Electron backscatter diffraction investigation of length‐fast chalcedony in agate: implications for agate genesis and growth mechanisms

Agates of volcanic origin contain a range of silica minerals, with chalcedony and quartz arranged in concentric bands. Although agates are abundant worldwide, little is known about the genesis of their characteristic banding patterns. Current hypotheses suggest the bands result either from precipitation from convecting siliceous hydrothermal influxes or by in situ crystallization of a silica gel. This study combines the use of a variety of analytical techniques, including electron backscatter diffraction (EBSD), cathodoluminescence (CL), and Fourier transform infrared (FT‐IR) spectroscopy, to characterize the silica minerals present and investigate their spatial and crystallographic relationships in the banding arrangement. Microstructural and spectroscopic observations reveal that chalcedony bands are composed of amorphous silica that also contains nanocrystalline and later‐formed microcrystalline quartz. Nano‐ and microcrystalline quartz grew with a‐axes perpendicular to the growth substrate, typical of length‐fast chalcedony. The bands formed as a result of discrete influxes of silica‐rich fluid. Within these individual bands, there is a sequence of minerals: chalcedony‐A (with amorphous silica and nanocrystalline quartz) → chalcedony‐MQ (with microcrystalline quartz) → quartz. This sequence is reflected in the degree of crystallinity, crystal orientations and water content and is analogous to a diagenetic cycle; the initial chalcedony portion of the band commences with amorphous silica with nanocrystalline quartz followed by fibrous microcrystalline quartz crystals; chalcedony then grades into larger equiaxial mesoquartz crystals. This paragenetic sequence suggests a viable model for the growth of chalcedony in agates.     

Experimental study of polycrystal growth from an advecting supersaturated fluid in a model fracture

We present real‐time observations of polycrystal growth experiments in transmitted light in an accurately controlled flow system with the analogue material alum [KAl(SO₄)₂·12H₂O]. The aim of the experiments is to obtain a better insight into the evolution of vein microstructures. A first series of experiments shows the evolution of a polycrystal at supersaturations between 0.095 and 0.263. The average growth rate of the crystals is influenced by growth competition and the depletion of the solute along fracture length. Growth competition is controlled by crystallographic orientation, crystal size and crystal location. In addition, the growth rate of an individual crystal facet also shows variations depending on the facet index, facet size and flow velocity. These variations can influence the morphology of the grain boundaries and the microstructures. The aim of the second series of experiments is to investigate the growth evolution of rough/dissolved facets in detail. The growth distance required for the development of facets is around 15 μm. In all the experiments, we observe that the measured growth rates have a much larger range than predicted by alum single‐crystal growth kinetics. This is due to the combined effect of the facet index and the crystal size. Furthermore, at high supersaturations, the facet growth rate measurements do not fit the same growth rate equation as for the experiments at lower supersaturations (<0.176). This can be explained by a change in the growth mechanism at high supersaturations with more influence of volume diffusion, relative to advection of the bulk solution on the growth rate. This effect can also cause a more homogeneous sealing pattern over fracture length. At high supersaturations, the larger crystals in these experiments incorporate regularly spaced fluid inclusion bands and we propose that these can be used as an indicator for high palaeo‐supersaturation. The final microstructures of the experiments show no asymmetry with respect to the flow direction.     

Hydrothermal dolomitization,mixing corrosion and deep burial porosity formation: numerical results from 1‐D reactive transport models

