow. Primary fluid inclusions indicate subsolvus unmixing of a homogenous H₂O–CO₂–CH₄–(N₂)–Na–(K)–Cl fluid into a H₂O–Na–(K)–Cl solution and a vapour-rich CO₂–(H₂O, CH₄, N₂) fluid. The aqueous end-member composition resembles that of metamorphic fluids of the Variscan front zone with salinities ranging from 4 to 7% NaCl equiv. and maximum homogenisation temperatures of close to 400°C. Pressure estimates indicate a burial depth between 4,500 and 8,000 m at geothermal gradients between 50 and 75°C/26 MPa, but pressure decrease to sublithostatic conditions is also indicated, probably as a consequence of fracture opening during episodic seismic activity. A second fluid system, mainly preserved in pseudo-secondary and secondary fluid inclusions, is characterised by fluid temperatures between 200 and 250°C and salinities of <5% NaCl equiv. Bulk stable isotope analyses of fluids released from vein quartz, calcite, and dolomite by decrepitation yielded δD_H2O values from −89 to −113 ‰, δ¹³C_CH4 from −26.9 to −28.9‰ (VPDB) and δ¹³C_CO2 from −12.8 to −23.3‰ (VPDB). The low δD and δ¹³C range of the fluids is considered to be due to interaction with cracked hydrocarbons. The second fluid influx caused partial isotope exchange and disequilibrium. It is envisaged that an initial short lived flux of hot metamorphic fluids expelled from the epizonal metamorphic domains of the Stavelot–Venn massif. The metamorphic fluid was focused along major thrust faults of the Variscan front zone such as the Aachen thrust. A second fluid influx was introduced from formation waters in the footwall of the Aachen thrust as a consequence of progressive deformation. Mixing of the cooler and lower salinity formation water with the hot metamorphic fluid during episodic fluid trapping resulted in an evolving range of physicochemical fluid inclusion characteristics.     

Directional chemical variations in diamonds showing octahedral following cuboid growth

A progression from cuboid to octahedral growth has been observed in 16 natural diamonds from Yakutian kimberlites. X-ray and cathodoluminescence topography have revealed that the change in morphology of diamonds with cloudy cuboid cores may occur without mixed-habit growth but via generation of numerous octahedral apices on cuboid surfaces and subsequent gradual transformation into regular octahedral morphology. Nitrogen aggregation in both cuboid and octahedral domains of such diamonds suggests that they have had a long residence time under mantle conditions. Micro-inclusions in the cuboid domains of the diamonds testify to the nucleation and growth of cuboid cores from a hydrous-carbonatitic (oxidized) fluid. The transition from cuboid hummocky growth rich in inclusions to octahedral growth without inclusions may be linked to decreasing supersaturation in the parent fluid. Measurements of δ¹³C and N_ppm by ion microprobe show that the chemical variations observed between inner cuboid domains and outer octahedral zones commonly have a systematic character and as such they are probably not due to purely kinetic effects. The peripheral octahedral zones are always enriched in ¹³C in comparison with inner cuboid ones, and the total nitrogen content decreases with the change from cuboid to octahedral growth. The octahedral outer zones show a gradual progressive increase in δ¹³C, with an overall change of up to 5‰ from the cuboid core (δ¹³C usually between −8 and −6‰) to the diamond margin (δ¹³C usually between −4 and −2‰). Decreases in δ¹³C of this magnitude with a gradual increase in ¹³C may be attributed to the Rayleigh fractionation operating on a single parent fluid of close to normal mantle δ¹³C composition with diamond precipitating by the reduction of carbonatitic fluid in a closed system. However, one sample shows a variation of δ¹³C of approximately −17 to −6‰ and therefore suggests a possible change of fluid source composition from one containing subducted crustal organic carbon to one with common mantle carbon. An erratum to this article can be found at     

Ore fluid geochemistry of the Jinlongshan Carlintype gold ore belt in Shaanxi Province, China

THEJINLONGSHANGOLDOREBELTINZHEN’ANCOUN TY,SOUTHERNSHAANXIPROVINCE,ISLOCATEDINTHEWEST ERNQINLINGGOLDPROVINCE(NO.16INFIG.1;CHEN YANJINGETAL.,2004).ITWASDISCOVEREDINTHEDEVO NIANSTRATAINTHELATE1980S).ITSGEOLOGICALSETTING ANDMETALLOGENICEVOLUTIONARESIMILARTOT…     

Genetic identification of natural gases from shallow reservoirs in some oil- and gas-bearing basins of China

Natural gases of shallow reservoirs with the carbon isotopic compositions of methane ranging from -50‰ to -60‰ (PDB) were considered as mixed gases of biogenic and thermogenic origins previously and some of them were considered as low-mature (or low temperature thermogenic) gases lately. In this paper natural gases with the carbon isotopic compositions of methane in the above range were identified using the molecular and stable carbon isotopic compositions of methane, ethane and propane. The mixed gases of biogenic and mature thermogenic origins display the characteristics of δ 13 C1 ranging from -50‰to -60‰,δ13C2 ＞ -35‰,Δvalues (δ13C3 -δ13C2) ＜ 5‰ and C1/∑C2 ratios ＜ 40. Immature to low-mature gases display the characteristics of δ 13 C1 ranging from - 50‰ to - 60‰, δ13 C2 ＜- 40‰,Δ values (δ13C3 -δ13C2) ＞7‰, and C1/∑C 2 ratios ＞60.     

