Volcanic degassing,hydrothermal circulation and the flourishing of early life on Earth: A review of the evidence from c. 3490-3240 Ma rocks of the Pilbara Supergroup,Pilbara Craton,Western Australia

New data gathered during mapping of c. 3490–3240 Ma rocks of the Pilbara Supergroup in the Pilbara Craton show that most bedded chert units originated as epiclastic and evaporative sedimentary rocks that were silicified by repeated pulses of hydrothermal fluids that circulated through the footwall basalts during hiatuses in volcanism. For most cherts, fossil hydrothermal fluid pathways are preserved as silica ± barite ± Fe-bearing veins that cut through the footwall and up to the level of individual bedded chert units, but not above, indicating the contemporaneity of hydrothermal silica veining and bedded chert deposition at the end of volcanic eruptive events. Silica ± barite ± Fe-bearing vein swarms are accompanied by extensive hydrothermal alteration of the footwall to the bedded chert units, and occurred under alternating high-sulphidation and low-sulphidation conditions. These veins provided pathways to the surface for elements leached from the footwall (e.g., Si, Ba, Fe) and volcanogenic emissions from underlying felsic magma chambers (e.g., CO₂, H₂S/HS⁻, SO₂).Stratigraphic evidence of shallowing upward and subsequent deepening associated with the deposition of Warrawoona Group cherts is interpreted to relate to the emplacement of subvolcanic laccoliths and subsequent eruption and/or degassing of these magmas. Heat from these intrusions drove episodes of hydrothermal circulation. Listric normal faulting during caldera collapse produced basins with restricted circulation of seawater. Eruption of volcanogenic emissions into these restricted basins formed brine pools with concentration of the volcanogenic components, thereby providing habitats suitable for early life forms.Fossil stromatolites from two distinct stratigraphic units in the North Pole Dome grew in shallow water conditions, but in two very different geological settings with different morphologies. Stratiform and domical stromatolites in the stratigraphically lower, c. 3490 Ma, Dresser Formation of the Warrawoona Group are intimately associated with barite and chert precipitates from hydrothermal vents, suggesting that component microbes may have been chemoautotrophic hyperthermophiles. Evidence of shallow water to periodically exposed conditions, active growth faulting and soft sediment deformation indicates that the volcanogenic emissions were erupted into a shallow water, tectonically active caldera and concentrated therein to produce an extreme habitat for early life.Widespread conical and pseudocolumnar stromatolites in the c. 3400 Ma, Strelley Pool Chert at the base of the unconformably overlying Kelly Group occur in shallow marine platform carbonates. Silicification was the result of later hydrothermal circulation driven by heat from the overlying, newly erupted Euro Basalt. The markedly different morphology and geological setting of these only slightly younger stromatolites, compared with the Dresser Formation, suggests a diversity of microbial life on early Earth.The biogenicity of putative microfossils from this and younger hydrothermal silica veins in the Warrawoona Group remains controversial and requires further detailed study.     

Fault-controlled dolomitization at Swan Hills Simonette oil field (Devonian), deep basin west-central Alberta, Canada

The partly dolomitized Swan Hills Formation (Middle‐Upper Devonian) in the Simonette oil field of west‐central Alberta underwent a complex diagenetic history, which occurred in environments ranging from near surface to deep (>2500 m) burial. Five petrographically and geochemically distinct dolomites that include both cementing and replacive varieties post‐date stylolites in limestones (depths >500 m). These include early planar varieties and later saddle dolomites. Fluid inclusion data from saddle dolomite cements (T_h=137–190 °C) suggest that some precipitated at burial temperatures higher than the temperatures indicated by reflectance data (T_peak=160 °C). Thus, at least some dolomitizing fluids were ‘hydrothermal’. Fluorescence microscopy identified three populations of primary hydrocarbon‐bearing fluid inclusions and confirms that saddle dolomitization overlapped with Upper Cretaceous oil migration. The source of early dolomitizing fluids probably was Devonian or Mississippian seawater that was mixed with a more ⁸⁷Sr‐rich fluid. Fabric‐destructive and fabric‐preserving dolostones are over 35 m thick in the Swan Hills buildup and basal platform adjacent to faults, thinning to less than 10 cm thick in the buildup between 5 and 8 km away from the faults. This ‘plume‐like’ geometry suggests that early and late dolomitization events were fault controlled. Late diagenetic fluids were, in part, derived from the crystalline basement or Palaeozoic siliciclastic aquifers, based on ⁸⁷Sr/⁸⁶Sr values up to 0·7370 from saddle dolomite, calcite and sphalerite cements, and ²⁰⁶Pb/²⁰⁴Pb of 22·86 from galena samples. Flow of dolomitizing and mineralizing fluids occurred during burial greater than 500 m, both vertically along reactivated faults and laterally in the buildup along units that retained primary and/or secondary porosity.     