Major corrosion has been found at depth in carbonate hydrocarbon reservoirs from different geologic provinces. Fluid inclusion microthermometry and stable isotopic compositions of carbonate cements, predating major corrosion, constrain the interpretation of the evolution of parental fluids during progressive burial and prior to the major corrosion event. Post‐major corrosion mineral paragenesis includes pyrite (‐marcasite), anhydrite, kaolinite (dickite) and fluorite. Although the post‐corrosion mineral paragenesis represents minor volumes of rock, it may provide valuable insights into the post‐corrosion brine chemistry. Using reactive transport numerical models, the roles of cooling and/or mixing of brines on corrosion have been evaluated as controls for dolomitization, deep burial corrosion and precipitation of the post‐corrosion mineral paragenesis. Modelling results show that cooling of deep‐seated fluids moving upward along a fracture may cause minor calcite dissolution and porosity generation. Significant dolomitization along a fracture zone and nearby host‐rock only occurs when deep‐seated fluids have high salinities (4 mol Cl kg^?1 of solution) and Darcian flow rates are relatively high (1 m³ m^?2 year^?1). Only minor volumes of quartz and fluorite precipitate in the newly formed porosity. Moreover, modelling results cannot reproduce the authigenic precipitation of kaolinite (dickite at high temperatures) by cooling. As an alternative to cooling as a cause of corrosion, mixing between two brines of different compositions and salinities is represented by two main cases. One case consists of the flow up along a fracture of deep‐seated fluids with higher salinities than the fluid in the wall rock. Dolomite does not precipitate at a fracture zone. Nevertheless, minor volumes of dolomite are formed away from the fracture. The post‐corrosion mineral paragenesis can be partly reproduced, and the results are comparable to those obtained from cooling calculations. Minor volumes of quartz and fluorite are formed, and kaolinite‐dickite does not precipitate. The major outputs of this scenario are calcite dissolution and slight net increase in porosity. A second case corresponds to the mixing of low salinity deep‐seated fluids, flowing up along fractures, with high salinity brines within the wall rock. Calculations predict major dissolution of calcite and precipitation of dolomite. The post‐corrosion mineral paragenesis can be reproduced. High volumes of quartz, fluorite and kaolinite‐dickite precipitate and may even completely occlude newly formed porosity.     

Experimental study of aqueous fluid infiltration into quartzite: implications for the kinetics of fluid redistribution and grain growth driven by interfacial energy reduction

To investigate the kinetics of interfacial energy‐driven fluid infiltration, experiments were carried out in a quartzite–water system at 621–925°C and 0.8 GPa. Infiltration couples were made by juxtaposing presynthesized dry quartzite cylinders and fluid reservoirs. The infiltration process was confirmed by the presence of pores at the quartzite grain edges. As predicted from theoretical considerations and previous experiments, wetting fluids such as pure water and NaCl aqueous solution infiltrated into quartzite, whereas nonwetting CO₂‐rich fluids did not. Newly precipitated quartz layers at the surfaces of the infiltrated sample proved that infiltration took place by a dissolution–precipitation mechanism. The enhancement of grain growth by fluid infiltration was observed over the entire range of experimental temperatures. The fluid fraction, gauged by the porosity of the run products, increases at the infiltration front and then decreases towards the fluid reservoir to form a high‐porosity zone with a maximum porosity of 2.3–2.9%. As infiltration proceeds, the high‐porosity zone advances like a travelling wave. This porosity wave is probably caused by a grain curvature gradient resulting from preferential grain growth in the infiltrated part of the quartzite, perhaps combined with other factors. The infiltration kinetics were modelled with a steady‐state diffusion model over the high‐porosity zone. The solubility difference between dissolving and precipitating grains was deduced to be 2 × 10^?2?3 × 10^?1 wt %. The experimentally obtained infiltration rate of aqueous fluid in the steady‐state diffusion regime (2 ± 0.5 × 10^?8 m sec^?1 at 823°C) is much faster than the estimated metamorphic fluid flux rates, so that interfacial energy‐driven fluid redistribution in quartz‐rich layers could significantly contribute to the fluid flux in high‐grade metamorphism, at least over a short distance. Cathodoluminescence observations of the run products revealed that the grain growth of quartzite in the presence of fluid proceeds extensively, which would promote the chemical equilibration between fluid and rock more effectively than would volume diffusion in quartz crystals.     