The Paleoproterozoic carbonate-hosted Pering Zn–Pb deposit, South Africa. II: fluid inclusion, fluid chemistry and stable isotope constraints

The Pering deposit is the prime example of Zn–Pb mineralisation hosted by stromatolitic dolostones of the Neoarchean to Paleoproterozoic Transvaal Supergroup. The hydrothermal deposit centers on subvertical breccia pipes that crosscut stromatolitic dolostones of the Reivilo Formation, the lowermost portion of the Campbellrand Subgroup. Four distinct stages of hydrothermal mineralisation are recognised. Early pyritic rock matrix brecciation is followed by collomorphous sphalerite mineralisation with replacive character, which, in turn, is succeeded by coarse grained open-space-infill of sphalerite, galena, sparry dolomite, and quartz. Together, the latter two stages account for ore-grade Zn–Pb mineralisation. The fourth and final paragenetic stage is characterised by open-space-infill by coarse sparry calcite. The present study documents the results of a detailed geochemical study of the Pering deposit, including fluid inclusion microthermometry, fluid chemistry and stable isotope geochemistry of sulphides (δ³⁴S) and carbonate gangue (δ¹³C and δ¹⁸O). Microthermometric fluid inclusion studies carried out on a series of coarsely grained crystalline quartz and sphalerite samples of the latter, open-space-infill stage of the main mineralisation event reveal the presence of three major fluid types: (1) a halite–saturated aqueous fluid H₂O–NaCl–CaCl₂ (>33 wt% NaCl equivalent) brine, (2) low-salinity meteoric fluid (<7 wt% NaCl) and (3) a carbonic CH₄–CO₂–HS⁻ fluid that may be derived from organic material present within the host dolostone. Mixing of these fluids have given rise to variable mixtures (H₂O–CaCl₂–NaCl ±(CH₄–CO₂–HS⁻), 2 to 25 wt% NaCl+CaCl₂). Heterogeneous trapping of the aqueous and carbonic fluids occurred under conditions of immiscibility. Fluid temperature and pressure conditions during mineralisation are determined to be 200–210°C and 1.1–1.4 kbar, corresponding to a depth of mineralisation of 4.1–5.2 km. Chemical analyses of the brine inclusions show them to be dominated by Na and Cl with lesser amounts of Ca, K and SO₄. Fluid ratios of Cl/Br indicate that they originated as halite saturated seawater brines that mixed with lower salinity fluids. Analyses of individual brine inclusions document high concentrations of Zn and Pb (∼1,500 and ∼200 ppm respectively) and identify the brine as responsible for the introduction of base metals. Stable isotope data were acquired for host rock and hydrothermal carbonates (dolomite, calcite) and sulphides (pyrite, sphalerite, galena and chalcopyrite). The ore-forming sulphides show a trend to ³⁴S enrichment from pyrite nodules in the pyritic rock matrix breccia (δ³⁴S = −9.9 to +3.7‰) to paragenetically late chalcopyrite of the main mineralisation event (δ³⁴S = +30.0‰). The observed trend is attributed to Rayleigh fractionation during the complete reduction of sulphate in a restricted reservoir by thermochemical sulphate reduction, and incremental precipitation of the generated sulphide. The initial sulphate reservoir is expected to have had an isotopic signature around 0‰, and may well represent magmatic sulphur, oxidised and leached by the metal-bearing brine. The δ¹⁸O values of successive generations of dolomite, from host dolostone to paragenetically late saddle dolomite follow a consistent trend that yields convincing evidence for extensive water rock interaction at variable fluid–rock ratios. Values of δ¹³C remain virtually unchanged and similar to the host dolostone, thus suggesting insignificant influx of CO₂ during the early and main stages of mineralisation. On the other hand, δ¹³C and δ¹⁸O of post-ore calcite define two distinct clusters that may be attributed to changes in the relative abundance in CH₄ and CO₂ during waning stages of hydrothermal fluid flow.     

Origin of the Rubian carbonate-hosted magnesite deposit, Galicia, NW Spain: mineralogical, REE, fluid inclusion and isotope evidence

