Timing and genesis of base-metal mineralisation in black shales of the Upper Permian Ravnefjeld Formation,Wegener Halvø, East Greenland

Bituminous mud shales of the Upper Permian Ravnefjeld Formation (Zechstein 1 equivalent) are mineralised with zinc, lead and copper within a ca. 50 km² area on Wegener Halvø in central East Greenland. The occurrence of base-metal sulphides in shale nodules cemented prior to compaction indicates an early commencement of base-metal mineralisation. In other cases, post-compactional sulphide textures are observed. Homogeneous lead isotope signatures of galena and sphalerite from the shales (²⁰⁶Pb/²⁰⁴Pb: 18.440–18.466; ²⁰⁷Pb/²⁰⁴Pb: 16.554–16.586; ²⁰⁸Pb/²⁰⁴Pb: 38.240–38.326) suggest that all base metals were introduced during a single hydrothermal event. Therefore, post-compactional textures are believed to result from recrystallisation of early diagenetic sulphides during deep burial in the Upper Cretaceous to Tertiary. Lead isotope signatures of galena hosted in Upper Permian carbonate build-ups are relatively heterogeneous compared to those of the shale-hosted sulphides. The observed relations indicate a shared lead source for the two types of mineralisation, but different degrees of homogenisation during mineralisation. This suggests that lead was introduced to the carbonate rocks and black shales during two separate events. δ³⁴S of base-metal sulphides in the Ravnefjeld Formation lie between –12 and –4‰, whereas synsedimentary and early diagenetic pyrite in unmineralised shales in general have δ³⁴S between –47 and –16.5‰. Early diagenetic pyrite in the Wegener Halvø area in general has δ³⁴S 15 to 20‰ higher than the same pyrite morphotype in Triaselv in the western part of the basin. This relatively high δ³⁴S can be explained by extensive microbial sulphate reduction within persistent euxinic (super-anoxic) bottom waters under which supply of isotopically light seawater sulphate (and disproportionation of intermediate sulphur compounds) was restricted. The sulphur in the base-metal sulphides is believed to represent sulphide-dominated pore water, enriched in ³⁴S due to preferential removal of ³²S by sulphate-reducing bacteria and precipitation of diagenetic pyrite in the near-seafloor environment. We suggest that the sulphide-dominated pore water was trapped in the shale formation prior to introduction of base-metal-bearing fluids through fractures in the underlying carbonates, and that sulphide precipitation took place when the two fluids met. δ³⁴S values of carbonate-hosted base-metal sulphides fall within the same range as the shale-hosted ones. The relationship between barite and sulphides and evidence for pre-mineralisation entrapment of liquid hydrocarbons in the carbonates suggest that the sulphide in this case is derived by in-situ thermochemical sulphate reduction (TSR). Measured fractionation between sulphide and sulphate ranges from 18.5 to 24.4‰, suggesting temperatures of TSR around 70 to 100 °C. Vitrinite reflectance measurements in mineralised shale samples are all between 1.7 and 2.0%, except for samples taken close to a Tertiary dyke giving ca. 3.0%. Vitrinite reflectance data are comparable to previously published data from unmineralised shale samples in the area and could not be proven to correlate with the degree of mineralisation. This indicates that any early hydrothermal effect has been overprinted later, probably during deep burial in the Late Cretaceous to Early Tertiary as previously proposed.     

Volatile characteristics of peralkaline rhyolites from Kenya: an ion microprobe,infrared spectroscopic and hydrogen isotope study

Peralkaline rhyolites of the Greater Olkaria Volcanic Complex, Kenya Rift Valley, were derived from separated, though closely related, magma chambers. Ion microprobe analyses of glass inclusions in quartz phenocrysts show pre-eruptive water contents of up to 3.4 wt% contrasting with previous estimates that the magmas were anhydrous. The values approach predicted solubility levels corresponding to water saturation at low crustal pressures (1 kbar). The glass matrices of the rhyolites have low water contents, ranging from 0.07 to 0.46 wt%, suggesting significant degassing during, or prior to, eruption. Infrared measurements of the matrix glasses show variation in the relative proportions of the two hydrous species dissolved in the glasses. The amount of molecular water, determined semi-quantitatively, apparently increases with increased fluorine content and peralkalinity. This suggests a competition between hydroxyl groups and fluoride ions for similar sites within the melt structure. The mechanism of degassing has been investigated using hydrogen isotopes. The range of D values in most rocks can be produced by varied degrees of open-system degassing of rhyolite melt initially in equilibrium with water of a fixed, or limited, D value. There is evidence to suggest that closed-system degassing may also have been a significant component in some rhyolites. The exact mechanisms of degassing remain uncertain. Particular problems include the relative contribution of open-and closed-system degassing during eruption and the initial vapour compositions and solubility relationships.     

