Fluid control on low‐temperature mineral formation in volcanic rocks of Kahrizak,Iran

The Kahrizak volcanic field, south Tehran, in Iran, is composed dominantly of basalt and basaltic andesite that experienced variable degrees of alteration because of the low‐grade metamorphism (stage I) and hydrothermal activity (stage II). Stage I alteration, which occurred in response to the burial of volcanic rocks and their interaction with heated groundwater, is characterized by the formation of low‐temperature zeolite facies minerals in vesicles consisting mainly of fine‐grained mafic phyllosilicate (smectite, chlorite/smectite mixed layer) and zeolites (thomsonite, chabazite, gonnardite, natrolite, analcime, heulandite, and mordenite). Stage II mineralization occurred because of the activity of hydrothermal fluids that formed large crystals of heulandite, stilbite, mesolite/scolecite, natrolite, and analcime along with quartz and calcite in cavities and fractures. The elements necessary for the formation of alteration minerals (i.e. zeolites and mafic phyllosilicates) in Kahrizak were derived from the hydrolysis of olivine and volcanic glass as well as the alteration of plagioclase. Various mineral assemblages formed during stages I and II reflect changes in temperature, pressure, and fluid composition. The change from mafic phyllosilicates to zeolites species is caused by the decrease in Mg and Fe relative to Ca fluid activities. Zeolite assemblages of stage I, known to be formed at lower temperatures, show the general sequential order from older to younger: chabazite, thomsonite, gonnardite, and natrolite. This sequence is consistent with a hypothetical fluid evolution path with increasing Na⁺ relative to Ca²⁺ activity. The change to stage II, which consists of zeolites species (stilbite, scolecite, natrolite, mesolite, analcime, and heulandite) that formed at higher temperatures, can be attributed to a temperature increase and fluid influx caused by hydrothermal activity related to a later magmatic event in the region.     

Archeometric characterization of prehistoric grindstones from Milazzo Bronze Age settlement (Sicily,Italy)

The results of a petrographic and geochemical study carried out on archeological grindstones allow to provide new constraints on protohistoric commercial exchanges over the Mediterranean area. Eleven grindstones, discovered in an archeological site located in Milazzo (Messina, Sicily) and dated from the Early Bronze Age, have been investigated by geochemical and petrographic techniques. The raw materials are mainly volcanic rocks characterized by calc-alkaline and K-alkaline affinities with volcanic arc geochemical signature. Only one sample, made of basalt belonging to the Na-alkaline series, shows an intraplate signature. The comparison with the available literature data for similar rocks allowed constraining the volcanic origin of the exploited lavas. While the intraplate-type raw material came from Mt. Etna Volcano (Sicily), the arc-type volcanic rocks are mostly trachyandesites, basaltic andesites, and one rhyolite. Although most of them come from the Aeolian Arc, a provenance of some samples from the Aegean Arc cannot be excluded. This last region could represent the most probable provenance area for the rhyolite sample.     

Decreasing CO2 partial pressure triggered Mg–Fe–Ca carbonate formation in ancient Martian crust preserved in the ALH84001 Meteorite

We retrace hydrogeochemical processes leading to the formation of Mg–Fe–Ca carbonate concretions (first distinct carbonate population, FDCP) in Martian meteorite ALH84001 by generic hydrogeochemical equilibrium and mass transfer modeling. Our simple conceptual models assume isochemical equilibration of orthopyroxenite minerals with pure water at varying water‐to‐rock ratios, temperatures and CO₂ partial pressures. Modeled scenarios include CO₂ partial pressures ranging from 10.1325 to 0.0001 MPa at water‐to‐rock ratios between 4380 and 43.8 mol mol^?1 and different temperatures (278, 303 and 348 K) and enable the precipitation of Mg–Fe–Ca solid solution carbonate. Modeled range and trend of carbonate compositional variation from magnesio‐siderite (core) to magnesite (rim), and the precipitation of amorphous SiO₂ and magnetite coupled to magnesite‐rich carbonate are similar to measured compositional variation. The results of this study suggest that the early Martian subsurface had been exposed to a dynamic gas pressure regime with decreasing CO₂ partial pressure at low temperatures (approximately 1.0133 to 0.0001 MPa at 278 K or 6 to 0.0001 MPa at 303 K). Moderate water‐to‐rock ratios of ca. 438 mol mol^?1 and isochemical weathering of orthopyroxenite are additional key prerequisites for the formation of secondary phase assemblages similar to ALH84001’s ‘FDCP’. Outbursts of water and CO_2(g) from confined ground water in fractured orthopyroxenite rocks below an unstable CO₂ hydrate‐containing cryosphere provide adequate environments on the early Martian surface.     