The Rubian magnesite deposit (West Asturian—Leonese Zone, Iberian Variscan belt) is hosted by a 100-m-thick folded and metamorphosed Lower Cambrian carbonate/siliciclastic metasedimentary sequence—the Cándana Limestone Formation. It comprises upper (20-m thickness) and lower (17-m thickness) lens-shaped ore bodies separated by 55 m of slates and micaceous schists. The main (lower) magnesite ore body comprises a package of magnesite beds with dolomite-rich intercalations, sandwiched between slates and micaceous schists. In the upper ore body, the magnesite beds are thinner (centimetre scale mainly) and occur between slate beds. Mafic dolerite dykes intrude the mineralisation. The mineralisation passes eastwards into sequence of bedded dolostone (Buxan) and laminated to banded calcitic marble (Mao). These show significant Variscan extensional shearing or fold-related deformation, whereas neither Rubian dolomite nor magnesite show evidence of tectonic disturbance. This suggests that the dolomitisation and magnesite formation postdate the main Variscan deformation. In addition, the morphology of magnesite crystals and primary fluid inclusions indicate that magnesite is a neoformed hydrothermal mineral. Magnesite contains irregularly distributed dolomite inclusions (<50 μm) and these are interpreted as relics of a metasomatically replaced dolostone precursor. The total rare earth element (REE) contents of magnesite are very similar to those of Buxan dolostone but are depleted in light rare earth elements (LREE); heavy rare earth element concentrations are comparable. However, magnesite REE chondrite normalised profiles lack any characteristic anomaly indicative of marine environment. Compared with Mao calcite, magnesite is distinct in terms of both REE concentrations and patterns. Fluid inclusion studies show that the mineralising fluids were MgCl₂–NaCl–CaCl₂–H₂O aqueous brines exhibiting highly variable salinities (3.3 to 29.5 wt.% salts). This may be the result of a combination of fluid mixing, migration of pulses of variable-salinity brines and/or local dissolution and replacement processes of the host dolostone. Fluid inclusion data and comparison with other N Iberian dolostone-hosted metasomatic deposits suggest that Rubian magnesite probably formed at temperatures between 160 and 200°C. This corresponds, at hydrostatic pressure (500 bar), to a depth of formation of ~~5 km. Mineralisation-related Rubian dolomite yields δ ¹⁸O values (δ ¹⁸O: 12.0–15.4‰, mean: 14.4±1.1‰) depleted by around 5‰ compared with barren Buxan dolomite (δ ¹⁸O: 17.1–20.2‰, mean: 19.4±1.0‰). This was interpreted to reflect an influx of ¹⁸O-depleted waters accompanied by a temperature increase in a fluid-dominated system. Overlapping calculated δ ¹⁸O_fluid values (~+5‰ at 200°C) for fluids in equilibrium with Rubian dolomite and magnesite show that they were formed by the same hydrothermal system at different temperatures. In terms of δ ¹³C values, Rubian dolomite (δ ¹³C: −1.4 to 1.9‰, mean: 0.4±1.3‰) and magnesite (δ ¹³C: −2.3 to 2.4‰, mean: 0.60±1.0‰) generally exhibit more negative δ ¹³C values compared with Buxan dolomite (δ ¹³C: −0.2 to 1.9‰, mean: 0.8±0.6‰) and Mao calcite (δ ¹³C: −0.3 to 1.5‰, mean: 0.6±0.6‰), indicating progressive modification to lower δ ¹³C values through interaction with hydrothermal fluids. ⁸⁷Sr/⁸⁶Sr ratios, calculated at 290 Ma, vary from 0.70849 to 0.70976 for the Mao calcite and from 0.70538 to 0.70880 for the Buxan dolostone. The ⁸⁷Sr/⁸⁶Sr ratios in Rubian magnesite are more radiogenic and range from 0.71123 to 0.71494. The combined δ ¹⁸O–δ ¹³C and ⁸⁷Sr/⁸⁶Sr data indicate that the magnesite-related fluids were modified basinal brines that have reacted and equilibrated with intercalated siliciclastic rocks. Magnesite formation is genetically linked to regional hydrothermal dolomitisation associated with lithospheric delamination, late-Variscan high heat flow and extensional tectonics in the NW Iberian Belt. A comparison with genetic models for the Puebla de Lillo talc deposits suggests that the formation of hydrothermal replacive magnesite at Rubian resulted from a metasomatic column with magnesite forming at higher fluid/rock ratios than dolomite. In this study, magnesite generation took place via the local reaction of hydrothermal dolostone with the same hydrothermal fluids in very high permeability zones at high fluid/rock ratios (e.g. faults). It was also possibly aided by additional heat from intrusive dykes or sub-cropping igneous bodies. This would locally raise isotherms enabling a transition from the dolomite stability field to that of magnesite.Editorial handling: F. Tornos     

Isotope geochemistry of ore fluids for the Dongsheng sandstone-type uranium deposit, China

The Dongsheng sandstone-type uranium deposit is one of the large-sized sandstone-type uranium deposits discovered in the northern part of the Ordos Basin of China in recent years. Geochemical characteristics of the Dongsheng uranium deposit are significantly different from those of the typical interlayered oxidized sandstone-type uranium ore deposits in the region of Middle Asia. Fluid inclusion studies of the uranium deposit showed that the uranium ore-forming temperatures are within the range of 150–160℃. Their 3He/4He ratios are within the range of 0.02–1.00 R/Ra, about 5–40 times those of the crust. Their 40Ar/36Ar ratios vary from 584 to 1243, much higher than the values of atmospheric argon. The δ18OH2O and δD values of fluid inclusions from the uranium deposit are -3.0‰– -8.75‰ and -55.8‰– -71.3‰, respectively, reflecting the characteristics of mixed fluid of meteoric water and magmatic water. The δ18OH2O and δD values of kaolinite layer at the bottom of the uranium ore deposit are 6.1‰ and -77‰, respectively, showing the characteristics of magmatic water. The δ13CV-PDB and δ18OH2O values of calcite veins in uranium ores are -8.0‰ and 5.76‰, respectively, showing the characteristics of mantle source. Geochemical characteristics of fluid inclusions indicated that the ore-formation fluid for the Dongsheng uranium deposit was a mixed fluid of meteoric water and deep-source fluid from the crust. It was proposed that the Jurassic-Cretaceous U-rich metamorphic rocks and granites widespread in the northern uplift area of the Ordos Basin had been weathered and denudated and the ore-forming elements, mainly uranium, were transported by meteoric waters to the Dongsheng region, where uranium ores were formed. Tectonothermal events and magmatic activities in the Ordos Basin during the Mesozoic made fluids in the deep interior and oil/gas at shallow levels upwarp along the fault zone and activated fractures, filling into U-bearing clastic sandstones, thus providing necessary energy for the formation of uranium ores.     