Aragonite stromatolitic buildups from Santorini (Aegean Sea,Greece): Geochemical and palaeontological constraints of the caldera palaeoenvironment prior to the Minoan eruption (ca 3600 yr bp)

The pyroclastic deposits of the Minoan eruption (ca 3600 yr bp ) in Santorini contain abundant xenoliths. Most of these deposits are calcareous blocks of laminated‐botryoidal, stromatolite‐like buildups that formed in the shallow waters of the flooded pre‐Minoan caldera; they consist of (i) light laminae, of fibrous aragonite arranged perpendicular to layering, and (ii) dark laminae, with calcified filaments of probable biological origin. These microstructures are absent in the light laminae, suggesting a predominant inorganic precipitation of aragonite on substrates probably colonized by microbes. Internal cavities contain loose skeletal grains (molluscs, ostracods, foraminifera and diatoms) that comprise taxa typical of shallow marine and/or lagoon environments. Most of these forms are typical of warm water environments, although no typical taxa from hydrothermal vents have been observed. Past gasohydrothermal venting is recorded by the occurrence of barite, pyrolusite and pyrite traces. The most striking features of the stable isotopic data set are: (i) an overall wide range in δ¹³C_PDB (0·16 to 12·97‰) with a narrower variation for δ¹⁸O_PDB (?0·23 to 4·33‰); and (ii) a relatively uniform isotopic composition for the fibrous aragonite (δ¹³C = 12·40 ± 0·43‰ and δ¹⁸O = 2·42 ± 0·77‰, n = 21). The δ¹³C and δ¹⁸O values from molluscs and ostracods display a covariant trend, which reflects a mixing between sea water and a fluid influenced by volcano‐hydrothermal activity. Accordingly, ⁸⁷Sr/⁸⁶Sr from the studied carbonates (0·708758 to 0·709011 in fibrous aragonite and 0·708920 to 0·708991 in molluscs) suggests that the aragonite buildups developed in sea water under the influence of a hydrothermal/volcanic source. Significant differences in trace elements have been detected between the fibrous aragonite and modern marine aragonite cements. The caldera water from which the fibrous aragonite crusts formed received an input from a volcano‐hydrothermal system, probably producing diffuse venting of volcanogenic CO₂ gas and of a fluid enriched in Ca, Mn and Ba, and depleted in Mg and probably in Sr.     

Age and significance of the Platypus Tuff Bed,a regional reference horizon in the Upper Permian Moranbah Coal Measures,north Bowen Basin

The Platypus Tuff Bed in the Permian Moranbah Coal Measures provides a basin‐wide marker horizon traceable for over 300 km along strike. The bed is a tephra event unit, the product of a large‐scale volcanic eruptive episode involving a pyroclastic volume > 10 km³. The relatively even thickness (～1–1.5 m) of the tuff across the entire northern Bowen Basin (～10 000 km²) implies a distant source. The tuff is ash‐rich and its original geochemistry has been compromised by diagenetic alteration. Crystal content (10–15%) is dominated by quartz, suggesting a rhyolitic association. SHRIMP U–Pb analysis of zircons indicates an age of 258.9 ± 2.7 Ma for the Platypus Tuff Bed, confirming the Late Permian age that has generally been assigned to the Blackwater Group. The age framework now apparent for the coal‐bearing Blackwater Group suggests an average depositional rate ranging from ～133 m/10⁶ years for its eastern depocentre in the northern Bowen Basin to ～70 m/10⁶ years in more marginal settings to the west.     

Sedimentation and welding processes of dilute pyroclastic density currents and fallout during a large-scale silicic eruption, Kikai caldera, Japan

Sedimentation and welding processes of the high temperature dilute pyroclastic density currents and fallout erupted at 7.3 ka from the Kikai caldera are discussed based on the stratigraphy, texture, lithofacies characteristics, and components of the resulting deposits. The welded eruptive deposits, Unit B, were produced during the column collapse phase, following a large plinian eruption and preceding an ignimbrite eruption, and can be divided into two subunits, Units B_l and B_u. Unit B_l is primarily deposited in topographic depressions on proximal islands, and consists of multiple thin (< 1 m) flow units with stratified and cross-stratified facies with various degrees of welding. Each thin unit appears as a single aggradational unit, composed of a lower lithic-rich layer or pod and an upper welded pumice-rich layer. Lithic-rich parts are fines-depleted and are composed of altered country rock, fresh andesite lava, obsidian clasts with chilled margins, and boulders. The overlying Unit B_u shows densely welded stratified facies, composed of alternating lithic-rich and pumice-rich layers. The layers mantle lower units and are sometimes viscously deformed by ballistics. The sedimentary characteristics of Unit B_l such as welded stratified or cross-stratified facies indicate that high temperature dilute pyroclastic density currents were repeatedly generated from limited magma-water interactions. It is thought that dense brittle particles were segregated in a turbulent current and were immediately buried by deposition of hot, lighter pumice-rich particles, and that this process repeated many times. It is also suggested that the depositional temperature of eruptive materials was high and the eruptive style changed from a normal plinian eruption, through surge-generating explosions (Unit B_l), into an agglutinate-dominated fallout eruption (Unit B_u). On the basis of field data, welded pyroclastic surge deposits could be produced only under specific conditions, such as (1) rapid accumulation of pyroclastic particles sufficiently hot to weld instantaneously upon deposition, and (2) elastic particles' interactions with substrate deformation. These physical conditions may be achieved within high temperature and highly energetic pyroclastic density currents produced by large-scale explosive eruptions.     

The Mid-Cenomanian Event in shallow marine environments: Influence on carbonate producers and depositional sequences (northern Aquitaine Basin,France)