Precipitation of fracture fillings and cements in the Buntsandstein (NW Germany)

The relationship between fracturing and fracture filling in opening‐mode fractures in the Triassic Buntsandstein in the Lower Saxony Basin (LSB; NW Germany) has been studied by an integration of petrographic and structural analysis of core samples, strontium isotope analysis and microthermometry on fluid inclusions. This revealed the relationship between the timing of the fracturing and the precipitation of different mineral phases in the fractures by constraining the precipitation conditions and considering the possible fluid transport mechanisms. The core was studied from four different boreholes, located in different structural settings across the LSB. In the core samples from the four boreholes, fractures filled with calcite, quartz and anhydrite were found, in addition to pore‐filling calcite cementation. In boreholes 2 and 3, calcite‐filled fractures have a fibrous microstructure whereas in borehole 1, fractures are filled with elongate‐blocky calcite crystals. Anhydrite‐filled fractures have, in all samples, a blocky to elongate‐blocky microstructure. Fractures that are filled with quartz are observed in borehole 2 only where the quartz crystals are ‘stretched’ with an elongated habit. Fluid inclusion microthermometry of fracturing‐filling quartz crystals showed that quartz precipitation took place at temperatures of at least 140°C, from a fluid with NaCl–CaCl₂–H₂O composition. Melting phases are meta‐stable and suggest growth from high salinity formation water. Strontium isotopes, measured in leached host rock, indicate that, in boreholes 2 and 3, the fluid which precipitated the calcite cements and calcite‐filled fractures is most likely locally derived whereas in borehole 1, the ⁸⁷Sr/⁸⁶Sr ratios from the pore‐filling cements and in the elongate‐blocky calcite‐filled fracture can only be explained by mixing with externally derived fluids. The elongate‐blocky anhydrite‐filled fractures, present in boreholes 1, 3 and 4, precipitated from a mixture of locally derived pore fluids and a significant quantity of fluid with a lower, less radiogenic, ⁸⁷Sr/⁸⁶Sr ratio. Taking into account the structural evolution of the basin and accompanying salt tectonics, it is likely that the underlying Zechstein is a source for the less radiogenic fluids. Based on the samples in the LSB, it is probable that fibrous fracture fillings in sedimentary rocks most likely developed from locally derived pore fluids whereas elongate‐blocky fracture fillings with smooth walls developed from externally derived pore fluids.     

Mobilization of ore fluids during Alpine metamorphism: evidence from hydrothermal veins in the Variscan basement of Western Carpathians,Slovakia

Hydrothermal polymetallic veins of the Gemeric unit of the Western Carpathians are oriented coherently with the foliation of their low‐grade Variscan basement host. Early siderite precipitated from homogeneous NaCl‐KCl‐CaCl₂‐H₂O brines with minor CO₂, while immiscible gas–brine mixtures are indicative of the superimposed barite, quartz–tourmaline and quartz–sulphide stages. The high‐salinity aqueous fluid (18–35 wt%) found in all mineralization stages corresponds to formation water modified by interaction with crystalline basement rocks at temperatures between 140 and 300°C. High brominity (around 1000 ppm in average) resulted from evaporation and anhydrite precipitation in a Permo‐Triassic marine basin, and from secondary enrichment by dissolution of organic matter in the marine sediments at diagenetic temperatures. Sulphate depletion reflects thermogenic reduction during infiltration of the formation waters into the Variscan crystalline basement. Crystallization temperatures of the siderite fill (140–300°C) and oxygen isotope ratios of the parental fluids (4–10‰) increase towards the centre of the Gemeric cleavage fan, probably as a consequence of decreasing water/rock ratios in rock‐buffered hydrothermal systems operating during the initial stages of vein evolution. In contrast, buoyant gas–water mixtures, variable salinities and strongly fluctuating P–T parameters in the successive mineralization stages reflect transition from a closed to an open hydrothermal system and mixing of fluids from various sources. Depths of burial were 6–14 km (1.7–4.4 kbar, in a predominantly lithostatic fluid regime) during the siderite and barite sub‐stages of the north‐Gemeric veins, and up to 16 km (1.6–4.5 kbar, in a hydrostatic to lithostatic fluid regime) in the quartz–tourmaline stage of the south‐Gemeric veins. The fluid pressure decreased down to approximately 0.6 kbar during crystallization of sulphides. U‐Pb‐Th, ⁴⁰Ar/³⁹Ar and K/Ar geochronology applied to hydrothermal muscovite–phengite and monazite, as well as cleavage phyllosilicates in the adjacent basement rocks and deformed Permian conglomerates corroborated the opening of hydrothermal veins during Lower Cretaceous thrusting and their rejuvenation during Late Cretaceous sinistral transpressive shearing and extension.     

