The origins of salinity in metamorphic fluids

Evaluation of data on formation waters and metamorphic fluids sampled by drilling or preserved in fluid inclusions reveals little correlation between fluid salinity and metamorphic grade, but a strong link to original sedimentary setting. Sediments and metasediments deposited originally in shallow marine environments can contain fluids with a very wide range of salinities, but they are commonly near twice seawater salinity or higher. With increasing metamorphic grade, a very wide range of salinities may develop, with the highest levels tracking halite saturation. Oceanic and accretionary prism sequences yield low‐salinity fluids, close to seawater values, almost irrespective of metamorphic grade until extreme conditions are reached where removal of water may increase fluid salinity. The salinities of metamorphic fluids exert a fundamental control on both fluid phase equilibria and metal‐transporting capability, and appear, to a large degree, to reflect the original presence or absence of highly saline formation waters and/or evaporites in the initial sedimentary sequence.     

Large‐scale chemical stratification of fluids in the crust: hydraulic and chemical data from the geothermal research site Urach,Germany

The Urach 3 research borehole in SW Germany has been drilled through a sedimentary cover sequence and reached gneisses of the Variscan crystalline basement at 1604 m below surface. An additional 2840 m has been drilled through fractured basement rocks. The borehole has been used for hydraulic tests in the context of a ‘hot dry rock’ (HDR) project. The sedimentary cover ranges from the Carboniferous to the Middle Jurassic (Dogger) in age and comprises mostly clastic sediments in the Paleozoic and limestone and shale in the Mesozoic. Water composition data from 10 different depths include samples from all major lithological units. The total dissolved solids (TDS) increases from the surface to about 650 m where it reaches 4.1 g l^?1 in Triassic limestone. In lower Triassic sandstones, TDS increases very sharply to 28.5 g l^?1 and the water is saturated with pure CO₂ gas. With increasing depth, TDS does not change much in the clastic sediments of the Permian and Carboniferous. The crystalline basement is marked by a very sharp increase in TDS to 55.5 g l^?1 at about 1770 m depth. TDS increases within the basement to more than 78.5 g l^?1 at about 3500 m depth. The data suggest that there is limited vertical chemical communication over long periods of time. The CO₂ gas cap in the lower Triassic sandstones requires a gastight cover. The chemical stratification of the fluids relates to the permeability structure of the crust at the Urach site and fits well with hydraulic and thermal data from the site.     

Role of compressive tectonics on gas charging into the Ordovician sandstone reservoirs in the Sbaa Basin,Algeria: constrained by fluid inclusions and mineralogical data

Structure‐ and tectonic‐related gas migration into Ordovician sandstone reservoirs and its impact on diagenesis history were reconstructed in two gas fields in the Sbaa Basin, in SW Algeria. This was accomplished by petrographical observations, fluid inclusion microthermometry and stable isotope geochemistry on quartz, dickite and carbonate cements and veins. Two successive phases of quartz cementation (CQ1 and CQ2) occurred in the reservoirs. Two phase aqueous inclusions show an increase in temperatures and salinities from the first CQ1 diagenetic phase toward CQ2 in both fields. Microthermometric data on gas inclusions in quartz veins reveal the presence of an average of 92 ± 5 mole% of CH₄ considering a CH₄‐CO₂ system, which is similar to the present‐day gas composition in the reservoirs. The presence of primary methane inclusions in early quartz overgrowths and in quartz and calcite veins suggests that hydrocarbon migration into the reservoir occurred synchronically with early quartz cementation in the sandstones located near the contact with the Silurian gas source rock at 100–140°C during the Late Carboniferous period and the late Hercynian episode fracturing at temperatures between 117 and 185°C, which increased in the NW‐direction of the basin. During the fracture filling, three main types of fluids were identified with different salinities and formation temperatures. A supplementary phase of higher fluid temperature (up to 226°C) recorded in late quartz, and calcite veins is related to a Jurassic thermal event. The occurrence of dickite cements close to the Silurian base near the main fault areas in both fields is mainly correlated with the sandstones where the early gas was charged. It implies that dickite precipitation is related to acidic influx. Late carbonate cements and veins (calcite – siderite – ankerite and strontianite) occurred at the same depths resulting from the same groundwater precipitation. The absence of methane inclusions in calcite cements result from methane flushing by saline waters.     