The Mid-Cenomanian Event was a positive carbon-isotope (δ¹³C) excursion recorded in hemipelagic basins of the western Tethyan Sea, North to Tropical Atlantic Ocean, and Japan. It is thought of as a prelude to the Oceanic Anoxic Event 2. However, the Mid-Cenomanian Event has never been studied in detail in shallow marine platform deposits and it is not known how it relates to carbonate production and stratigraphic geometry. To better understand how this carbon cycle disruption influenced the neritic biological communities in shallow carbonates during the Cenomanian, a facies, geochemical, diagenetic, and sequence stratigraphic study of the northern Aquitaine platform has been conducted. Seventy-six δ¹³C and δ¹⁸O measurements have been made on micrite, rudists, and diagenetic cements. Fifteen sedimentary facies have been arranged into four depositional environments. Three third-order sequences (C_B, C_C, C_D) are defined from late early Cenomanian to early late Cenomanian and are well correlated with eustatic cycles in European basins. Two peaks of the Mid-Cenomanian Event (MCE1a, +1.2‰, and MCE1b, +1.7‰) have been identified for the first time in shallow marine carbonates. Analysis of diagenetic blocky calcite cements suggests that diagenesis did not affect the δ¹³C of micrite, which can be discussed in terms of the initial signal. The Mid-Cenomanian Event was synchronous with a turnover in neritic carbonate producers marking a transition from photozoan to heterozoan facies. This facies change resulted from the establishment of mesotrophic to eutrophic conditions at the early/mid-Cenomanian transition, reflecting a clear connection between the Mid-Cenomanian Event and neritic biological communities. Depositional geometry and carbonate production varied with δ¹³C during the Mid-Cenomanian Event on the Aquitaine platform. When δ¹³C values were between 2.5‰ and 3‰, the geometry was a flat platform with a high carbonate sedimentation rate leading to the formation of sandbars and rudist bioherms (Accommodation/Sedimentation ratio less than 1, A/S < 1). When the δ¹³C value exceeded 3‰, a carbonate demise occurred and clays and marls were deposited in the lower offshore environment (A/S >> 1). The general carbonate demise affecting the northern Aquitaine platform during the mid-Cenomanian can be explained by both a eustatic sea-level rise and the establishment of eutrophic conditions. The coincidence of the Mid-Cenomanian Event with both (1) the occurrence of mesotrophic to eutrophic conditions marked by carbonate producer turnover from photozoan to heterozoan facies and (2) the transgressive cycles, suggests that eustatic sea-level rise leading to high trophic conditions could explain this positive δ¹³C excursion in the Atlantic and western Tethyan domain. During the mid-Cenomanian, carbon cycle perturbations largely controlled the neritic biological communities on shallow carbonate platforms in a part of the western Tethyan domain.     

Diagenesis of spiculites and carbonates in a Permian temperate ramp succession – Tempelfjorden Group,Spitsbergen, Arctic Norway

This paper explores little investigated diagenesis of spicule‐dominated sediments, based on Permian spiculites and cool‐water carbonates of the Tempelfjorden Group in central Spitsbergen. Field observations, petrography, stable isotope geochemistry, and mineralogical and chemical analyses reveal that the strata have been subjected to multistage diagenesis as the result of silica phase transitions at medium burial depths and deep‐burial overprinting. The growth of silica concretions occurred during the opal‐A/opal‐CT conversion and was controlled by the content and distribution of clay and spicules in the sediment, resulting in a variety of megascopic silica fabrics. Opal‐CT was subsequently dissolved, and all silica is now in a stable quartz stage. Petrographically, the rocks are characterized by a variety of chalcedony and quartz cements which perfectly preserve precursor textures. Most cements precipitated from silica‐oversaturated fluids, and their shapes reflect the silica saturation state and geometry of the pore space. Some microquartz and cryptoquartz also formed by a solid–solid inversion (recrystallization) of chalcedony. The cements have δ ¹⁸O values between +30‰ and +20‰ Standard Mean Ocean Water and display a systematic depletion in ¹⁸O from the first to the last crystallized, interpreted to reflect a gradual increase in temperature during burial. The precipitation of quartz cements started in the Middle Triassic when the strata passed the 19°C isotherm at burial depths of ca 600 m, and was completed in the mid‐Cretaceous, 2·3 km beneath the sea floor at temperatures of 75°C. Late diagenetic overprinting of the chert includes fracturing, brecciation and cementation with carbonate cements having δ ¹⁸O values between +2‰ and −30‰ Pee Dee Belemnite and δ ¹³C values between +4‰ and −14‰ Pee Dee Belemnite; they are linked to hot solutions introduced during Cretaceous volcanism or Palaeogene tectonism. This study illustrates the diagenetic pathway during burial of spicule‐rich sediments in a closed system and thereby provides a baseline for studies of more complexly altered chert deposits.     

Basin‐scale thermal and fluid flow histories revealed by carbonate clumped isotopes (Δ47) – Middle Jurassic carbonates of the Paris Basin depocentre

The reconstruction of past diagenetic conditions in sedimentary basins is often under‐constrained. This results from both the analytical challenge of performing the required analyses on the minute sample amounts available from diagenetic mineral phases and the lack of tracers for some of the diagenetic parameters. The carbonate clumped isotope thermometry (Δ₄₇) opens new perspectives for unravelling the temperatures of diagenetic phases together with the source of their parent fluids, two parameters that are otherwise impossible to constrain in the absence of exploitable fluid inclusions. Here is reported the study of a large number of sedimentary and diagenetic carbonate phases (from Middle Jurassic reservoirs of the Paris Basin depocentre) by combining detailed petrographic observations with a large number of Δ₄₇ data (n  > 45) on a well‐documented paragenetic sequence, including calcite and dolomite burial cements. The data reveal carbonate crystallization at temperatures between 29°C and 98°C from fluids with δ ¹⁸O_water values between −7‰ and +2‰, in response to the progressive burial and uplift of the Paris Basin, throughout 165 Myr of basin evolution. Coupled with the time–temperature evolution previously estimated from thermal maturity modelling, these temperatures allow determining the timing of four successive cementation episodes. The overall data set indicates a history of complex water mixing with a significant contribution of hypersaline waters from the Triassic aquifers migrated upward along faults during the Cretaceous subsidence of the basin. Subsequent large‐scale infiltrations of meteoric waters induced a dilution of these pre‐existing brines in response to the Paris Basin uplift in the Tertiary. Overall, the data presented here allow proposing an integrated approach to characterize the cementation events affecting the studied carbonate reservoir units, based on temperature, oxygen isotope composition and salinity of the parent fluids as well as on petrographic grounds.     