Re‐equilibration of fluid inclusions in diagenetic‐anchizonal rocks of the Ciñera‐Matallana coal basin (NW Spain)

Thermally re‐equilibrated fluid inclusions are reported in natural fissure quartz (qtz1) from polymineralic veins in the diagenetic‐anchizonal clastic sedimentary rocks of the Ciñera‐Matallana coal basin (Variscan, NW Spain). Euhedral quartz formed during early fissure opening from an immiscible fluid mixture composed of a low salinity aqueous solution and a CH₄‐rich vapour phase, at temperatures of about 110–120°C and pressures ranging from 15 to 56 MPa. Five textural types of re‐equilibration are recognised in progressive order of inclusion modification: scalloped, hairy, annular‐ring shaped, haloes and decrepitation clusters. These textures resulted from a combination of brittle fracturing and dissolution and re‐precipitation of quartz, with preferential loss of water. The thermal peak was short‐lived, but was high enough to induce extensive decrepitation of fluid inclusions in vein quartz throughout the entire basin. Enhanced temperatures can be related to the intrusion of diorites in the basin. Careful analysis of textural features in fluid inclusions from diagenetic and very low‐grade metamorphism environments constitutes a useful tool for recording basin thermal history.     

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.     

Gas breakthrough experiments on pelitic rocks: comparative study with N2, CO2 and CH4

The capillary‐sealing efficiency of intermediate‐ to low‐permeable sedimentary rocks has been investigated by N₂, CO₂ and CH₄ breakthrough experiments on initially fully water‐saturated rocks of different lithological compositions. Differential gas pressures up to 20 MPa were imposed across samples of 10–20 mm thickness, and the decline of the differential pressures was monitored over time. Absolute (single‐phase) permeability coefficients (k_abs), determined by steady‐state fluid flow tests, ranged between 10^?22 and 10^?15 m². Maximum effective permeabilities to the gas phase k_eff(max), measured after gas breakthrough at maximum gas saturation, extended from 10^?26 to 10^?18 m². Because of re‐imbibition of water into the interconnected gas‐conducting pore system, the effective permeability to the gas phase decreases with decreasing differential (capillary) pressure. At the end of the breakthrough experiments, a residual pressure difference persists, indicating the shut‐off of the gas‐conducting pore system. These pressures, referred to as the ‘minimum capillary displacement pressures’ (P_d), ranged from 0.1 up to 6.7 MPa. Correlations were established between (i) absolute and effective permeability coefficients and (ii) effective or absolute permeability and capillary displacement pressure. Results indicate systematic differences in gas breakthrough behaviour of N₂, CO₂ and CH₄, reflecting differences in wettability and interfacial tension. Additionally, a simple dynamic model for gas leakage through a capillary seal is presented, taking into account the variation of effective permeability as a function of buoyancy pressure exerted by a gas column underneath the seal.     