The evolution of fluorine-rich felsic magmas: source dichotomy, magmatic convergence and the origins of topaz granite

Topaz granite is alkali-feldspar granite that contains essential albite, quartz, K-feldspar, lithium-mica, and topaz. As a group topaz granites are characterized by their extreme enrichment in F (up to 3 wt%) and a wide variety of lithophile elements. They can be subdivided into a 'low-P₂O₅ subtype' (P₂O₅ < 0.1 wt%, Al₂O₃ < 14.5 wt%, SiO₂ > 73 wt%) and a 'high-P₂O₅ subtype' (P₂O₅ > 0.4 wt%, Al₂O₃ > 14.5 wt%, SiO₂ < 73 wt%), the δ¹⁸O values of which indicate a dichotomy of source rock: the low-P₂O₅ subtype (δ¹⁸O < 10‰) having a meta-igneous protolith and the high-P₂O₅ subtype (δ¹⁸O > 10 ‰) a source with a significant component of pelitic material. The unusually high F contents enhance the efficacy of melt segregation and crystal-melt fractionation and so facilitate extreme differentiation in topaz granite magmas. Very low melt volumes restrict the bulk composition of the partial melts regardless of the nature of the source; and extreme fractionation forces them along a path of magmatic convergence, to produce a group of granitic rocks with near-minimum compositions so enriched in a variety of lithophile elements (Li, Nb, Ta, Sn) that economic mineralization often results.     

Laser microprobe sulphur isotope analysis of arsenopyrite: experimental calibration and application to the Boliden Au–Cu–As massive sulphide deposit

Metamorphic remobilization of arsenopyrite-rich ores is a globally important process which can lead to significant concentrations of gold. In order to understand this and related processes, relations of sulphur isotopes can give a number of important clues. To resolve such relations in detail, we have successfully calibrated and applied a laser combustion system for in situ analysis of sulphur isotopic compositions of arsenopyrite. Experimental calibration of the laser fractionation factor (+0.4‰) was obtained by using compositionally and isotopically homogeneous natural samples from ore deposits at Boliden (Sweden) and Freiberg (Germany); subsequent to detailed microscopic study, the S isotope ratios of these samples were measured by conventional and laser combustion techniques.The present application to different types of arsenopyrite in the Palaeoproterozoic metamorphosed VHMS ores of the Boliden Au–Cu–As deposit, Skellefte district, northern Sweden, shows that the sulphur isotope composition of arsenopyrite is essentially unmodified during medium-grade metamorphic recrystallization and remobilization. Here, massive arsenopyrite ore is crosscut by later veins that carry a complex quartz–sulphosalt–sulphide assemblage. The latter ore type is markedly Au-rich compared to the host ore, and thus of significant economic interest. We find that both ore types exhibit very similar sulphur isotope compositions, ca. +2‰ to +3‰ (V-CDT), which is similar to most massive sulphide deposits in the Skellefte district. Thus, the crosscutting Au-rich vein ore has inherited the sulphur isotope composition from sulphur liberated by metamorphic reactions affecting the massive ore, and most likely also inherited the Au through this mechanism. The latter finding clearly has important implications both for the general discussion on, and the prospecting for, similar high-grade Au ores in this world-class mining region.     