Exploring the impact of diagenesis on (isotope) geochemical and microstructural alteration features in biogenic aragonite

For the Quaternary and Neogene, aragonitic biogenic and abiogenic carbonates are frequently exploited as archives of their environment. Conversely, pre‐Neogene aragonite is often diagenetically altered and calcite archives are studied instead. Nevertheless, the exact sequence of diagenetic processes and products is difficult to disclose from naturally altered material. Here, experiments were performed to understand biogenic aragonite alteration processes and products. Shell subsamples of the bivalve Arctica islandica were exposed to hydrothermal alteration. Thermal boundary conditions were set at 100°C, 175°C and 200°C. These comparably high temperatures were chosen to shorten experimental durations. Subsamples were exposed to different ¹⁸O‐depleted fluids for durations between two and twenty weeks. Alteration was documented using X‐ray diffraction, cathodoluminescence, fluorescence and scanning electron microscopy, as well as conventional and clumped isotope analyses. Experiments performed at 100°C show redistribution and darkening of organic matter, but lack evidence for diagenetic alteration, except in Δ₄₇ which show the effects of annealing processes. At 175°C, valves undergo significant aragonite to calcite transformation and neomorphism. The δ¹⁸O signature supports transformation via dissolution and reprecipitation, but isotopic exchange is limited by fluid migration through the subsamples. Individual growth increments in these subsamples exhibit bright orange luminescence. At 200°C, valves are fully transformed to calcite and exhibit purple‐blue luminescence with orange bands. The δ¹⁸O and Δ₄₇ signatures reveal exchange with the aqueous fluid, whereas δ¹³C remains unaltered in all experiments, indicating a carbonate‐buffered system. Clumped isotope temperatures in high‐temperature experiments show compositions in broad agreement with the measured temperature. Experimentally induced alteration patterns are comparable with individual features present in Pleistocene shells. This study represents a significant step towards sequential analysis of diagenetic features in biogenic aragonites and sheds light on reaction times and threshold limits. The limitations of a study restricted to a single test organism are acknowledged and call for refined follow‐up experiments.     

Multistage hydrothermal dolomites in the Middle Devonian (Givetian) carbonates from the Guilin area, South China

Pervasive dolomites occur preferentially in the stromatoporoid biostromal (or reefal) facies in the basal Devonian (Givetian) carbonate rocks in the Guilin area, South China. The amount of dolomites, however, decreases sharply in the overlying Frasnian carbonate rocks. Dolostones are dominated by replacement dolomites with minor dolomite cements. Replacement dolomites include: (1) fine to medium, planar‐e floating dolomite rhombs (Rd1); (2) medium to coarse, planar‐s patchy/mosaic dolomites (Rd2); and (3) medium to very coarse non‐planar anhedral mosaic dolomites (Rd3). They post‐date early submarine cements and overlap with stylolites. Two types of dolomite cements were identified: planar coarse euhedral dolomite cements (Cd1) and non‐planar (saddle) dolomite cements (Cd2); they post‐date replacement dolomites and predate late‐stage calcite cements that line mouldic vugs and fractures. The replacement dolomites have δ¹⁸O values from ?13·7 to ?9·7‰ VPDB, δ¹³C values from ?2·7 to + 1·5‰ VPDB and ⁸⁷Sr/⁸⁶Sr ratios from 0·7082 to 0·7114. Fluid inclusion data of Rd3 dolomites yield homogenization temperatures (T_h) of 136–149 °C and salinities of 7·2–11·2 wt% NaCl equivalent. These data suggest that the replacive dolomitization could have occurred from slightly modified sea water and/or saline basinal fluids at relatively high temperatures, probably related to hydrothermal activities during the latest Givetian–middle Fammenian and Early Carboniferous times. Compared with replacement dolomites, Cd2 cements yield lower δ¹⁸O values (?14·2 to ?9·3‰ VPDB), lower δ¹³C values (?3·0 to ?0·7‰ VPDB), higher ⁸⁷Sr/⁸⁶Sr ratios (≈ 0·7100) and higher T_h values (171–209 °C), which correspond to trapping temperatures (T_r) between 260 and 300 °C after pressure corrections. These data suggest that the dolomite cements precipitated from higher temperature hydrothermal fluids, derived from underlying siliciclastic deposits, and were associated with more intense hydrothermal events during Permian–Early Triassic time, when the host dolostones were deeply buried. The petrographic similarities between some replacement dolomites and Cd2 dolomite cements and the partial overlap in ⁸⁷Sr/⁸⁶Sr and δ¹⁸O values suggest neomorphism of early formed replacement dolomites that were exposed to later dolomitizing fluids. However, the dolomitization was finally stopped through invasion of meteoric water as a result of basin uplift induced by the Indosinian Orogeny from the early Middle Triassic, as indicated by the decrease in salinities in the dolomite cements in veins (5·1–0·4 wt% NaCl equivalent). Calcite cements generally yield the lowest δ¹⁸O values (?18·5 to ?14·3‰ VPDB), variable δ¹³C values (?11·3 to ?1·2‰ VPDB) and high T_h values (145–170 °C) and low salinities (0–0·2 wt% NaCl equivalent), indicating an origin of high‐temperature, dilute fluids recharged by meteoric water in the course of basin uplift during the Indosinian Orogeny. Faults were probably important conduits that channelled dolomitizing fluids from the deeply buried siliciclastic sediments into the basal carbonates, leading to intense dolomitization (i.e. Rd3, Cd1 and Cd2).     