Geology and geochemistry of jasperoids from the Gold Bar district, Nevada

Gold Bar is one of several Carlin-type gold mining districts located in the Battle Mountain–Eureka trend, Nevada. It is composed of one main deposit, Gold Bar; five satellite deposits; and four resources that contain 1.6 Moz (50 t) of gold. All of the deposits and resources occur at the intersection of north-northwest- and northeast-trending high-angle faults in slope facies limestones of the Devonian Nevada Group exposed in windows through Ordovician basin facies siliciclastic rocks of the Roberts Mountains allochthon. Igneous intrusions and magnetic anomalies are notably absent. The Gold Bar district contains a variety of discordant and stratabound jasperoid bodies, especially along the Wall Fault zone, that were mapped and studied in some detail to identify the attributes of those most closely associated with gold ore and to constrain genetic models. Four types of jasperoids, J₀, J₁, J₂, and J₃, were distinguished on the basis of their geologic and structural settings and appearance. Field relations suggest that J₀ formed during an early event. Petrographic observations, geochemistry, and δ¹⁸O values of quartz suggest it was overprinted by the hydrothermal event that produced ore-related J₁, J₂, and J₃ jasperoids and associated gold deposits. The greater amount of siliciclastic detritus present in J₀ jasperoids caused them to have higher δ¹⁸O values than J_1,2,3 jasperoids hosted in underlying limestones. Ore-related jasperoids are composed of main-ore-stage replacements and late-ore-stage open-space filling quartz with variable geochemistry and an enormous range of δ¹⁸O values (24.5 and −3.7‰). Jasperoids hosted in limestones with the most anomalous Au, Ag, Hg, ±(As, Sb, Tl) concentrations and the highest δ¹⁸O values are associated with the largest deposits. The 28‰ range of jasperoid δ¹⁸O values is best explained by mixing between an ¹⁸O-enriched fluid and an ¹⁸O-depleted fluid. The positive correlation between the sizes of gold deposits and the δ¹⁸O composition of jasperoids indicates that gold was introduced by the ¹⁸O-enriched fluid. The lowest calculated δ¹⁸O value for water in equilibrium with late-ore-stage quartz at 200°C (−15‰) and the measured δD value of fluid inclusion water extracted from late-ore-stage orpiment and realgar (−116‰) indicate that the ¹⁸O-depleted fluid was composed of relatively unexchanged meteoric water. The source of the ¹⁸O-enriched ore fluid is not constrained. The δ³⁴S values of late-ore-stage realgar, orpiment, and stibnite (5.7–15.5‰) and barite (31.5–40.9‰) suggest that H₂S and sulfate were derived from sedimentary sources. Likewise, the δ¹³C and δ¹⁸O values of late-stage calcite (−4.8 to 1.5‰ and 11.5 to 17.4‰, respectively) suggest that CO₂ was derived from marine limestones. Based on these data and the apparent absence of any Eocene intrusions in the district, Gold Bar may be the product of a nonmagmatic hydrothermal system.     

Fluid inclusion and stable isotope (O, H, C, and S) constraints on the genesis of the Serrinha gold deposit, Gurupi Belt, northern Brazil

The Serrinha gold deposit of the Gurupi Belt, northern Brazil, belongs to the class of orogenic gold deposits. The deposit is hosted in highly strained graphitic schist belonging to a Paleoproterozoic (∼2,160 Ma) metavolcano-sedimentary sequence. The ore-zones are up to 11 m thick, parallel to the regional NW–SE schistosity, and characterized by quartz-carbonate-sulfide veinlets and minor disseminations. Textural and structural data indicate that mineralization was syn- to late-tectonic and postmetamorphic. Fluid inclusion studies identified early CO₂ (CH₄-N₂) and CO₂ (CH₄-N₂)-H₂O-NaCl inclusions that show highly variable phase ratios, CO₂ homogenization, and total homogenization temperatures both to liquid and vapor, interpreted as the product of fluid immiscibility under fluctuating pressure conditions, more or less associated with postentrapment modifications. The ore-bearing fluid typically has 18–33mol% of CO₂, up to 4mol% of N₂, and less than 2mol% of CH₄ and displays moderate to high densities with salinity around 4.5wt% NaCl equiv. Mineralization occurred around 310 to 335°C and 1.3 to 3.0 kbar, based on fluid inclusion homogenization temperatures and oxygen isotope thermometry with estimated oxygen fugacity indicating relatively reduced conditions. Stable isotope data on quartz, carbonate, and fluid inclusions suggest that veins formed from fluids with δ¹⁸O_H2O and δD_H2O (310–335°C) values of +6.2 to +8.4‰ and −19 to −80‰, respectively, which might be metamorphic and/or magmatic and/or mantle-derived. The carbon isotope composition (δ¹³C) varies from −14.2 to −15.7‰ in carbonates; it is −17.6‰ in fluid inclusion CO₂ and −23.6‰ in graphite from the host rock. The δ³⁴S values of pyrite are −2.6 to −7.9‰. The strongly to moderately negative carbon isotope composition of the carbonates and inclusion fluid CO₂ reflects variable contribution of organic carbon to an originally heavier fluid (magmatic, metamorphic, or mantle-derived) at the site of deposition and sulfur isotopes indicate some oxidation of the originally reduced fluid. The deposition of gold is interpreted to have occurred mainly in response to phase separation and fluid-rock interactions such as CO₂ removal and desulfidation reactions that provoked variations in the fluid pH and redox conditions.     