Origin of palaeo‐waters in the Ordovician carbonates in Tahe oilfield,Tarim Basin: constraints from fluid inclusions and Sr,C and O isotopes

Petrographic features, isotopes, and trace elements were determined, and fluid inclusions were analyzed on fracture‐filling, karst‐filling and interparticle calcite cement from the Ordovician carbonates in Tahe oilfield, Tarim basin, NW China. The aim was to assess the origin and evolution of palaeo‐waters in the carbonates. The initial water was seawater diluted by meteoric water, as indicated by bright cathodoluminescence (CL) in low‐temperature calcite. The palaeoseawater was further buried to temperatures from 57 to 110°C, nonluminescent calcite precipitated during the Silurian to middle Devonian. Infiltration of meteoric water of late Devonian age into the carbonate rocks was recorded in the first generation of fracture‐ and karst‐filling dull red CL calcite with temperatures from <50°C to 83°C, low salinities (<9.0 wt%), high Mn contents and high ⁸⁶Sr/⁸⁷Sr ratios from 0.7090 to 0.7099. During the early Permian, ⁸⁷Sr‐rich hydrothermal water may have entered the carbonate rocks, from which precipitated a second generation of fracture‐filling and interparticle calcite and barite cements with salinities greater than 22.4 wt%, and temperatures from 120°C to 180°C. The hydrothermal water may have collected isotopically light CO₂ (possibly of TSR‐origin) during upward migration, resulting in hydrothermal calcite and the present‐day oilfield water having δ¹³C values from ?4.3 to ?13.8‰ and showing negative relationships of ⁸⁷Sr/⁸⁶Sr ratios to δ¹³C and δ¹⁸O values. However, higher temperatures (up to 187°C) and much lower salinities (down to 0.5 wt%) measured from some karst‐filling, giant, nonluminescent calcite crystals may suggest that hydrothermal water was deeply recycled, reduced (Fe‐bearing) meteoric water heated in deeper strata, or water generated from TSR during hydrothermal water activity. Mixing of hydrothermal and local basinal water (or diagenetically altered connate water) with meteoric waters of late Permian age and/or later may have resulted in large variations in salinity of the present oilfield waters with the lowest salinity formation waters in the palaeohighs.     

Numerical simulation of mylonitization and structural controls on fluid flow and mineralization of the Hetai gold deposit,west Guangdong,China

The Hetai gold deposit (HGD) is a typical altered mylonite type gold mine in a ductile shear zone in western Guangdong, China. Geomechanical simulations of the HGD were carried out in this paper to examine the importance of the dilation‐driven fluid circulation in gold mineralization. The results show that three evenly‐spaced NNE shear zones of enhanced dilation are produced in the study area. The calculated principal compressive stress in the X direction in these zones ranges between ?420 and ?650 MPa, in line with estimates of ore‐forming pressure (fluid pressure). Ore forming fluid is focused into these features, as observed in the field. The calculated differential stress decreases from 275~350 to 148~225 MPa during the formation of mylonite zones. These, together with geological structural analysis and fluid pressure measurements, indicate that the mylonitization zone can provide a place of fluid focusing and a favorable environment for gold mineralization.     

Hydrothermal activity associated with the Ries impact event, Germany

Combined field studies, optical and scanning electron microscopy, and electron microprobe studies of impactites from the Ries impact structure, Germany, have allowed a clearer picture of the hydrothermal system associated with the Ries impact event to be made. Hydrothermal alteration is concentrated within impact‐generated suevites in the interior of the crater (crater suevites) and around the periphery (surficial suevites), with minor alteration in the overlying sedimentary crater‐fill deposits. The major heat source for the Ries hydrothermal system was the suevite units themselves. Hydrothermal alteration of crater‐fill suevites is pervasive in nature and comprises several distinct alteration phases that vary with depth. An early phase of K‐metasomatism accompanied by minor albitization of crystalline basement clasts and minor chloritization, was followed by pervasive intermediate argillic alteration (predominantly montmorillonite, saponite, and illite) and zeolitization (predominantly analcite, erionite, and clinoptilolite). Hydrothermal fluids were typically weakly alkaline during the main stage of alteration. In contrast to the crater‐fill suevites, alteration within surficial suevites was typically restricted to montmorillonite and phillipsite deposition within cavities and fractures. The pervasive nature of the alteration within the crater‐fill suevites was likely due to the presence of an overlying crater lake; whereas alteration within surficial suevites typically occurred under undersaturated conditions with the main source of water being from precipitation. There are exceptional outcrops of more pervasively altered surficial suevites, which can be explained as locations where water pooled for longer periods of time. Hydrothermal fluids were likely a combination of meteoric waters that percolated down from the overlying crater lake and groundwaters that flowed in from the surrounding country rocks.     