Meteoric diagenesis and dedolomite fabrics in precursor primary dolomicrite in a mixed carbonate–evaporite system

Dedolomitization is a common diagenetic process in shallow burial environments and is often associated with sulphates in mixed carbonate‐evaporite successions. In these settings, elevated Ca²⁺/Mg²⁺ ratios necessary for dedolomitization result from the dissolution of sulphate phases by the incursion of undersaturated groundwater. Reported dedolomite textures from other studies are varied, but the most prevalent is a rhombic texture interpreted to result from the partial to complete pseudomorphic replacement of secondary dolomite rhombs formed in the burial diagenetic realm. In this study of primary cryptocrystalline to finely crystalline dolomicrites in the Prairie Evaporite Formation of north‐eastern Alberta, dedolomitization has resulted in sutured to loosely packed mosaics of dedolomite that range from subhedral to distinctly euhedral (rhombic) crystal fabrics; however, no prior aggrading neomorphism producing dolomite rhombs is evident in the precursor dolomicrites. Non‐pseudomorphic dedolomitization of the dolomicrites results in textures that include rhombic dedolomite crystals with cloudy cores comprising remnant dolomicrite and clear rims. These textures are similar to those observed in the pseudomorphic dedolomitization of secondary dolomite rhombs. The Prairie Evaporite Formation of north‐eastern Alberta has experienced extensive karstification near the erosional margin of the sedimentary succession. Dedolomitization of dolomicrites occurs in marker beds within the Prairie Evaporite succession associated with evaporite karstification. Along with stratigraphic and petrographic considerations, stable isotope results support the interpretation of a shallow dedolomitization event influenced by meteoric waters derived from the basin margin. Negative δ ¹⁸O and low δ ¹³C values (averages of −13·6‰_VPDB and 0·5‰_VPDB, respectively) of the dedolomite, compared with those of the primary dolomicrite (averages of −6·0‰_VPDB and 1·2‰_VPDB, respectively), point to isotopically light diagenetic fluids. These results show that rhombic dedolomite textures can form through shallow, non‐pseudomorphic dedolomitization of dolomicrites by meteoric fluids in the presence of sulphates, with resulting textures that are similar to the pseudomorphic dedolomitization of secondary dolomite rhombs.     

Hydrothermal Dolomite in the Upper Sinian (Upper Proterozoic) Dengying Formation,East Sichuan Basin,China

Hydrothermal Dolomite （HTD） is present in the Upper Sinian （Upper Proterozoic） Dengying Formation, east Sichuan Basin, China. The strata are comprised by primary dolomite. The HTD has various textures, including zebra dolomite, subhorizontal sheet-like cavities filled by saddle dolomite and breccias cemented by saddle dolomites as well occur as a fill of veins and fractures. Also co-occur MVT type lead-zinc ores in the study area. The δ13C and δ18O isotopes of HTD in the Upper Sinian Dengying Formation are lighter than those of the host rocks, while STSr/86Sr is higher. The apparent difference in carbon, oxygen and strontium isotopes, especially the large difference in S7Sr/S6Sr isotopes ratio indicate crystallization from hot basinal and/or hydrothermal fluids. Saddle dolomite was precipitated at temperatures of 270-320℃. The diagenetic parasequences of mineral assemblage deposited in the Dengying Formation are： （1） dolomite host rock →sphalerite-galena-barite-fluorite; （2） dolomite host rock →saddle dolomite →quartz; （3） dolomite host rock →saddle dolomite→bitumen; （4） dolomite host rock →saddle dolomite →barite. The mean chemical composition of the host dolomite matrix and HTD didn＇t change much during hydrothermal process. The fluids forming the HTDs in the Dengying Formation were mixtures of freshwater from the unconformity at the top of Sinian, fluids from diagenetic compaction and hydrocarbon generation ＆ expulsion from the Lower Cambrian Niutitang Formation mudstones or the Doushantuo Formation silty mudstones, and hydrothermal fluids from the basement. The hydrocarbon reservoirs associated with the HTD were mostly controlled by the basement faults and fractures and karsting processes at the unconformity separating Sinian and Cambrian strata. The hydrocarbon storage spaces of HTD included dissolved cavities and intercrystalline pores. Dissolution cavities are extensive at the top of Dengying Formation, up to about 46m below the unconformity between Sinian an     

The Cerro Morado Andesites: Volcanic history and eruptive styles of a mafic volcanic field from northern Puna, Argentina

The Upper Miocene Cerro Morado Andesites constitutes a mafic volcanic field (100 km²) composed of andesite to basaltic andesite rocks that crop out 75 km to the east from the current arc, in the northern Puna of Argentina. The volcanic field comprises lavas and scoria cones resulting from three different eruptive phases developed without long interruptions between each other. Lavas and pyroclastic rocks are thought to be sourced from the same vents, located where orogen-parallel north-south faults crosscut transverse structures.The first eruptive phase involved the effusion of extensive andesitic flows, and minor Hawaiian-style fountaining which formed subordinate clastogenic lavas. The second phase represents the eruption of slightly less evolved andesite lavas and pyroclastic deposits, only distributed to the north and central sectors of the volcanic field. The third phase represents the discharge of basaltic andesite magmas which occurred as both pyroclastic eruptions and lava effusion from scattered vents distributed throughout the entire volcanic field. The interpreted facies model for scoria cones fits well with products of typical Strombolian-type activity, with minor fountaining episodes to the final stages of eruptions.Petrographic and chemical features suggest that the andesitic units (SiO₂ > 57%) evolved by crystal fractionation. In contrast, characteristics of basaltic andesite rocks are inconsistent with residence in upper-crustal chambers, suggesting that batches of magmas with different origins or evolutive histories arrived at the surface and erupted coevally.Based on the eruptive styles and lack of volcanic quiescence gaps between eruptions, the Cerro Morado Andesites can be classified as a mafic volcanic field constructed from the concurrent activity of several small, probably short-lived, monogenetic centers.     