Chemical evolution of metamorphic fluids in the Central Alps,Switzerland: insight from LA‐ICPMS analysis of fluid inclusions

The chemical evolution of fluids in Alpine fissure veins (open cavities with large free‐standing crystals) has been studied by combination of fluid inclusion petrography, microthermometry, LA‐ICPMS microanalysis, and thermodynamic modeling. The quartz vein systems cover a metamorphic cross section through the Central Alps (Switzerland), ranging from subgreenschist‐ to amphibolite‐facies conditions. Fluid compositions change from aqueous inclusions in subgreenschist‐ and greenschist‐facies rocks to aqueous–carbonic inclusions in amphibolite‐facies rocks. The fluid composition is constant for each vein, across several fluid inclusion generations that record the growth history of the quartz crystals. Chemical solute geothermometry, fluid inclusion isochores, and constraints from fluid–mineral equilibria modeling were used to reconstruct the pressure–temperature conditions of the Alpine fissure veins and to compare them with the metamorphic path of their host rocks. The data demonstrate that fluids in the Aar massif were trapped close to the metamorphic peak whereas the fluids in the Penninic nappes record early cooling, consistent with retrograde alteration. The good agreement between the fluid–mineral equilibria modeling and observed fluid compositions and host‐rock mineralogy suggests that the fluid inclusions were entrapped under rock‐buffered conditions. The molar Cl/Br ratios of the fluid inclusions are below the seawater value and would require unrealistically high degrees of evaporation and subsequent dilution if they were derived from seawater. The halogen data may thus be better explained by interaction between metamorphic fluids and organic matter or graphite in metasedimentary rocks. The volatile content (CO₂, sulfur) in the fluid inclusions increases systematically as function of the metamorphic grade, suggesting that the fluids have been produced by prograde devolatilization reactions. Only the fluids in the highest grade rocks were partly modified by retrograde fluid–rock interactions, and all major element compositions reflect equilibration with the local host rocks during the earliest stages of postmetamorphic uplift.     

Fluid evolution along multistage composite fault systems at the southern margin of the Lower Palaeozoic Anglo-Brabant fold belt, Belgium

Mineralised vein systems have been investigated at nine localities at the southern margin of the Anglo‐Brabant fold belt in Belgium. During the late Silurian to early Middle Devonian Caledonian orogeny, shear zones formed, inferred to be associated with granitoid basement blocks in the subsurface. The circulation of a metamorphic fluid, possibly originating in the Cambrian core of the fold belt, along these shear zones resulted in the formation of mesozonal orogenic mineralisation at the southern margin of the Anglo‐Brabant fold belt. The fluid had a composition dominated by H₂O–CO₂–X–NaCl–KCl. The shear zones form part of a greater fault zone, the Nieuwpoort–Asquempont fault zone, which is characterised by normal faulting that started before the Givetian and by the reactivation of the shear zones. Two fluid generations are associated with this normal faulting. First, a low salinity H₂O–NaCl(–KCl) fluid migrated through the Palaeozoic rocks after the Silurian. Based on the isotopic composition, this fluid could be a late‐metamorphic Caledonian fluid or a younger fluid that originated from the Rhenohercynian basin and interacted with Lower Devonian rocks along its migration path. Second, a high salinity H₂O–NaCl–CaCl₂ fluid was identified in the fault systems. Similar fluids have been found in southern and eastern Belgium, where they produced Mississippi Valley‐type Zn–Pb deposits. These fluids are interpreted as evaporative brines that infiltrated the Lower Palaeozoic basement, from where they were expelled during extensional tectonism in the Mesozoic.     

Controls on fluid movement in crustal lithologies: evidence from zircon in metaconglomerates from Shetland

An investigation of the morphology of zircon in clasts and matrix of a greenschist facies metaconglomerate from Shetland has revealed a history of alteration of radiation‐damaged grains, partial dissolution and growth of new zircon. These processes are linked to the generation of chemically modified dark backscattered electron (BSE) zircon that is spatially related to fractures generated during radiation damage; embayments and rounding of zircon margins; and late overgrowths of original grains. These late modifications of zircon are all linked to the presence of fluids and so zircon morphology is used to track fluid behaviour in different lithologies in the metaconglomerate. Alteration is unrelated to clast margins and radically different in various clast types. This reflects a difference in permeability and suggests that deformation strongly controls fluid influx into quartzite, whereas zircon alteration in granite is associated with a restricted permeability reflecting the more limited response to deformation events.     