Recognising burnt vein quartz artefacts in archaeological assemblages

The primary aims of this study were to determine how vein quartz behaves in an open wood fire and to suggest how burnt quartz may reliably be distinguished from unburnt quartz. Experimental burning was conducted on 10–50 mm pieces of knapped quartz collected from outcrops and beach cobbles near a later Mesolithic and Neolithic quartz scatter at Belderrig, north County Mayo, Ireland. Burning resulted in considerable fragmentation, with the majority of post-burning fragments <10 mm in size. Compared to experiments with flint, few quartz pieces were expelled from the hearth during burning, probably due to lower water content. Burning reduced the lustre and transparency of quartz and oxidized any iron-bearing rock impurities to a red-brown or pink colour, but these changes could only be diagnostic of burning where unburnt quartz of the same type is available for comparison. Burning did not affect the texture of the quartz, though quartz grain boundaries became more visible in some samples. Under the microscope, all >5 μm fluid inclusions in quartz lost their fluid contents, often with the development of fluid escape structures, and this is likely to be a reliable discriminant between burnt and unburnt vein quartz generally, even in the absence of unburnt material for comparison. Burning also creates microfractures, but this feature does not provide a diagnostic test of burning as there is considerable overlap between burnt and unburnt samples in microfracture density.     

Numerical modelling of 3D fluid flow and oxygen isotope exchange in fractured media: spatial distribution of isotope patterns

An understanding of fluid flow, mass transport and isotopic exchange in fractured rock is required to understand the origin of several geological processes including hydrothermal mineral deposits. The numerical model HydroGeoSphere simulates 3D advection, molecular diffusion, mechanical dispersion and isotopic exchange in a discretely fractured porous media, and can be used to better understand the processes of mass transport and isotopic exchange in fractured rocks. Study of ¹⁸O isopleth patterns for different types of fractures and fracture networks with a range of structural complexity and hydraulic properties shows that fracture properties and geometry control mass transport and isotopic exchange. The hydraulic properties, as well as the density, spacing, and connectivity of fractures determine the isotopic patterns. Asymmetries in the geometry of oxygen isotope patterns could be used to determine the direction of hydrothermal fluid flow.     

Quartz recrystallization and fluid flow during contact metamorphism: a cathodoluminescence study

Cathodoluminescence (CL) images of quartz grains in the Appin Quartzite from the aureole of the Ballachulish Igneous Complex (Scotland) reveal a textural complexity that we interpret in the light of published models of the evolution of the contact aureole. Five distinct generations of quartz can be discriminated in CL. The oldest of these is a dark luminescing mottled quartz (Type 1 quartz) that occurs in the centres of pre‐existing grains, in samples collected from 210 m to 0.1 m from the contact. Dark mottled quartz is interpreted to be unrecrystallized material and has a regional metamorphic CL spectral signature. The onset of contact metamorphism resulted in grain growth visible in CL as a series of fine‐scale alternating bands of bright and dark luminescing material (Type 2 quartz), which we attribute to infiltration of repeated pulses of small amounts of H₂O along grain boundaries. Close to the intrusion, a subgrain‐scale network of intragranular, bright luminescing features could have resulted from either intragranular microcrack‐controlled infiltration of H₂O at high temperatures or intergranular cracking followed by grain growth (Type 3 quartz). Broad bands of bright material on grain boundaries in samples that are inferred to have undergone partial melting are interpreted as quartz crystallized from the melt phase (Type 4 quartz). The final stage in the textural development is marked by a series of aligned fractures, detected in CL by nonluminescing material (Type 5 quartz) and corresponding closely with trails of fluid inclusions. These fractures are interpreted as the pathways for late‐stage, low‐temperature, retrogressive fluids.     