Epithermal gold veins in a caldera setting: Banská Hodruša, Slovakia

The central zone of the large Miocene tiavnica stratovolcano in the Western Carpathians hosts epithermal Au mineralization of intermediate-sulfidation type, located at deep levels of the historic Rozália base-metal mine at Banská Hodrua. The Au mineralization occurs as subhorizontal veins at the base of pre-caldera andesites, close to the roof of a subvolcanic granodiorite intrusion. The veins are dismembered by a set of quartz–diorite porphyry sills and displaced by the younger, steeply dipping, Rozália base-metal vein, and parallel structures. The base-metal vein structures are related to resurgent horst uplift in the caldera center. The Au mineralization formed during two stages. Based on fluid inclusion evidence, both stages formed from fluids of low salinity (0–3 wt% NaCl eq.), which underwent extensive boiling at moderate temperatures (280–330°C). Variable pressure conditions (39–95 bars, neglecting the effect of CO₂) indicate continual opening of the system and a transition from suprahydrostatic towards hydrodynamic conditions at shallow depths (~550 m). The fluid inclusions of the Rozália base-metal vein show homogenization temperature peaks at ~285 and 187°C and salinities between 1 and 4 wt% NaCl eq. Precipitation of Au is considered to be the result of prolonged boiling of fluids and associated decrease in Au solubility. Oxygen and hydrogen isotope data for quartz and carbonate from the Au veins show a relatively homogeneous fluid composition (–2.7 to 1.1¹⁸O, –78 to –62D). The combined ¹⁸O_fluid and D_fluid values suggest a mixed character of fluids, falling between the fields of typical magmatic and meteoric water influenced by ¹⁸O_fluid shift due to fluid–rock isotopic exchange. End stages of open-system boiling and fractionation could have been reached, at least locally. Significantly lower isotopic composition of meteoric fluids associated with Au mineralization compared to those associated with the intrusion-related mineralizations could have resulted from changing paleoclimate and/or analytical problems of extraction of water from fluid inclusions. The proposed genetic model for the Au deposit at Rozália mine highlights the importance of hydrothermal activity during the early stage of caldera collapse. Caldera subsidence established new, convective, fluid-flow paths along marginal caldera faults, which acted as infiltration zones. Major metal precipitation occurred within subhorizontal structures that formed as the result of a collapse-related stress field. A shallow, differentiated magma chamber at the base of the volcano was the likely source of heat and magmatic components for the mineralizing fluids.Editorial handling: S. Nicolescu     

Formation of the Vysoká–Zlatno Cu–Au skarn–porphyry deposit, Slovakia

The central zone of the Miocene Štiavnica stratovolcano hosts several occurrences of Cu–Au skarn–porphyry mineralisation, related to granodiorite/quartz–diorite porphyry dyke clusters and stocks. Vysoká–Zlatno is the largest deposit (13.4 Mt at 0.52% Cu), with mineralised Mg–Ca exo- and endoskarns, developed at the prevolcanic basement level. The alteration pattern includes an internal K- and Na–Ca silicate zone, surrounded by phyllic and argillic zones, laterally grading into a propylitic zone. Fluid inclusions in quartz veinlets in the internal zone contain mostly saline brines with 31–70 wt.% NaCl eq. and temperatures of liquid–vapour homogenization (Th) of 186–575°C, indicating fluid heterogenisation. Garnet contains inclusions of variable salinity with 1–31 wt.% NaCl eq. and Th of 320–360°C. Quartz–chalcopyrite veinlets host mostly low-salinity fluid inclusions with 0–3 wt.% NaCl eq. and Th of 323–364°C. Data from sphalerite from the margin of the system indicate mixing with dilute and cooler fluids. The isotopic composition of fluids in equilibrium with K-alteration and most skarn minerals (both prograde and retrograde) indicates predominantly a magmatic origin (δ¹⁸O_fluid 2.5–12.3‰) with a minor meteoric component. Corresponding low δD_fluid values are probably related to isotopic fractionation during exsolution of the fluid from crystallising magma in an open system. The data suggest the general pattern of a distant source of magmatic fluids that ascended above a zone of hydraulic fracturing below the temperature of ductile–brittle transition. The magma chamber at ∼5–6 km depth exsolved single-phase fluids, whose properties were controlled by changing PT conditions along their fluid paths. During early stages, ascending fluids display liquid–vapour immiscibility, followed by physical separation of both phases. Low-salinity liquid associated with ore veinlets probably represents a single-phase magmatic fluid/magmatic vapour which contracted into liquid upon its ascent.     

The Enåsen gold deposit,central Sweden

Stable isotope analyses of quartz, sulphides, and magnetite were conducted to provide information on thermal history and source of hydrothermal fluids in the Palaeoproterozoic Enåsen gold deposit. Reequilibration and homogenization of oxygen isotopes throughout the rock have apparently not occurred despite the upper amphibolite to granulite facies regional metamorphism that has affected the rocks. However, oxygen isotope geothermometry on a coexisting quartz-magnetite pair gave a minimum temperature for peak metamorphism of around 650 °C which agrees with Fe-Mg geothermometry. This suggests that grain-scale equilibrium is achieved. The variation in oxygen isotope ratios (¹⁸O = 7.3 – 10.5) on quartz from the metamorphosed acid sulphate alteration zone is suggested to represent a cooling trend in the fossil hydrothermal system with higher ¹⁸O-values in more superficial parts. Temperatures of alteration and silicification and isotopic composition of hydrothermal fluids could not be defined from the present data but it was recognized that the data is compatible with a epithermal genesis for the deposit. It is suggested that alteration, silicification, and mineralization at the Enåsen gold deposit took place in a high sulphidation epithermal environment at temperatures of around 200–250 °C and that the hydrothermal fluids consisted of meteoric and magmatic water. A tentative reconstruction of the fossil hydrothermal system is presented. Sulphur isotope ratios of sulphides from the fold-bearing quartz-sillimanite gneiss gave ³⁴S-values close to zero indicating a magmatic source of the sulphur.     