Metamorphic and basin fluids in quartz–carbonate–sulphide veins in the SW Scottish Highlands: a stable isotope and fluid inclusion study

Metalliferous (Fe–Cu–Pb–Zn) quartz–carbonate–sulphide veins cut greenschist to epidote–amphibolite facies metamorphic rocks of the Dalradian, SW Scottish Highlands, with NE–SW to NW–SE trends, approximately parallel or perpendicular to regional structures. Early quartz was followed by pyrite, chalcopyrite, sphalerite, galena, barite, late dolomite–ankerite and clays. Both quartz–sulphide and carbonate vein mineralisation is associated with brecciation, indicating rapid release of fluid overpressure and hydraulic fracturing. Two distinct mineralising fluids were identified from fluid inclusion and stable isotope studies. High temperature (>350°C) quartz‐precipitating fluids were moderately saline (4.0–12.7 wt.% NaCl equivalent) with low (approximately 0.05). Quartz δ¹⁸O (+11.7 to +16.5‰) and sulphide δ³⁴S (?13.6 to ?1.1‰) indicate isotopic equilibrium with host metasediments (rock buffering) and a local metasedimentary source of sulphur. Later, low‐temperature (T_H = 120–200°C) fluids, probably associated with secondary carbonate, barite and clay formation, were also moderately saline (3.8–9.1 wt.% NaCl equivalent), but were strongly enriched in ¹⁸O relative to host Dalradian lithologies, as indicated by secondary dolomite–ankerite (δ¹⁸O = +17.0 to +29.0‰, δ¹³C = ?1.0 to ?3.0‰). Compositions of carbonate–forming fluids were externally buffered. The veins record the fluid–rock interaction history of metamorphic host rocks during cooling, uplift and later extension. Early vein quartz precipitated under retrograde greenschist facies conditions from fluids probably derived by syn‐metamorphic dehydration of deeper, higher‐grade rocks during uplift and cooling of the Caledonian metamorphic complex. Veins are similar to those of mesothermal veins in younger Phanerozoic metamorphic belts, but are rare in the Scottish Dalradian. Early quartz veins were reactivated by deep penetration of low‐temperature basin fluids that precipitated carbonate and clays in veins and adjacent Dalradian metasediments throughout the SW Highlands, probably in the Permo‐Carboniferous. This event is consistent with paragenetically ambiguous barite with δ³⁴S characteristic of late Palaeozoic basinal brines.     

Apatite grain boundary morphology and its response to low-temperature fluid infiltration in crystalline basement

Apatite grain boundaries on fractured rock surfaces have been examined in an amphibolite facies regional metamorphic granite gneiss from the central Swiss Alps. The morphology of apatite has been characterized using a scanning electron microscope and matched to surface textures in adjoining silicates. Apatites show a wide variety of different surface features ranging from planar crystal faces, to small-scale ridges and dimples, to extensive irregular pitting. Many of these features form in response to the periodic infiltration of fluids along open grain boundaries during the cooling history of the gneiss. Apatite shows evidence of both dissolution and re-precipitation that is controlled by the nature of the grain boundary, the structure of the adjoining silicate phase and the alteration of the host rock. Fracturing occurs in a range of retrograde conditions and is common both within the apatite and along grain boundaries. This coupled to the evidence of fluid interaction with mineral surfaces suggests that extensive permeable networks may be typical of cooling crystalline basement rocks. Grain boundary textures have the potential to reveal a unique record of fluid infiltration in the crust that would be very difficult to decipher using traditional petrographic methods.     