Epithermal mineralization and ore controls of the Shasta Au-Ag deposit, Toodoggone District, British Columbia, Canada

The Shasta gold-silver deposit, British Columbia, Canada, is an adularia-sericite-type epithermal deposit in which deposition of precious metals coincided with the transition of quartz- to calcite-dominant gangue. Mineralization is associated with stockwork-breccia zones in potassically altered dacitic lapilli tuffs and flows, and consists of pyrite, sphalerite, chalcopyrite, galena, acanthite, electrum and native silver. Pre- and post-ore veins consist solely of quartz and calcite, respectively. Fluid inclusion microthermometry indicates that ore minerals were deposited between 280 ° and 225 °C, from a relatively dilute hydrothermal fluid (˜1.5 wt.% NaCl equivalent). Abundant vapor-rich inclusions in ore-stage calcite are consistent with boiling. Oxygen and hydrogen isotopic data (δ¹⁸O_fluid = −1.5 to −4.1‰; δD_fluid = −148 to −171‰) suggest that the fluid had a meteoric origin, but was ¹⁸O-enriched by interaction with volcanic wallrocks. Initial (˜280 °C) fluid pH and log f O₂ conditions are estimated at 5.3 to 6.0, and −32.5 to −33 bar, respectively; during ore deposition, the fluid became more alkaline and oxidizing. Ore deposition at Shasta is attributed to localization of meteoric hydrothermal fluids by extensional faults; mineralization was controlled by boiling in response to hydraulic brecciation. Calcite and base metal sulfides precipitated due to the increase in pH that accompanied boiling, and the associated decrease in H₂S concentration led to precipitation of gold and silver. Received: 23 February 1995 / Accepted: 16 April 1996     

Diamonds and eclogites of the Jericho kimberlite (Northern Canada)

We studied diamonds and barren and diamondiferous eclogite xenoliths from the Jericho kimberlite (Northern Slave craton). The majority of the diamonds are non-resorbed octahedral crystals, with moderately aggregated N (IaB < 50%, N < 300 ppm) and δ¹³C = −5 to −41‰. The diamonds belong to “eclogitic” (90% of the studied samples), “websteritic” (7%) and “peridotitic” (3%) assemblages. The Jericho diamonds differ from the majority of “eclogitic” diamonds worldwide in magnesian compositions of associated minerals and extremely light C isotopic compositions (δ¹³C = −24 to −41‰). We propose that metasomatism triggered by H₂O fluids may have been involved in the diamond formation. Multiple episodes of the metasomatism and associated melt extraction of various ages are evident in Jericho eclogite xenoliths where primary garnet and clinopyroxene have been recrystallized to more magnesian minerals with higher contents of some incompatible trace elements and to hydrous secondary phases. The model is supported by the general similarity of mineral compositions in diamondiferous eclogites to those in diamond inclusions and to secondary magnesian garnet and clinopyroxene in recrystallized barren eclogites. The ultimate products of the metasomatism could be “websteritic” diamond assemblages sourced from magnesian eclogites. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Mineral inclusions in sublithospheric diamonds from Collier 4 kimberlite pipe, Juina, Brazil: subducted protoliths, carbonated melts and primary kimberlite magmatism

We report on a suite of diamonds from the Cretaceous Collier 4 kimberlite pipe, Juina, Brazil, that are predominantly nitrogen-free type II crystals showing complex internal growth structures. Syngenetic mineral inclusions comprise calcium- and titanium-rich phases with perovskite stoichiometry, Ca-rich majoritic-garnet, clinopyroxene, olivine, TAPP phase, minerals with stoichiometries of CAS and K-hollandite phases, SiO₂, FeO, native iron, low-Ni sulfides, and Ca–Mg-carbonate. We divide the diamonds into three groups on the basis of the carbon isotope compositions (δ¹³C) of diamond core zones. Group 1 diamonds have heavy, mantle-like δ¹³C (−5 to −10‰) with mineral inclusions indicating a transition zone origin from mafic protoliths. Group 2 diamonds have intermediate δ¹³C (−12 to −15‰), with inclusion compositions indicating crystallization from near-primary and differentiated carbonated melts derived from oceanic crust in the deep upper mantle or transition zone. A ²⁰⁶Pb/²³⁸U age of 101 ± 7 Ma on a CaTiSi-perovskite inclusion (Group 2) is close to the kimberlite emplacement time (93.1 ± 1.5 Ma). Group 3 diamonds have extremely light δ¹³C (−25‰), and host inclusions have compositions akin to high-pressure–temperature phases expected to be stable in pelagic sediments subducted to transition zone depths. Collectively, the Collier 4 diamonds and their inclusions indicate multi-stage, polybaric growth histories in dynamically changing chemical environments. The young inclusion age, the ubiquitous chemical and isotopic characteristics indicative of subducted materials, and the regional tectonic history, suggest a model in which generation of sublithospheric diamonds and their inclusions, and the proto-kimberlite magmas, are related genetically, temporally and geographically to the interaction of subducted lithosphere and a Cretaceous plume.     