Trace Element Classification Diagrams of Pyroclastic Rocks from the Volcanic Districts of Central Italy: the Case Study of the Ancient Roman Ships of Pisa

Identification of the volcanic material (pozzolan) stored in a Roman ship of the fourth to third century bce , wrecked in the ancient harbour of Pisa (central Italy), was based on ratios of selected trace elements. The compositions of the major volcanic products erupted by the volcanoes of the Roman province, including the volcanic districts of Latium (Vulsini, Vico, Monti Sabatini and the Alban Hills) and Campania (Roccamonfina, the Phlegraean Fields, Ischia, Procida and Vesuvius) are compared with the pozzolan from the Pisa ship. Superposition of the Zr/Y, Nb/Y and Nb/Zr ratios of the pyroclastic material from the wrecked ship (computed from the published literature) allows correlation with the products of the Onano eruption from the Vulsini Volcanic District. The Vulsini rocks outcrop extensively in a sector drained by the hydrographic network of the Fiora River, which has been a well‐developed commercial water trade route since Etruscan times, with a river port and a sea port connected to the important town of Vulci, and, since 273 bce , part of the larger Roman harbour system of Cosa.     

Granite‐related overpressure and volatile release in the mid crust: fluidized breccias from the Cloncurry District,Australia

The source and transport regions of fluidized (transported) breccias outcrop in the Cloncurry Fe‐oxide–Cu–Au district. Discordant dykes and pipes with rounded clasts of metasedimentary calc–silicate rocks and minor felsic and mafic intrusions extend several kilometres upwards and outwards from the contact aureole of the 1530 Ma Williams Batholith into overlying schists and amphibolites. We used analytical equations for particle transport to estimate clast velocities (≥20 m sec^?1), approaching volcanic ejecta rates. An abrupt release of overpressured magmatic‐hydrothermal fluid is suggested by the localization of the base of the breccias in intensely veined contact aureoles (at around 10 km, constrained by mineral equilibria), incorporation of juvenile magmatic clasts, the scale and discordancy of the bodies, and the wide range of pressure variation (up to 150 MPa) inferred from CO₂ fluid inclusion densities and related decrepitation textures. The abundance of clasts derived from depth, rather than from the adjacent wallrocks, suggests that the pressure in the pipes was sufficient to restrict the inwards spalling of fragments from breccia walls; that is, the breccias were explosive rather than implosive, and some may have vented to the surface. At these depths, such extreme behaviour may have been achieved by release of dissolved fluids from crystallizing magma, in combination with a strongly fractured and fluid‐laden carapace, sitting under a strong, low permeability barrier. The relationship of these breccias to the Ernest Henry iron‐oxide–Cu–Au deposit suggests they may have been sources of fluids or mechanical energy for ore genesis, or alternately provided permeable pathways for later ore fluids.     

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.     

ANALYSING ARCHAEOLOGICAL BASALT USING NON‐DESTRUCTIVE ENERGY‐DISPERSIVE X‐RAY FLUORESCENCE (EDXRF): EFFECTS OF POST‐DEPOSITIONAL CHEMICAL WEATHERING AND SAMPLE SIZE ON ANALYTICAL PRECISION*

Energy‐dispersive X‐ray fluorescence (EDXRF) has been commonly used to determine geological sources of volcanic glass artefacts, but its ability to discriminate between basaltic sources is less developed. We examine the precision and accuracy of non‐destructive EDXRF for basalt artefacts by analysing varying size and weathering characteristics. The experiments identified no appreciable effect in reproducibility or measured composition due to thickness (down to 1 mm) or natural weathering of pre‐contact flake scars for the 17 elements measured in this study. Samples with surface area less than 100 mm², however, show significant variability in measured composition and reproducibility.     