Fluids,basin analysis,and mineral deposits

Sedimentary basins are the largest structures on the surface of our planet and the most significant sources of energy‐related commodities. With time, sedimentary successions in basins normally are subjected to increasingly intense diagenesis that results in differential evolution of basin hydrology. This hydrologic structure is in turn vitally important in determining how and where deposition of metals may occur. Fluids in all basins originate and flow as a result of sedimentological and tectonic events, so that fluid histories should reflect the control of both lithology and tectonism on ore deposition. Sandstone lithologies, in particular, reflect fluid‐flow events because they are normally the major aquifers in basins. However, early cementation results in occlusion of primary permeability in some facies (diagenetic aquitards) whereas in others, permeability develops due to the dissolution of unstable grains (diagenetic aquifers). Particularly for ore deposits in Precambrian basins, identification of paleohydrologic systems during basin evolution requires the integration of data derived from tectonics, sedimentology, stratigraphy, diagenesis, geochemistry and geology. Assessment of all these data is a prerequisite for the ‘holistic basin analysis’ needed to guide the search for basin‐hosted ores. Recent results from the Paleoproterozoic Mt Isa and McArthur basins in northern Australia serve as a template for exploring for mineral deposits in basins. Basinal fluids were saline, 200–300°C and evolved primarily from meteoric water in the Mt Isa Basin and from seawater in the McArthur Basin during burial to depths of 4–12 km. The δD_fluid and δ¹⁸O_fluid values in these brines were isotopically identical to those in the Zn‐Pb, Cu and U deposits. Geochemical changes of various lithologies during alteration support detrital minerals as the major source of the U, and volcanic units proximal to diagenetic aquifers as a source for the transition metals. Ages of diagenetic phases extracted from aquifer lithologies reveal that fluid migration from the diagenetic aquifers effectively covers the period of formation for U, Zn‐Pb and Cu mineralization, and that the deposits formed in response to tectonic events reflected in the apparent polar wandering path for the area. Sequence stratigraphic analysis and models of fluid flow also indicate that basinal reservoirs were likely sources for the mineralizing fluids. Thus, diagenetic aquifer lithologies were being drained of fluids at the same time as the deposits were forming from fluids that were chemically and isotopically similar, linking diagenesis and fluid events within the basin to the formation of the deposits.     

Principal features of impact-generated hydrothermal circulation systems: mineralogical and geochemical evidence

Any hypervelocity impact generates a hydrothermal circulation system in resulting craters. Common characteristics of hydrothermal fluids mobilized within impact structures are considered, based on mineralogical and geochemical investigations, to date. There is similarity between the hydrothermal mineral associations in the majority of terrestrial craters; an assemblage of clay minerals–zeolites–calcite–pyrite is predominant. Combining mineralogical, geochemical, fluid inclusion, and stable isotope data, the distinctive characteristics of impact‐generated hydrothermal fluids can be distinguished as follows: (i) superficial, meteoric and ground water and, possibly, products of dehydration and degassing of minerals under shock are the sources of hot water solutions; (ii) shocked target rocks are sources of the mineral components of the solutions; (iii) flow of fluids occurs mainly in the liquid state; (iv) high rates of flow are likely (10^?4 to 10^?3 m s^?1); (v) fluids are predominantly aqueous and of low salinity; (vi) fluids are weakly alkaline to near‐neutral (pH 6–8) and are supersaturated in silica during the entire hydrothermal process because of the strong predominance of shock‐disordered aluminosilicates and fusion glasses in the host rocks; and (vii) variations in the properties of the circulating solutions, as well as the spatial distribution of secondary mineral assemblages are controlled by temperature gradients within the circulation cell and by a progressive cooling of the impact crater. Products of impact‐generated hydrothermal processes are similar to the hydrothermal mineralization in volcanic areas, as well as in modern geothermal systems, but impacts are always characterized by a retrograde sequence of alteration minerals.     

Long‐term chemical evolution and modification of continental basement brines – a field study from the Schwarzwald,SW Germany