Geology and geochemistry of telluride-bearing Au deposits in the Pingyi area, Western Shandong, China

Summary Telluride-bearing gold deposits of the Pingyi area, western Shandong, China, are located on the southeastern margin of the North China Craton. There are two main types of deposits: (i) mineralized cryptoexplosive breccia, e.g., Guilaizhuang; and (ii) stratified, finely-disseminated mineralization hosted in carbonate rocks, e.g., Lifanggou and Mofanggou deposits. In Guilaizhuang, the cryptoexplosive breccia is formed within rocks of the Tongshi complex and Ordovician dolomite. The mineralization is controlled by an E–W-trending listric fault. Stratified orebodies of the Lifanggou and Mofanggou deposits are placed along a NE-trending, secondary detachment zone. They are hosted within dolomitic limestone, micrite and dolomite of the Early-Middle Cambrian Changqing Group. The mineralization in the ore districts is considered to be related to the Early Jurassic Tongshi magmatic complex that formed in a continental arc setting on the margin of the North China Craton. The host rocks are porphyritic and consist predominantly of medium- to fine-grained diorite and pyroxene (hornblende)-bearing monzonite. SHRIMP U–Pb zircon dating of diorites give a ²⁰⁶Pb/²³⁸U weighted mean age of 175.7 ± 3.8 Ma. This is interpreted as representing the crystallization age of the Tongshi magmatic complex. Considering the contact relationships between the magmatic and host sedimentary rocks, as well as the genetic link with the deposits, we conclude that this age is relevant also for the formation of mineralization in the Pingyi area. We hence consider that the deposits formed in the Jurassic. The principal gold minerals are native gold, electrum and calaverite. Wall-rock alteration comprises pyritization, fluoritization, silicification, carbonatization and chloritization. Fluid inclusion studies indicate that all the analyzed inclusions are of two-phase vapor–liquid NaCl–H₂O type. Homogenization temperatures of the fluid inclusions vary from 103 °C to 250 °C, and the ice melting temperatures range from −2.5 °C to −13.5 °C, corresponding to a salinity range of 4.65 to 17.26 wt.% NaCl equiv. The δ³⁴S values of pyrite associated with gold mineralization exhibit a narrow range of −0.71 to + 2.99‰, implying that the sulfur was probably derived from the mantle and/or dioritic magma. The δ¹³C_PDB values of the fluid inclusions in calcite range from −7.3 to 0.0‰. The δ¹⁸O_SMOW values of vein quartz and calcite range from 11.5 to 21.5‰, corresponding to δ¹⁸O_fluid values of −1.1 to 10.9‰; δD values of the fluid inclusions vary between −70 and −48‰. The isotope data for all three deposits suggest mixing of ore-forming fluids derived from the mantle and/or magma with different types of fluids at shallow levels. Pressure release and boiling of the fluids, as well as fluid-rock interaction (Lifanggou and Mofanggou) and mixing of magmatically-derived fluids with meteoritic waters (Guilaizhuang) played an important role in the ore-forming processes.     

Water-rock interactions and chemical compositional variations during ductile deformation of the NW-striking shear zone in the Jiapigou gold belt,China

Two kinds of mylonite series rocks, felsic and mafic, have been recognized in the NW-striking shear zone of the Jiapigou gold belt. During ductile deformation, a large amount of fluid interacted intensively with the mylonite series rocks: plagioclases were sericitized and theAn values declined rapidly, finally all of them were transformed to albites; dark minerals were gradually replaced by chlorites (mostly ripidolite). Meanwhile, large-scale and extensive carbonation also took place, and the carbonatization minerals varied from calcite to dolomite and ankerite with the development of deformation. The δ¹³C values of the carbonates are −3.0‰ – −5.6‰ suggesting a deep source of carbon. The ductile deformation is nearly an iso-volume one (f _v≈1). With the enhancement of shear deformation, SiO₂ in the two mylonite series rocks was depleted, while volatile components suchs as CO₂ and H₂O, and some ore-forming elements such as Au and S were obviously enriched. But it is noted that the enrichment of Au in both the mylonite series rocks did not reach the paygrade of gold. The released SiO₂ from water-rock interactions occurred in the form of colloids and absorbed gold in the fluid. When brittle structures were formed locally in the ductile shear zone, the ore-forming fluids migrated to the structures along microfractures, and preciptated auriferous quartz because of reduction of pressure and temperature. Fluid inclusion study shows that the temperature and pressure of the ore-forming fluids are 245–292°C and 95.4–131.7 MPa respectively; the salinity is 12.88–16.33wt% NaCl; the fluid-phase is rich in Ca²⁺, K⁺, Na⁺, Mg²⁺, F⁻ and Cl⁻, while the gaseous phases are rich in CO₂ and CH₄. The δD and δ¹⁸O, values of the ore-forming fluid are −84.48‰ – −91.73‰ and −0.247‰ – +2.715‰ respectively, suggesting that the fluid is composed predominantly of meteoric water. This project is financially supported by the National Natural Science Foundation of China (No. 9488010).     

Sulphur, carbon and oxygen isotope studies of early Variscan mineralisation and Pb-Sb vein deposits in the Cornubian orefield: implications for the scale of fluid movements during Variscan deformation