Relationship of brines in the Kinnarot Basin,Jordan‐Dead Sea Rift Valley

Element ratios and water stable isotopes reveal the presence of only two independent deep brines in the Kinnarot Basin, Israel: the evaporite dissolution brine of Zemah‐1 and the inferred Ha’on mother brine (HMB) with low and high Br/Cl ratios, respectively. HMB is considered to be a representative of the Late Pliocene evaporated Sedom Sea. The freshwater‐diluted evaporation brine emerges as Ha’on brine on the eastern shore of Lake Tiberias and is also identified in the pore water of lake sediments. HMB is converted into Tiberias mother brine (TMB) by dolomitization of limestones and alteration of abundant volcanic rocks occurring along the western side of the lake. The Ha’on and Tiberias brines, both characterized by high δD and δ¹⁸O values, are similar in Na/Cl and Br/Cl ratios but are dissimilar in Br/K ratios because these brines were subjected to different degrees of interactions with rocks and sediments. Excepting the brine from KIN 8, all brines from the Tabigha area including the nearby off‐shore Barbutim brine are related to the TMB. The brine KIN 8 and all brines from the Fuliya and Hammat Gader areas are related to the HMB. The brine encountered in wildcat borehole Zemah‐1 is generated by halite‐anhydrite/gypsum dissolution and is independent from the HMB system.     

Late Ordovician and Early Silurian conodonts from the “Uralba Beds”, northern New South Wales

Limestone outcrops that form a north-south belt approximately 1.4 km long, 15 km east of Manilla and previously referred to as the Uralba Beds, and associated rocks, are shown to be an olistostromal component of the Wisemans Arm Formation. Elongate olistoliths up to 100 m in length are flanked by limestone conglomerate with clasts set in a volcaniclastic matrix derived from a range of volcanic rock types. Volcanic olistoliths, including a mass of ankaramitic basalt, are also present. Conodont faunas of differing ages were obtained from various outcrops. A Late Ordovician (Eastonian, Ea3) fauna of over 400 elements from some outcrops is identical to one recently documented from elsewhere in the Wisemans Arm Formation. A small Early Silurian (late Llandovery-early Wenlock) fauna from four outcrops (including two formerly thought to be Ordovician) comprises the first documented conodont fauna of this age from the New England Fold Belt.     

A Comparative Study of the Early High‐Fired Ceramic Shards from Dongtiaoxi,Zhejiang (China)

There is a generally accepted view that there is an obvious distinction between proto‐porcelain and stamped stoneware. However, some early shards unearthed from the Dongtiaoxi region (northern Zhejiang) inspire people to rediscuss the relationship between them, because it is difficult to identify them as proto‐porcelain or stamped stoneware. In this work, we have collected samples from three of the earliest kiln sites (Piaoshan, Beijiashan and Nanshan) in the Dongtiaoxi region. We have analysed the chemical composition, firing temperature and phase composition of the samples. Comparing samples from the three kiln sites, we find that, from Piaoshan and Beijiashan to Nanshan, there has been progression in the manufacturing technology. The Shang proto‐porcelain and the stamped stoneware from Nanshan have similar raw materials, firing temperatures and body phase compositions—and they have obviously different decorative appearances, such as glazing or stamping. For ceramics from Piaoshan and Beijiashan, there is no clear distinction between glazed and unglazed samples. We believe that in the Dongtiaoxi region, the difference in the decoration between proto‐porcelain and stoneware became obvious up to the time of the Nanshan production but that, subsequently, two different paths for the development of high‐fired ceramics began to diverge.     