Stable–unstable flow of geothermal fluids in fractured rock

Density-driven geothermal flow in 3-D fractured rock is investigated and compared with density-driven haline flow. For typical matrix and fracture hydraulic conductivities, haline flow tends to be unstable (convecting) while geothermal flow is stable (non-convecting). Thermal diffusivity is generally three orders of magnitude larger than haline diffusivity and, as a result, large heat conduction diminishes growth of geothermal instabilities while low mass diffusion enables formation of unstable haline 'fingering' within fractures. A series of thermal flow simulations is presented to identify stable and unstable conditions for a wide range of hydraulic conductivities for matrix and fractures. The classic Rayleigh stability criterion can be applied to classify these simulations when fracture aperture is very small. However, the Rayleigh criterion is not applicable when the porous matrix hydraulic conductivity is very small, because stabilizing fracture–matrix heat conduction is independent of matrix hydraulic conductivity. In that case, the numerically estimated critical fracture conductivity is nine orders of magnitude larger than the theoretically calculated critical fracture conductivity based on Rayleigh theory. The numerical stability analysis presented here may be used as a guideline to predict if a geothermal system in 3-D fractured rock is stable or unstable.     

Petroleum infiltration of high-grade basement, South Norway: Pressure-Temperature-time-composition (P–T–t–X) constraints

Fluid inclusion data provide pressure–temperature–time–composition (P–T–t–X) constraints for an episode of petroleum infiltration of the crystalline basement in South Norway. Petroleum inclusions associated with pyrobitumen occur in postmetamorphic quartz veins in the Modum Complex. Three groups of fluid compositions have been shown, ranging from CH₄ ± CO₂ to condensates with alkanes up to C₁₅. The range in fluid composition is a result of petroleum decomposition at high temperature. Globular and massive pyrobitumen occurs in the quartz veins or in associated vein systems. Reflectance (%Rm) measurements of 3.20–3.35 correspond to a maximum temperature of 207–214°C for the pyrobitumen associated with group II and III inclusions. Geothermometry of chlorites included in the quartz show results of 226–231°C. Pressure conditions of trapping for all three groups of inclusion fluids have been estimated to 520–985 bar at 220°C. The pressure range is probably a result of fluctuations caused by repeated fracture opening and sealing due to seismic activity coupled with mineral growth. A lack of systematic textural relationships between the three groups of inclusions and similar pressure–temperature estimates for all fluid types indicate trapping at similar times and a process of rapid change. Fluid migration in fractures from an overlying, overpressured sedimentary basin into a dry, crystalline basement best explains the observed P–T–t–X constraints.     