The strongly deformed Middle Devonian-Lower Carboniferous metasedimentary-volcanic successions of the Trevone Basin (SW England) contain stratiform and Pb-Sb vein deposits that reveal a wide variation in δ³⁴S and δ¹³C, reflecting mineral deposition during diagenesis, regional metamorphism and basin inversion. Pre-Variscan metasedimentary sulphide (δ³⁴S=−33.7 to −26.7‰) and metabasite sulphide (δ³⁴S=+4.0 to +10.8‰) suggest two accessible source reservoirs for sulphur which were available for Sb-As-(Au) and Pb-Zn-(Ag) mineralisation (δ³⁴S=−3.3 to −15.0‰) during late Variscan semiductile-brittle shear. On the basis of pressure-corrected fluid inclusion temperatures, the calculated composition of fluid sulphur reveals an enrichment in δ³⁴S_H2S in the individual vein parageneses and depletion of the fluid sulphur reservoir during evolution of the vein systems. Carbonates in the same veins are partly contemporaneous with Pb-Sb mineralisation and late tensional deformation; their isotopic composition (δ¹³C=−3.2 and −13.4‰) appears strongly influenced by the host formation. Fluid inclusions in post-tensional quartz show a marked reduction in CO₂, suggesting that episodes of CO₂ degassing in response to punctuated reductions in pressure during uplift and brittle deformation was an important mechanism for vein carbonation. An origin for the Pb-Sb mineralisation involving local remobilisation of sulphur from the mixed metasedimentary-volcanic succession is probably inseparable from processes connected with Variscan metamorphism and deformation. Although the N Cornish Variscan deformation is part of a spatially large-scale event, the isotopic evidence suggests compartmentalisation of sulphur and carbon isotope features and short distances between sources and sinks. Received: 15 August 1998 / Accepted: 8 October 1999     

Gold mineralization in the Mazowe area, Harare-Bindura-Shamva greenstone belt, Zimbabwe: II. Genetic relationships deduced from mineralogical, fluid inclusion and stable isotope studies, and the Sm-Nd isotopic composition of scheelites

In the Mazowe area some 40 km NW of Harare in Zimbabwe, gold mineralization is hosted in a variety of lithologies of the Archean Harare-Bindura-Shamva greenstone belt, in structures related to the late Archean regional D2/3 event. Conspicuous mineralzogical differences exist between the mines; the mainly granodiorite-hosted workings at Mazowe mine are on pyrite-rich reefs, mines of the Bernheim group have metabasalt host rocks and are characterized by arsenopyrite-rich ores, and Stori's Golden Shaft and Alice mine, both in metabasalts, work sulfide-poor quartz veins. In contrast to the mineralogical diversity, near-identical fluid inventories were found at the different mines. Both H₂O-CO₂-CH₄ fluids of low salinity, and highly saline fluids are present and are regarded to indicate fluid mixing during the formation of the deposits. Notably, these fluid compositions in the Mazowe gold field markedly contrast to ore fluids “typical” of Archean mesothermal gold deposits on other cratons. Stable isotope compositions of quartz from the various deposits (δ¹⁸O=10.8 to 13.2‰ SMOW), calcite (δ¹⁸O=9.5 to 11.9‰ SMOW and δ¹³C=−3.2 to −8.0‰ PDB), inclusion water (δD=−28 to −40‰ SMOW) and sulfides (δ³⁴S=1.3 to 3.2‰ CDT) are uniform within the range typical for Archean lode gold deposits worldwide. The fluid and stable isotope compositions support the statement that the mineralization in the Mazowe gold field formed from relatively reduced fluids with a “metamorphic” signature during a single event of gold mineralization. Microthermometric data further indicate that the deposits formed in the PT range of 1.65–2.3 kbar and 250–380 °C. Ages obtained by using the Sm/Nd and Rb/Sr isotope systems on scheelites are 2604 ± 84 Ma for the mineralization at Stori's Golden Shaft mine, and 2.40 ± 0.20 Ga for Mazowe mine. The Archean age at Stori's is regarded as close to the true age of gold mineralization in the area, whereas the Proterozoic age at Mazowe mine probably reflects later resetting. Received: 30 September 1998 / Accepted: 17 August 1999     

Fluid inclusion and stable isotope evidence for the genesis of quartz-scheelite veins, Metaggitsi area, central Chalkidiki Peninsula, N. Greece

Scheelite mineralization accompanied by muscovite and albite, and traces of Mo-stolzite and stolzite occurs in epigenetic quartz vein systems hosted by two-mica gneissic schists, and locally amphibolites, of the Paleozoic or older Vertiskos Formation, in the Metaggitsi area, central Chalkidiki, N Greece. Three types of primary fluid inclusions coexist in quartz and scheelite: type 1, the most abundant, consists of mixed H₂O-CO₂ inclusions with highly variable (20–90 vol.%) CO₂ contents and salinities between 0.2 and 8.3 equivalent weight % NaCl. Densities range from 0.79 to 0.99 g/cc; type 1 inclusions contain also traces (<2 mol%) of CH₄. Type 2 inclusions are nearly 100 vol.% liquid CO_2, with traces of CH₄, and densities between 0.75 and 0.88 g/cc. Type 3 inclusions, the least abundant, contain an aqueous liquid of low salinity (0.5 to 8.5 equivalent weight% NaCl) with 10–30 vol.% H₂O gas infrequently containing also small amounts of CO₂ (<2 mol%); densities range from 0.72 to 0.99 g/cc. The wide range of coexisting fluid inclusion compositions is interpreted as a result of fluid immiscibility during entrapment. Immiscibility is documented by the partitioning of CH₄ and CO₂, into gas-rich (CO₂-rich) type 1 inclusions, and the conformity of end-member compositions trapped in type 1 inclusions to chemical equilibrium fractionation at the minimum measured homogenization temperatures, and calculated homogenization pressures. Minimum measured homogenization temperatures of aqueous and gas-rich type 1 inclusions of 220°–250 °C, either to the H₂O, or to the CO₂ phase, is considered the best estimate of temperature of formation of the veins, and temperature of scheelite deposition. Corresponding fluid pressures were between 1.2 and 2.6 kbar. Oxygen fugacities during mineralization varied from 10⁻³⁵ to 10⁻³¹ bar and were slightly above the synthetic Ni-NiO buffer values. The fluid inclusion data combined with δ¹⁸O water values of 3 to 6 per mil (SMOW) and δ¹³C CO₂₋ fluid of −1.2 to +4.3 per mil (PDB), together with geologic data, indicate generation of mineralizing fluids primarily by late- to post-metamorphic devolatilization reactions. Received: 8 April 1997 / Accepted: 8 July 1997     