Highly saline, deep‐seated basement brines are of major importance for ore‐forming processes, but their genesis is controversial. Based on studies of fluid inclusions from hydrothermal veins of various ages, we reconstruct the temporal evolution of continental basement fluids from the Variscan Schwarzwald (Germany). During the Carboniferous (vein type i), quartz–tourmaline veins precipitated from low‐salinity (<4.5wt% NaCl + CaCl₂), high‐temperature (≤390°C) H₂O‐NaCl‐(CO₂‐CH₄) fluids with Cl/Br mass ratios = 50–146. In the Permian (vein type ii), cooling of H₂O‐NaCl‐(KCl‐CaCl₂) metamorphic fluids (T ≤ 310°C, 2–4.5wt% NaCl + CaCl₂, Cl/Br mass ratios = 90) leads to the precipitation of quartz‐Sb‐Au veins. Around the Triassic–Jurassic boundary (vein type iii), quartz–haematite veins formed from two distinct fluids: a low‐salinity fluid (similar to (ii)) and a high‐salinity fluid (T = 100–320°C, >20wt% NaCl + CaCl₂, Cl/Br mass ratios = 60–110). Both fluids types were present during vein formation but did not mix with each other (because of hydrogeological reasons). Jurassic–Cretaceous veins (vein type iv) record fluid mixing between an older bittern brine (Cl/Br mass ratios ~80) and a younger halite dissolution brine (Cl/Br mass ratios >1000) of similar salinity, resulting in a mixed H₂O‐NaCl‐CaCl₂ brine (50–140°C, 23–26wt% NaCl + CaCl₂, Cl/Br mass ratios = 80–520). During post‐Cretaceous times (vein type v), the opening of the Upper Rhine Graben and the concomitant juxtaposition of various aquifers, which enabled mixing of high‐ and low‐salinity fluids and resulted in vein formation (multicomponent fluid H₂O‐NaCl‐CaCl₂‐(SO₄‐HCO₃), 70–190°C, 5–25wt% NaCl‐CaCl₂ and Cl/Br mass ratios = 2–140). The first occurrence of highly saline brines is recorded in veins that formed shortly after deposition of halite in the Muschelkalk Ocean above the basement, suggesting an external source of the brine's salinity. Hence, today's brines in the European basement probably developed from inherited evaporitic bittern brines. These were afterwards extensively modified by fluid–rock interaction on their migration paths through the crystalline basement and later by mixing with younger meteoric fluids and halite dissolution brines.     

Solubility of corundum + kyanite in H2O at 700°C and 10 kbar: evidence for Al‐Si complexing at high pressure and temperature

The solubility of the assemblage corundum + kyanite in H₂O was determined at 700°C and 10 kbar, using a piston‐cylinder apparatus and rapid‐quench/fluid‐extraction techniques. Weighted mean concentrations of total Al and Si were 5.80 ± 0.03 mmol kg^?1 H₂O and 0.308 ± 0.003 mol kg^?1 H₂O, respectively (1σ errors). The Al concentration is nearly five times higher than that of corundum solubility in pure H₂O. This difference is interpreted to arise from complexing between Si and Al to form HAlSiO_4,aq species. Charged or more polymerized species are also possible, but their abundance cannot be constrained based on these experiments. Assumption of a single aqueous aluminosilicate complex permits calculation of the thermodynamic consequences of Al‐Si interaction in high‐pressure fluids, as well as phase diagrams for the system Al‐Si‐O‐H. Formation of Al‐Si complexes leads to a large increase in dissolved Al with increasing Si in solution, such that Al concentration in equilibrium with kyanite + quartz is predicted to be 7.1 mmolal, higher than with kyanite + corundum. The elevated concentration of Si in deep‐crustal and mantle aqueous fluids suggests that Al must readily be dissolved and transported by Al‐Si complexing in high‐pressure metamorphic and metasomatic environments. The results provide a simple explanation for the common observation of kyanite + quartz segregations in eclogites and Barrovian metamorphic rocks.     

Geodynamically induced variations in the emission of CO2 gas at San Faustino (Central Apennines,Italy)

The Central Apennines are affected by frequent earthquakes of moderate magnitude that occur mainly within the upper part of the crust at depths of <15 km. A large number of cold gas emissions that are rich in CO₂ are also found in the region. One particular vent with a high rate of degassing was equipped with a sensor to measure flow rates, which were recorded for a number of different periods between 2005 and 2010. Factors that could affect potentially CO₂ flow rates include barometric pressure, atmospheric temperature, precipitation and local seismicity. Our analysis indicates that the periods of anomalous flow rate were related not to the environmental factors but probably to the deformative processes of the crust associated with the local seismicity. Local seismic events as expression of geodynamic processes occurred always before and during these anomalous gas flow periods. This correlation exists only for events that occurred eastwards of the gas emission site close to the Martana fault zone. We herein consider this correlation as indication for a continuous interaction between the field of static strain and the deep fluid pressure. An approximation of the fluid pressure transmission towards the gas emission site gives reasonable values of 1–10 m² sec^?1. To make comparisons with the long‐term effects of the static strain, we also recorded the short‐term effects of the dynamic release of strain induced by the series of strong earthquakes that took place in L’Aquila in 2009. We detected a significant anomalous flow rate that occurred at the same time as this seismic sequence, during which widespread degassing was induced around the focal zone.     