Numerical model of pore‐pressure diffusion associated with the initiation of the 2010–2011 Guy–Greenbrier,Arkansas earthquakes

We model pore‐pressure diffusion caused by pressurized waste‐fluid injection at two nearby wells and then compare the buildup of pressure with the observed initiation and migration of earthquakes during the early part of the 2010–2011 Guy–Greenbrier earthquake swarm. Pore‐pressure diffusion is calculated using MODFLOW 2005 that allows the actual injection histories (volume/day) at the two wells to diffuse through a fractured and faulted 3D aquifer system representing the eastern Arkoma basin. The aquifer system is calibrated using the observed water‐level recovery following well shut‐in at three wells. We estimate that the hydraulic conductivities of the Boone Formation and Arbuckle Group are 2.2 × 10^?2 and 2.03 × 10^?3 m day^?1, respectively, with a hydraulic conductivity of 1.92 × 10^?2 m day^?1 in the Hunton Group when considering 1.72 × 10^?3 m day^?1 in the Chattanooga Shale. Based on the simulated pressure field, injection near the relatively conductive Enders and Guy–Greenbrier faults (that hydraulically connect the Arbuckle Group with the underlying basement) permits pressure diffusion into the crystalline basement, but the effective radius of influence is limited in depth by the vertical anisotropy of the hydraulic diffusivity. Comparing spatial/temporal changes in the simulated pore‐pressure field to the observed seismicity suggests that minimum pore‐pressure changes of approximately 0.009 and 0.035 MPa are sufficient to initiate seismic activity within the basement and sedimentary sections of the Guy–Greenbrier fault, respectively. Further, the migration of a second front of seismicity appears to follow the approximately 0.012 MPa and 0.055 MPa pore‐pressure fronts within the basement and sedimentary sections, respectively.     

Sources and composition of fluids associated with fluorite deposits of Asturias (N Spain)

The fluorite deposits of Asturias (northern Iberian Peninsula) are hosted by rocks of Permo‐Triassic and Palaeozoic age. Fluid inclusions in ore and gangue minerals show homogenization temperatures from 80 to 170°C and the presence of two types of fluids: an H₂O–NaCl low‐salinity fluid (<8 eq. wt% NaCl) and an H₂O–NaCl–CaCl₂ fluid (7–13 wt% NaCl and 11–14 wt% CaCl₂). The low salinity and the Cl/Br and Na/Br ratios (Cl/Br_molar 100–700 and Na/Br_molar 20–700) are consistent with an evaporated sea water origin of this fluid. The other end‐member of the mixture was highly saline brine with high Cl/Br and Na/Br ratios (Cl/Br_molar 700–13 000 and Na/Br_molar 700–11 000) generated after dissolution of Triassic age evaporites. LA‐ICP‐MS analyses of fluid inclusions in fluorite reveal higher Zn, Pb and Ba contents in the high‐salinity fluids (160–500, 90–170, 320–480 p.p.m. respectively) than in the low‐salinity fluid (75–230, 25–150 and 100–300 p.p.m. respectively). The metal content of the fluids appears to decrease from E to W, from Berbes to La Collada and to Villabona. The source of F is probably related to leaching of volcanic rocks of Permian age. Brines circulated along faults into the Palaeozoic basement. Evaporated sea water was present in permeable rocks and faults along or above the unconformity between the Permo‐Triassic sediments and the Palaeozoic basement. Mineralization formed when the deep brines mixed with the surficial fluids in carbonates, breccias and fractures resulting in the formation of veins and stratabound bodies of fluorite, barite, calcite, dolomite and quartz and minor amounts of sulphides. Fluid movement and mineralization occurred between Late Triassic and Late Jurassic times, probably associated with rifting events related to the opening of the Atlantic Ocean. This model is also consistent with the geodynamic setting of other fluorite‐rich districts in Europe.     