Rb-Sr, K-Ar, H-and O-Isotope systematics of the Middle Riphean shales from the Debengda Formation, the Olenek Uplift, North Sibera

Clay subfractions (SFs) of <0.1, 0.1–0.2, 0.2–0.3, 0.3–0.6, 0.6–2 and 2–5 μm separated from Middle Riphean shales of the Debengda Formation are studied using the TEM, XRD, K-Ar and Rb-Sr isotopic methods. The oxygen and hydrogen isotope compositions in the SFs are studied as well. The low-temperature illite-smectite is dominant mineral in all the SFs except for the coarsest ones. The XRD, chemical and isotopic data imply that two generations of authigenic illite-smectite different in age are mixed in the SFs. The illite crystallinity index decreases in parallel with size diminishing of clay particles. As compared to coarser SFs, illite of fine-grained subfractions is enriched in Al relative to Fe and Mg, contains more K, and reveals higher K/Rb and Rb/Sr ratios. The Rb-Sr age calculated by means of the leachochron (“inner isochron”) method declines gradually from 1254-1272 Ma in the coarsest SFs to 1038-1044 Ma in finest ones, while the K-Ar age decreases simultaneously from 1225–1240 to 1080 Ma. The established positive correlation of δ¹⁸O and δD values with dimensions of clay particles in the SFs seems to be also consistent with the mixing systematics. The isotopic systematics along with data on mineral composition and morphology lead to the conclusion that mixedlayer illite-smectite was formed in the Debengda shales during two periods 1211–1272 and 1038–1080 Ma ago. The first period is likely close to the deposition time of sediments and corresponds to events of burial catagenesis, whereas the second one is correlative with the regional uplift and changes in hydrological regime during the pre-Khaipakh break in sedimentation.     

Fluids in early stage hydrothermal alteration of high-sulfidation epithermal systems: A view from the Vulcano active hydrothermal system (Aeolian Island,Italy)

High-sulfidation (HS) epithermal systems have elements in common with passively degassing volcanoes associated with high T, acid fumarole fields or acid crater lakes. They are considered to form in two stages, the first of which involves advanced argillic alteration resulting from intense, strongly acidic fluid–rock interaction. The La Fossa hydrothermal system (Vulcano Island) represents a classic example of such an active HS system and can be considered as a modern analogue of this early stage of alteration, resulting in a core of intense silicic (90–95% pure SiO₂) alteration surrounded by alunitic alteration zones.     

The Cherty Rock,Elgin: A petrographic and isotopic study of a Permo-Triassic calcrete

The Cherty Rock is a laterally persistent horizon that extends across the Inner Moray Firth Basin, northeastern Scotland. The southern exposures of the Cherty Rock near Elgin reveal an indurated carbonate and silica-rich horizon (0·75-10m thick) developed in the uppermost part of the largely aeolian Lossiemouth Sandstone Formation. Laminated, pisolitic, and brecciated textures within the Cherty Rock confirm that the horizon represents an analogue to Recent calcretes of semiarid areas. Textures characteristic of silcretes are widespread in the Cherty Rock but these originate from silica replacement of calcite. The carbon and oxygen stable isotopic composition of micrite in the Cherty Rock (mean σ ¹³C = -6·9%°, mean σ ¹⁸O = -5·7%°, both relative to PDB) is comparable to that of other Permo-Triassic calcretes and modern soil carbonate, suggesting that similar processes were responsible for their formation. The σ ¹³C and σ ¹⁸O values for calcite in the Cherty Rock may indicate that evaporative processes contributed to its development. σ ¹⁸O data from spar (mean σ ¹⁸O = -9·8%° PDB) and macroquartz (mean σ ¹⁸O = 19·7% SMOW) indicate that these are later (burial) cements. The Cherty Rock is a useful stratigraphical and palaeoclimatic indicator, and its presence in the Inner Moray Firth basin suggests a period of tectonic stability in the basin during late Triassic times.