Fluid trapping at the brittle–ductile transition re-examined

The brittle–ductile transition has been suggested to provide a mechanical trap to deep crustal fluids. The mechanism was advanced as a way of reconciling the geophysical case for a wet lower crust, founded on the revelation of deep crustal electrical conductors and seismic reflectors, with the problem of maintaining interconnected, low‐density fluids in stable crust for geologically significant timescales. Although some deep crustal conductors are now attributed to graphite, the hypothesis of fluid trapping at the brittle–ductile transition has been widely adopted in electromagnetic literature, with no regard to tectonic regime, and in association with standardized temperatures of 300–450°C. Meanwhile, petrologists continue to argue that the lower crust is dry. This paper re‐examines the arguments on which the hypothesis of fluid trapping at the brittle–ductile transition has been founded, and concludes that there is a geophysical case for a dry lower crust based on electromagnetic studies. The magnetotelluric (MT) technique yields electrical conductances (conductivity–thickness products) that are direction dependent (or anisotropic). The necessity of considering direction‐dependent conductances, rather than a bulk conductance, is demonstrated using data from Saxothuringia, Germany. A quantitative model is developed to facilitate joint interpretation of the maximum conductance and the anisotropy of conductance (ratio of maximum to minimum conductance). The model yields quantitative arguments against fluids being the principal cause of deep crustal electrical conductivity, because unreasonably thick layers and unreasonably high porosities are required.     

Bodies that sweat: the affective responses of young women in Wollongong,New South Wales,Australia

I argue that people's bodily sensations of sweat – smell, touch and sight – can provide insights to the relations between subjectivity and space. I draw on feminist ideas of the body as a physiological, psychological and sociological assemblage out of which spatially situated knowledge, ethics, subjectivities and social relations are forged. Empirical evidence is drawn from self-reflexive accounts of 21 young women living in Wollongong, New South Wales, Australia. Their narratives convey how sweat and sweatiness are integral to negotiating everyday life. First, participants' narratives illustrate the way the sweaty body-as-seen is bound up with gendered identities and self-disgust. Second, visceral experiences of the materialities of sweat and sweatiness often give rise to a heightened sense of bodily awareness, self and spatial marginalisation in the course of everyday lives. Third, participants' narratives highlight the tensions of spatial experience of sweat and sweatiness that simultaneously attract and repel bodies. Visceral experiences of sweat and sweatiness are central to better understanding of the spatiality of subjectivity.     

Chemical profiling of a 130-year-old manuscript reveals the early use of synthetic lead white correction fluid in ancient China

In practice, correction fluid to mask text errors has been continuously in demand since papers began to be predominantly used since the late fourth century AD in ancient China. However, research on the trajectory of correction fluid composition has been largely overlooked and has not been revealed currently. In this study, a multianalytical approach was used to investigate a thin whiteout layer, used as correction fluids applied in 1890, on a book page from the famous Imperial Encyclopedia (1726 bronze-type repaint version). The results showed that the white layer was composed of hydrocerussite ((PbCO₃)₂·Pb (OH)₂) in mixture with plant oil and a tiny portion of calcium carbonate, which had been applied to conceal the originally printed Chinese characters upon which they were rewritten in preparing photographic negatives for reprinting using photolithography. The analysis results also suggest that lead white was likely domestically made using a local lead ore source by the wet synthetic process. Considering the prolonged use of orpiment (As₂S₃) as a correction fluid ingredient in Chinese tradition, a trajectory to lead white suggests not only advances in pulping and papermaking technology but also a shift in cultural habits and aesthetic psychology in the late Qing Dynasty.     