Study on the Physical and Chemical Conditions of Ore Formation of Hetai Ductile Shear Zone—Hosted Gold Deposit and Discovery of Melt Inclusions

The Hetai ductile shear zone-hosted gold deposit occurs in the deep-seated fault mylonite zone of the Sinian-Silurian metamorphic rock series. In this study there have been discovered melt inclusions, fluid-melt inclusions and organic inclusions in ore-bearing quartz veins of the ore deposit and mylonite for the first time. The homogenization temperatures of the various types of inclusions are 160℃, 180 - 350℃, 530℃ and 870℃ for organic inclusions, liquid inclusions, two-phase immiscible liquid inclusions and melt inclusions, respectively. Ore fluid is categorized as the neutral to basic K+ -Ca2+ -Mg2+ -Na+ - SO2- 4-HCO3-Cl- system. The contents of trace gases follow a descending order of H2O＞CO2＞CH4＞(or ＜ ) H2＞CO＞C2H2＞C2I-I6＞O2＞N2.The concentrations of K , Ca2 + ,SO2-4,HCO3-,Cl- H2O and C2H2 in fluid inclusions are related to the contents of gold and the Au/Ag ratios in ores from different levels of the gold deposit. This is significant for deep ore prospecting in the region. Daughter minerals in melt inclusions were analyzed using SEM. Quartz, orthoclase, wollastonite and other silicate minerals were identified. They were formed in different mineral assemblages.This analysis further proves the existence of melt inclusions in ore veins. Sedimentary metamorphic rocks could form silicate melts during metamorphic anatexis and dynamic metamorphism, which possess melt-solution characteristics. Ore formation is related to the multi-stage forming process of silicate melt and fluid.     

Biogeochemistry of the Russian Arctic. Kara Sea: Research results under the SIRRO project, 1995–2003

The Kara Sea is an area uniquely suitable for studying processes in the river-sea system. This is a shallow sea into which two great Siberian rivers, Yenisei and Ob, flow. From 1995 to 2003, the sea was studied by six international expeditions aboard the R/V Akademik Boris Petrov. This publication summarizes the results obtained, within the framework of this project, at the Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences. Various hydrogeochemical parameters, concentrations and isotopic composition of organic and carbonate carbon of the sediments, plankton, particulate organic matter, hydrocarbons, and dissolved CO₂ were examined throughout the whole sea area at more than 200 sites. The δ¹³C varies from −22 and −24‰ where Atlantic waters enter the Kara Sea and in the North-eastern part of the water area to −27‰ in the Yenisei and Ob estuaries. The value of δ¹³C of the plankton is only weakly correlated with the δ¹³C of the organic matter from the sediments and is lower by as much as 3–4‰. The paper presents the results obtained from a number of meridional river-sea profiles. It was determined from the relations between the isotopic compositions of plankton and particulate matter that the riverwaters carry material consisting of 70% detrital-humus matter and 30% planktonogenic material in the river part, and the material contained in the off-shore waters consists of 30% terrigenous components, with the contribution of bioproducers amounting to 70%. The carbon isotopic composition of the plankton ranges from −29 to −35‰ in the riverine part, from −28 to −27‰ in the estuaries, and from −27.0 to −25% in the marine part. The relative lightness of the carbon isotopic composition of plankton in Arctic waters is explained by the temperature effect, elevated CO₂ concentrations, and long-distance CO₂ supply to the sea with riverwaters. The data obtained on the isotopic composition of CO₂ in the surface waters of the Kara Sea were used to map the distribution of δ¹³C_{CO 2}. The complex of hydrocarbon gases extracted from the waters included methane, C₂–C₅, and unsaturated C₂₌–C₄₌ hydrocarbons, for which variations in the concentrations in the waters were studied along river-estuary-sea profiles. The geochemistry of hydrocarbon gases in surface fresh waters is characterized by comparable concentrations of methane (0.3–5 μl/l) and heavier hydrocarbons, including unsaturated ones. Microbiological methane with δ¹³C from −105 to −90‰ first occurs in the sediments at depths of 40–200 cm. The sediments practically everywhere display traces of methane oxidation in the form of a shift of the δ¹³C of methane toward higher values and the occurrence of autogenic carbonate material, including ikaite, enriched in the light isotope. Ikaite (δ¹³C from −25 to −60‰) was found and examined in several profiles. The redox conditions in the sediments varied from normal in the southern part of the sea to highly oxidized along the Novaya Zemlya Trough. Vertical sections through the sediments of the latter exemplify the complete suppression of the biochemical activity of microorganisms. Our data provide insight into the biogeochemistry of the Kara Sea and make it possible to specify the background values needed for ecological control during the future exploration operations and extraction of hydrocarbons in the Kara Sea. Original Russian Text ? E.M. Galimov, L.A. Kodina, O.V. Stepanets, G.S. Korobeinik, 2006, published in Geokhimiya, 2006, No. 11, pp. 1139–1191.