Criteria for recognition of localization and timing of multiple events of hydrothermal alteration in sandstones illustrated by petrographic,fluid inclusion,and isotopic analysis of the Tera Group,Northern Spain

Stratigraphic relations, detailed petrography, microthermometry of fluid inclusions, and fine-scale isotopic analysis of diagenetic phases indicate a complex thermal history in Tithonian fluvial sandstones and lacustrine limestones of the Tera Group (North Spain). Two different thermal events have been recognized and characterized, which are likely associated with hydrothermal events that affected the Cameros Basin during the mid-Cretaceous and the Eocene. Multiple stages of quartz cementation were identified using scanning electron microscope cathodoluminescence on sandstones and fracture fills. Primary fluid inclusions reveal homogenization temperatures (Th) from 195 to 350°C in the quartz cements of extensional fracture fillings. The high variability of Th data in each particular fluid inclusion assemblage is related to natural reequilibration of the fluid inclusions, probably due to Cretaceous hydrothermal metamorphism. Some secondary fluid inclusion assemblages show very consistent data (Th = 281–305°C) and are considered not to have reequilibrated. They are likely related to an Eocene hydrothermal event or to a retrograde stage of the Cretaceous hydrothermalism. This approach shows how multiple thermal events can be discriminated. A very steep thermal gradient of 97–214°C/km can be deduced from δ¹⁸O values of ferroan calcites (δ¹⁸O −14.2/−11.8‰ V-PDB) that postdate quartz cements in fracture fillings. Furthermore, illite crystallinity data (anchizone–epizone boundary) are out of equilibrium with high fluid inclusion Th. These observations are consistent with heat-flux related to short-lived events of hydrothermal alteration focused by permeability contrasts, rather than to regional heat-flux associated with dynamo-thermal metamorphism. These results illustrate how thermal data from fracture systems can yield thermal histories markedly different from host-rock values, a finding indicative of hydrothermal fluid flow.     

Fluid Inclusion and Stable Isotope Studies at Don Sixto,a Precious Metal Low Sulfidation Deposit in Mendoza Province,Argentina

The Don Sixto mining area in Mendoza province, central‐western Argentina, contains an epithermal low sulfidation Au–Ag deposit. It is a small deposit (～4 km²), with a gold resource of 36 t. In Don Sixto, ore minerals are disseminated in the hydrothermal quartz veins and hydrothermally altered volcanic‐pyroclastic rock units of Permian–Triassic age. On the basis of the texture, ore mineral paragenesis and cross cutting relationship of gangue minerals, seven stages of mineralization were recognized and described. The first six stages are characterized by quartz veins with minor amounts of base metal minerals and the last stage is represented by fluorite veins with minimal quantities of base metal minerals; the precious metal mineralization is mainly related to the fourth stage. The hydrothermal veins exhibit mainly massive, crustiform and comb infilling textures; the presence of bladed quartz replacement textures and quartz veins with adularia crystals are indicative of boiling processes in the system. Fluid inclusion and complementary stable isotope studies were performed in quartz, fluorite, and pyrite samples from the vein systems. The microthermometric data were obtained from primary, biphasic (liquid‐vapor) fluid inclusion assemblages in quartz and fluorite. The maximum values for salinity and homogenization temperature (T_h) came from the stage IV where quartz with petrographic evidence of boiling has average values of 4.96 wt% NaCl_equiv. and 286.9°C respectively. The lower values are related to the last stage of mineralization, where the fluid inclusions in fluorite have average salinities of 1.05 wt% NaCl_equiv. and average homogenization temperatures of 173.1°C. The oxygen and sulfur isotopic fractionation was analyzed in quartz and pyrite. The calculated isotopic fractionation for oxygen in the hydrothermal fluid is in the range of δ¹⁸O_H2O = ?6.92 up to ?3.08‰, which indicates dominance of a meteoric source for the water, while sulfur reaches δ³⁴S_H2S = 1.09‰, which could be reflecting a possible magmatic, or even a mixed source.     

Acid-sulphate Type Alteration and Mineralization in the Desmos Caldera, Manus Back-arc Basin, Papua New Guinea

Abstract: The Onsen acid‐sulphate type of mineralization is located in the Desmos caldera, Manus back‐arc basin. Hydrothermal precipitates, fresh and altered basaltic andesite collected from the Desmos caldera were studied to determine mineralization and mobility of elements under seawater dominated condition of hydrothermal alteration. The mineralization is characterized by three stages of advanced argillic alteration. Alteration stage I is characterized by coarse subhedral pyrophyllite with disseminated anhedral pyrite and enargite which were formed in the temperature range of 260–340°C. Alteration stage II which overprinted alteration stage I was formed in the temperature range of 270–310°C and is characterized by euhedral pyrite, quartz, natroalunite, cristobalite and mixed layer minerals of smectite and mica with 14–15 Å XRD peak. Alteration stage III is characterized by amorphous silica, native sulphur, covellite, marcasite and euhedral pyrite, which has overprinted alteration stages I and II. Relative to the fresh basaltic andesite samples, the rims and cores of the partly altered basaltic andesite samples have very low major, minor and rare earth elements content except for SiO₂ which is much higher (58–78 wt%) than SiO₂ content of the fresh basaltic andesite (55 wt%). REE patterns of the partly altered basaltic andesite specimens are variably depleted in LREE and have pronounced negative Eu anomalies. Normalization of major, minor and REE content of the partly altered basaltic andesites to the fresh basaltic andesite indicates that all the elements except for SiO2 in the partly altered basaltic andesite are strongly lost (e.g. Al₂O₃ = ‐8.3 to ‐10.9 g/100cm³, Ba = ‐2.2 to ‐5.6 mg/100cm³, La = ‐130 to ‐200 μg/100cm³) during the alteration process. Abnormal depletion of MgO, total Fe as Fe₂O₃, LREE especially Eu and enrichment of SiO₂ in the altered basaltic andesites from the Desmos caldera seafloor is caused by interaction of hot acidic hydrothermal fluid, which originates from a mixing of magmatic fluid and seawater.     