Evidence for SiO2‐NaCl complexing in H2O‐NaCl solutions at high pressure and temperature

Experimental studies reveal complex dissolution behavior of quartz in aqueous NaCl solutions at high temperature and pressure, involving variation from salting‐in to salting‐out that changes with temperature, pressure, and salt concentration. The behavior is not explainable by traditional electrostatic theory. An alternative hypothesis appeals to complexing of SiO₂ with NaCl and can explain the observations. However, the hypothesis of complexing, as previously applied, is inadequate in several respects: it neglects polymerization of solute silica, regards the SiO₂‐NaCl hybrid complex(es) as anhydrous, which seems unlikely, and invokes an incorrect stoichiometry of the hydrated silica monomer, now known to be Si(OH)₄?2H₂O. These neglected features can be incorporated into the complexing model in a revised formulation based on a simple thermodynamic analysis using existing quartz solubility data. The analysis leads to a quasi‐ideal solution model with silica monomers, dimers, and two distinct hydrous SiO₂‐NaCl hybrid complexes with overall NaCl:H₂O = 1:6, one Na‐bearing and one Cl‐bearing. Their (equal) molar concentrations (X_hc) are governed by a pressure‐ and temperature‐dependent equilibrium constant, , where a_Nacl and are the respective activities of the solvent components. The stability of the hybrid complexes (i.e., their concentration) is very sensitive to H₂O activity. The entire set of experimental quartz‐solubility data at 700°C, 1–15 kbar, is reproduced with high fidelity by the expression (P is pressure in kbar), including the transition from low‐pressure salting‐in to high pressure salting‐out. The results indicate that hybrid SiO₂‐NaCl complexes are the main hosts for dissolved silica at NaCl concentrations greater than 6 wt%, which are likely common in crustal fluids. At higher temperatures, approaching the critical end point in the system SiO₂‐H₂O, the model becomes progressively inaccurate, probably because polymers higher than the dimer become significant as SiO₂ concentration increases.     

Invasion of a karst aquifer by hydrothermal fluids: evidence from stable isotopic compositions of cave mineralization

Mineral deposits in the Cupp‐Coutunn/Promeszutochnaya cave system (Turkmenia, central Asia) record a phase of hydrothermal activity within a pre‐existing karstic groundwater conduit system. Hydrothermal fluids entered the caves through fault zones and deposited sulphate, sulphide and carbonate minerals under phreatic conditions. Locally, intense alteration of limestone wall rocks also occurred at this stage. Elsewhere in the region, similar faults contain economic quantities of galena and elemental sulphur mineralization. Comparisons between the Pb and S isotope compositions of minerals found in cave and ore deposits confirm the link between economic mineralization and hydrothermal activity at Cupp‐Coutunn. The predominance of sulphate mineralization in Cupp‐Coutunn implies that the fluids were more oxidized in the higher permeability zone associated with the karst aquifer. A slight increase in the δ³⁴S of sulphate minerals and a corresponding δ³⁴S decrease in sulphides suggest that partial isotopic equilibration occurred during oxidation. Carbonate minerals indicate that the hydrothermal fluid was enriched in ¹⁸O (δ¹⁸O_SMOW ～ + 10‰) relative to meteoric groundwater and seawater. Estimated values for δ¹³C_DIC (δ¹³C_PDB ～ ? 13‰) are consistent with compositions expected for dissolved inorganic carbon (DIC) derived from the products of thermal decomposition of organic matter and dissolution of marine carbonate. Values derived for δ¹³C_DIC and δ¹⁸O_water indicate that the hydrothermal fluid was of basinal brine origin, generated by extensive water–rock interaction. Following the hydrothermal phase, speleothemic minerals were precipitated under vadose conditions. Speleothemic sulphates show a bimodal sulphur isotope distribution. One group has compositions similar to the hydrothermal sulphates, whilst the second group is characterized by higher δ³⁴S values. This latter group may either record the effects of microbial sulphate reduction, or reflect the introduction of sulphate‐rich groundwater generated by the dissolution of overlying evaporites. Oxygen isotope compositions show that calcite speleothems were precipitated from nonthermal groundwater of meteoric origin. Carbonate speleothems are relatively enriched in ¹³C compared to most cave deposits, but can be explained by normal speleothem‐forming processes under thin, arid‐zone soils dominated by C4 vegetation. However, the presence of sulphate speleothems, with isotopic compositions indicative of the oxidation of hydrothermal sulphide, implies that CO₂ derived by reaction of limestone with sulphuric acid (‘condensation corrosion’) contributed to the formation of ¹³C‐enriched speleothem deposits.