The origins of two purportedly pre-Columbian Mexican crystal skulls

The well-known life-size rock crystal skull in the British Museum was purchased in 1897 as an example of genuine pre-Columbian workmanship, but its authenticity has been the subject of increasing speculation since the 1930s. This paper is concerned with the history, technology and material of the skull and another larger white quartz skull, donated recently to the Smithsonian Institution. Manufacturing techniques were investigated, using scanning electron microscopy to examine tool marks on the artefacts, and compared with Mesoamerican material from secure contexts. A Mixtec rock crystal goblet and a group of Aztec/Mixtec rock crystal beads show no evidence of lapidary wheels. They were probably worked with stone and wood tools charged with abrasives, some of which may have been as hard as corundum. Textual evidence for Mexican lapidary techniques during the early colonial period, supported by limited archaeological evidence, also indicates a technology without the wheel, probably based on natural tool materials. In contrast, the two skulls under consideration were carved with rotary wheels. The British Museum skull was worked with hard abrasives such as corundum or diamond, whereas X-ray diffraction revealed traces of carborundum (SiC), a hard modern synthetic abrasive, on the Smithsonian skull. Investigation of fluid and solid inclusions in the quartz of the British Museum skull, using microscopy and Raman spectroscopy, shows that the material formed in a mesothermal metamorphic environment equivalent to greenschist facies. This suggests that the quartz was obtained from Brazil or Madagascar, areas far outside pre-Columbian trade networks. Recent archival research revealed that the British Museum skull was rejected as a modern artefact by the Museo Nacional de Mexico in 1885, when offered for sale by the collector and dealer, Eugène Boban. These findings led to the conclusion that the British Museum skull was worked in Europe during the nineteenth century. The Smithsonian Institution skull was probably manufactured shortly before it was bought in Mexico City in 1960; large blocks of white quartz would have been available from deposits in Mexico and the USA.     

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.     

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.     

The relevance of vein texture in understanding the past hydraulic behaviour of a crystalline rock mass: reconstruction of the palaeohydrology of the Mecsekalja Zone,south Hungary

This study reconstructs the palaeohydrogeologic evolution of the shallow‐to‐moderate Mesozoic subsidence history for the Mecsekalja Zone (MZ), a narrow metamorphic belt in the eastern Mecsek Mountains, Hungary. Brittle deformation of the MZ produced a vein system with a cement history consisting of five sequential carbonate generations and one quartz phase. Vein textures suggest different fluid‐flow mechanisms for the parent fluids of subsequent cement generations. Combined microthermometric and stable‐isotope measurements permit reconstruction of the character of subsequent fluid generations with different flow types, as defined by vein textures, yielding new information regarding the hydraulic behaviour of a metamorphic crystalline complex. Textural observations and geochemical data suggest that fracture‐controlled flow pathways and externally derived fluids were typical of some flow events, while percolation through the rock matrix and the relationship to the Cretaceous volcanism and dyke emplacement were typical of others. The difference in the mode of calcite deposition from pervasive fluids (i.e. pervasive carbonatisation along grain boundaries versus deposition in antitaxial veins) between two calcite generations related to the volcanism inspired a stress‐dependent model of antitaxial vein growth. Textural and isotope variations in a vein generation produced by the same parent fluid indicate rock‐dependent hydraulic behaviour for different rock types, distinct action of the contemporaneous fracture systems and different extents of fluid–rock interaction. Cathodoluminescence microscopy and fluid‐inclusion microthermometry shed light on the possible role of hydraulic fracturing in the formation of massive calcite. The time of formation was estimated from the isotope composition of the oldest calcite generation and its presumptive relationship with the sedimentary sequences to the north, whereas microthermometry permitted conciliation of the reconstructed flow sequence with the Mesozoic subsidence history of the Mórágy Block (including the MZ).     

Hydrothermal control on organic matter alteration and illite precipitation, Mt Isa Basin, Australia