Hydrocarbon- and ore-bearing basinal fluids: a possible link between gold mineralization and hydrocarbon accumulation in the Youjiang basin,South China

The Youjiang basin, which flanks the southwest edge of the Yangtze craton in South China, contains many Carlin-type gold deposits and abundant paleo-oil reservoirs. The gold deposits and paleo-oil reservoirs are restricted to the same tectonic units, commonly at the basinal margins and within the intrabasinal isolated platforms and/or bioherms. The gold deposits are hosted by Permian to Triassic carbonate and siliciclastic rocks that typically contain high contents of organic carbon. Paragenetic relationships indicate that most of the deposits exhibit an early stage of barren quartz ± pyrite (stage I), a main stage of auriferous quartz + arsenian pyrite + arsenopyrite + marcasite (stage II), and a late stage of quartz + calcite + realgar ± orpiment ± native arsenic ± stibnite ± cinnabar ± dolomite (stage III). Bitumen in the gold deposits is commonly present as a migrated hydrocarbon product in mineralized host rocks, particularly close to high grade ores, but is absent in barren sedimentary rocks. Bitumen dispersed in the mineralized rocks is closely associated and/or intergrown with the main stage jasperoidal quartz, arsenian pyrite, and arsenopyrite. Bitumen occurring in hydrothermal veins and veinlets is paragenetically associated with stages II and III mineral assemblages. These observations suggest an intimate relationship between bitumen precipitation and gold mineralization. In the paleo-petroleum reservoirs that typically occur in Permian reef limestones, bitumen is most commonly observed in open spaces, either alone or associated with calcite. Where bitumen occurs with calcite, it is typically concentrated along pore/vein centers as well as along the wall of pores and fractures, indicating approximately coeval precipitation. In the gold deposits, aqueous fluid inclusions are dominant in the early stage barren quartz veins (stage I), with a homogenization temperature range typically of 230°C to 270°C and a salinity range of 2.6 to 7.2 wt% NaCl eq. Fluid inclusions in the main and late-stage quartz and calcite are dominated by aqueous inclusions as well as hydrocarbon- and CO₂-rich inclusions. The presence of abundant hydrocarbon fluid inclusions in the gold deposits provides evidence that at least during main periods of the hydrothermal activity responsible for gold mineralization, the ore fluids consisted of an aqueous solution and an immiscible hydrocarbon phase. Aqueous inclusions in the main stage quartz associated with gold mineralization (stage II) typically have a homogenization temperature range of 200–230°C and a modal salinity around 5.3 wt% NaCl eq. Homogenization temperatures and salinities of aqueous inclusions in the late-stage drusy quartz and calcite (stage III) typically range from 120°C to 160°C and from 2.0 to 5.6 wt% NaCl eq., respectively. In the paleo-oil reservoirs, aqueous fluid inclusions with an average homogenization temperature of 80°C are dominant in early diagenetic calcite. Fluid inclusions in late diagenetic pore- and fissure-filling calcite associated with bitumen are dominated by liquid C₂H₆, vapor CH₄, CH₄–H₂O, and aqueous inclusions, with a typical homogenization temperature range of 90°C to 180°C and a salinity range of 2–8 wt% NaCl eq. It is suggested that the hydrocarbons may have been trapped at relatively low temperatures, while the formation of gold deposits could have occurred under a wider and higher range of temperatures. The timing of gold mineralization in the Youjiang basin is still in dispute and a wide range of ages has been reported for individual deposits. Among the limited isotopic data, the Rb–Sr date of 206 ± 12 Ma for Au-bearing hydrothermal sericite at Jinya as well as the Re–Os date of 193 ± 13 Ma on auriferous arsenian pyrite and ⁴⁰Ar/³⁹Ar date of 194.6 ± 2 Ma on vein-filling sericite at Lannigou may provide the most reliable age constraints on gold mineralization. This age range is comparable with the estimated petroleum charging age range of 238–185 Ma and the Sm–Nd date of 182 ± 21 Ma for the pore- and fissure-filling calcite associated with bitumen at the Shitouzhai paleo-oil reservoir, corresponding to the late Indosinian to early Yanshanian orogenies in South China. The close association of Carlin-type gold deposits and paleo-oil reservoirs, the paragenetic coexistence of bitumens with ore-stage minerals, the presence of abundant hydrocarbons in the ore fluids, and the temporal coincidence of gold mineralization and hydrocarbon accumulation all support a coeval model in which the gold originated, migrated, and precipitated along with the hydrocarbons in an immiscible, gold- and hydrocarbon-bearing, basinal fluid system.     