Molecular transport of methane, ethane and nitrogen and the influence of diffusion on the chemical and isotopic composition of natural gas accumulations

Laboratory experiments have been performed to determine diffusion coefficients of natural gas components (methane, ethane and nitrogen) and isotope fractionation effects under simulated in situ pressure (up to 45 MPa effective stress) and temperature conditions (50–200°C) in water‐saturated pelitic and coarse‐grained rocks. Effective diffusion coefficients of molecular nitrogen (0.39 × 10^?11 to 21.6 × 10^?11 m² sec^?1 at 90°C) are higher than those for methane (0.18 × 10^?11 to 18.2 × 10^?11 m² sec^?1 at 90°C). Diffusive flux rates expressed in mass units are generally higher for N₂ than for CH₄. Both methane and (to a lesser extent) nitrogen diffusion coefficients decrease with increasing total organic carbon (TOC) content of the rock samples because of sorption processes on the organic matter. This effect decreases with increasing temperature. Effective diffusion coefficients increase upon a temperature increase from 50 to 200°C by a factor of four. Effective diffusion coefficients and steady‐state diffusive flux decrease with effective stress. Stationary diffusive fluxes drop by 50–70% for methane and 45–62% for nitrogen while effective diffusion coefficients are reduced by 38% (CH₄) and 32–48% (N₂), respectively. Isotope fractionation coefficients of diffusive transport are higher for methane (?1.56 and ?2.77‰) than for ethane (?0.84 and ?1.62‰). Application of the experimental results to geological systems show that diffusive transport has only a low transport efficiency. Significant depletion of natural gas reservoirs by molecular diffusion is only expected in cases of very poor caprock qualities (in terms of thickness and/or porosity) and over extended periods of geological time. Under these circumstances, the chemical and isotopic composition of a gas reservoir will change and maturity estimates based on these parameters may be deceptive. To account for these potential effects, nomograms have been developed to estimate diffusive losses and apply maturity corrections.     

New and past geochemical data on fresh to brine waters of the Salar de Atacama and Andean Altiplano,northern Chile

The paper deals with the major chemistry and stable isotopes (hydrogen, oxygen, carbon, sulfur, strontium) of waters and solutes from the Salar de Atacama basin (Rio Pedro, Honar Creek and Laguna Chaxa) and Andean Altiplano (Laguna Miñique and Laguna Miscanti). The water inflows of the Salar are chemically quite different, the Rio San Pedro being of Na‐Cl type and the Honar Creek of Na‐HCO₃ type, in keeping with the sedimentary‐evaporitic and volcanic nature of the catchment rocks respectively. The δ³⁴S and δ¹⁸O values of sulfate and the ⁸⁷Sr/⁸⁶Sr ratio of strontium in the streams match those of drained rocks, whereas the δ¹³C values of dissolved carbonate are largely controlled by vegetation. The lagoons are evaporated meteoric water bodies, and the relative air humidity estimated from the slope of the isotopic evaporation line is in accordance with historical data on air humidity in the area. The Laguna Chaxa is Na‐Cl rich, and its isotopic composition are consistent with a mixed sedimentary‐volcanic provenance of sulfur and strontium solutes. The Laguna Miñique is Na‐SO₄ rich, and its sulfate δ³⁴S is nearly identical to that of Laguna Chaxa. The δ¹³C(HCO₃) values are quite different in the Laguna Chaxa and Laguna Miñique, with the former being notably enriched in ¹³C probably because of preferential uptake of ¹²C by the high biological productivity occurring in the lagoon. The limited set of new data is interpreted in the context of a much larger literature database. In particular, previous chemical data on inflows and brines in the Salar de Atacama were revisited, and compared with evaporation path models and mineral stability diagrams (boron, lithium and Mg‐minerals) computed using updated software and thermodynamic databases. The modeling shows that the removal of boron and lithium from sulfate‐rich brines possibly occurs, respectively, as ulexite and sulfate salts, and carnallite should be the final magnesium phase of the brine evolution.