Diagenetic evolution of the volcaniclastic deposits: an example from Neoproterozoic Dokhan Volcanics in Wadi Queih basin,central Eastern Desert,Egypt

Wadi Queih basin hosts a ～2,500-m thick Neoproterozoic volcanoclastic successions that unconformably lie over the oldest Precambrian basement. These successions were deposited in alluvial fan, fluviatile, lacustrine, and aeolian depositional environments. Diagenetic minerals from these volcaniclastic successions were studied by X-ray diffractometry, scanning electron microscopy, and analytical electron microscopy. The diagenetic processes recognized include mechanical compaction, cementation, and dissolution. Based on the framework grain–cement relationships, precipitation of the early calcite cement was either accompanied or followed by the development of part of the pore-lining and pore-filling clay cements. Secondary porosity development occurred due to partial to complete dissolution of early calcite cement and feldspar grains. In addition to calcite, several different clay minerals including kaolinite, illite, and chlorite with minor smectite occur as pore-filling and pore-lining cements. Chlorite coating grains helps to retain primary porosity by retarding the envelopment of quartz overgrowths. Clay minerals and their diagenetic assemblages has been distinguished between primary volcaniclastics directly produced by pyroclastic eruptions and epiclastic volcaniclastics derived from erosion of the pre-existing volcanic rocks. Phyllosilicates of the epiclastic rocks display wider compositional variations owing to wide variations in the mineralogical and chemical compositions of the parent material. Most of the phyllosilicates (kaolinite, illite, chlorite, mica, and smectite) are inherited minerals derived from the erosion of the volcanic basement complex, which had undergone hydrothermal alteration. Smectites of the epiclastic rocks are beidellite–montmorillonite derived from the altered volcanic materials of the sedimentary environment. Conversely, phyllosilicate minerals of the pyroclastic rocks are dominated by kaolinite, illite, and mica, which were formed by pedogenetic processes through the hydrothermal influence.     

Geochemistry of carbonate cements in the Sag River and Shublik Formations (Triassic/Jurassic), North Slope, Alaska: implications for the geochemical evolution of formation waters

Carbonate cements (calcite, siderite, dolomite, and ankerite) formed throughout the diagenetic history of the Sag River and Shublik Formations. The trace element and isotopic geochemistry of these cements varies as a function of the timing of precipitation. Earliest calcites, formed prior to significant compaction of the sediment, are relatively enriched in Mg (up to 4·4 mol%), and have ⁸⁷Sr/⁸⁶Sr values (mean = 0·707898) compatible with the original marine pore waters. Later calcites are relatively Fe-rich (up to 5·0 mol%) and are characterized by increasing ⁸⁷Sr/⁸⁶Sr values (up to 0·712823) and Sr content with decreasing age. The Fe content of zoned siderite and dolomite/ankerite rhombs increases towards the outside of the rhombs (i.e. increasing Fe content with decreasing age). These geochemical variations appear principally to result from changes in pore-water chemistry during diagenesis. The increase in ⁸⁷Sr/⁸⁶ Sr and Sr content of the cements is most likely due to interaction between pore waters and ⁸⁷ Sr-rich clay and possibly feldspar in Ellesmerian mudrocks (whole rock ⁸⁷Sr/⁸⁶ Sr signatures for the mudrocks are > 0·716). Pore-water Fe²⁺ concentration was probably controlled by diagenetic alterations involving Fe-bearing minerals (e.g. pyrite precipitation). A reconnaissance examination of carbonate cements in the overlying Kingak Shale indicates that similar alterations occurred in the Kingak. The low δ¹⁸ O value of some calcite cements (-11·96% PDB) suggests that an influx of meteoric water may have occurred in the mid-Neocomian, though the low value could also result from an abnormally high geothermal gradient associated with mid-Neocomian rifting.     

Dolomitization by hypersaline reflux into dense groundwaters as revealed by vertical trends in strontium and oxygen isotopes: Upper Muschelkalk,Switzerland

The Trigonodus Dolomit is the dolomitized portion of the homoclinal ramp sediments of the Middle Triassic Upper Muschelkalk in the south‐east Central European Basin. Various dolomitizing mechanisms, followed by recrystallization, have been previously invoked to explain the low δ¹⁸O, high ⁸⁷Sr/⁸⁶Sr, extensive spatial distribution and early nature of the replacive matrix dolomites. This study re‐evaluates the origin, timing and characteristics of the dolomitizing fluids by examining petrographic and isotopic trends in the Trigonodus Dolomit at 11 boreholes in northern Switzerland. In each borehole the ca 30 m thick unit displays the same vertical trends with increasing depth: crystal size increase, change from anhedral to euhedral textures, ultraviolet‐fluorescence decrease, δ¹⁸O_VPDB decrease from ?1·0‰ at the top to ?6·7‰ at the base and an ⁸⁷Sr/⁸⁶Sr increase from 0·7080 at the top to 0·7117 at the base. Thus, dolomites at the top of the unit record isotopic values similar to Middle Triassic seawater (δ¹⁸O_VSMOW = 0‰; ⁸⁷Sr/⁸⁶Sr = 0·70775) while dolomites at the base record values similar to meteoric groundwaters from the nearby Vindelician High (δ¹⁸O_VSMOW = ?4·0‰; ⁸⁷Sr/⁸⁶Sr = >0·712). According to water–rock interaction modelling, a single dolomitizing or recrystallizing fluid cannot have produced the observed isotopic trends. Instead, the combined isotopic, geochemical and petrographic data can be explained by dolomitization via seepage‐reflux of hypersaline brines into dense, horizontally‐advecting groundwaters that already had negative δ¹⁸O and high ⁸⁷Sr/⁸⁶Sr values. Evidence for the early groundwaters is found in meteoric calcite cements that preceded dolomitization and in fully recrystallized dolomites with isotopic characteristics identical to the groundwaters following matrix dolomitization. This study demonstrates that early groundwaters can play a decisive role in the formation and recrystallization of massive dolomites and that the isotopic and textural signatures of pre‐existing groundwaters can be preserved during seepage‐reflux dolomitization in low‐angle carbonate ramps.