Abundant illite precipitation in Proterozoic rocks from Northern Lawn Hill Platform, Mt Isa Basin, Australia, occurred in organic matter‐rich black shales rather than in sandstones, siltstones and organic matter‐poor shales. Sandstones and siltstones acted as impermeable rocks, as early diagenetic quartz and carbonate minerals reduced the porosity–permeability. Scanning and transmission electron microscopy (SEM and TEM) studies indicate a relation between creation of microporosity–permeability and organic matter alteration, suitable for subsequent mineral precipitation. K–Ar data indicate that organic matter alteration and the subsequent illite precipitation within the organic matter occurred during the regional hydrothermal event at 1172 ± 50 (2σ) Ma. Hot circulating fluids are considered to be responsible for organic matter alteration, migration and removal of volatile hydrocarbon, and consequently porosity–permeability creation. Those rocks lacking sufficient porosity–permeability, such as sandstones, siltstones and organic matter poor shales, may not have been affected by fluid movement. In hydrothermal systems, shales and mudstones may not be impermeable as usually assumed because of hydrocarbons being rapidly removed by fluid, even with relatively low total organic carbon.     

Inferring intermediate‐scale fluid flow in a heterogeneous metasedimentary multilayer sequence during progressive deformation: evidence from the Monts d’Arrée slate belt (Brittany,France)

Quartz veins in the early Variscan Monts d’Arrée slate belt (Central Armorican Terrane, Western France), have been used to determine fluid‐flow characteristics. A combination of a detailed structural analysis, fluid inclusion microthermometry and stable isotope analyses provides insights in the scale of fluid flow and the water–rock interactions. This research suggests that fluids were expelled during progressive deformation and underwent an evolution in fluid chemistry because of changing redox conditions. Seven quartz‐vein generations were identified in the metasedimentary multilayer sequence of the Upper Silurian to Lower Devonian Plougastel Formation, and placed within the time frame of the deformation history. Fluid inclusion data of primary inclusions in syn‐ to post‐tectonic vein generations indicate a gradual increase in methane content of the aqueous–gaseous H₂O–CO₂–NaCl–CH₄–N₂ fluid during similar P–T conditions (350–400°C and 2–3.5 kbar). The heterogeneous centimetre‐ to metre‐scale multilayer sequence of quartzites and phyllites has a range of oxygen‐isotope values (8.0–14.1‰ Vienna Standard Mean Ocean Water), which is comparable with the range in the crosscutting quartz veins (10.5–14.7‰ V‐SMOW). Significant differences between oxygen‐isotope values of veins and adjacent host rock (Δ = ?2.8‰ to +4.9‰ V‐SMOW) suggest an absence of host‐rock buffering on a centimetre scale, but based on the similar range of isotope values in the Plougastel Formation, an intraformational buffering and an intermediate‐scale fluid‐flow system could be inferred. The abundance of veins, their well‐distributed and isolated occurrence, and their direct relationship with the progressive deformation suggests that the intermediate‐scale fluid‐flow system primarily occurred in a dynamically generated network of temporarily open fractures.     

Computing geochemical mass transfer and water/rock ratios in submarine hydrothermal systems: implications for estimating the vigour of convection

A method of calculating chemical water/rock ratios is presented that enables the estimation of fluid velocities in open, flow‐through hydrologic systems. The approach is based on relating the gain/loss of a chemical species per kilogram of solid phase to the loss/gain of that species in the fluid phase, integrated across a specified length of the flowpath. After examining the underlying approximations of the approach using a one‐dimensional model of seawater moving through a basalt under nonisothermal conditions, the method is applied to representative zones within a two‐dimensional hydrothermal convective system. The method requires that regions within the flow system can be identified in which the direction of flow is steady for an extended period of time. Estimates of fluid velocity are spatial and temporal averages for the length of the flowpath used in the calculation. The location within the flow system and the nature of the alteration reactions determine which species can provide reliable values of the chemical water/rock ratio and useful estimates of fluid velocities. Over the length of the flowpath considered, the calculation of water/rock ratios works best when a species is controlled by a single reaction. Accurate estimates are favoured if the concentration profile of a species along the flowpath increases or decreases monotonically. If the length of the flowpath extends over more than one reaction zone, then erroneous estimates of the water/rock ratio and fluid velocity are more likely. Model calculations suggest that the quartz/silica system should provide reliable estimates for fluid velocity under a wide range of temperature and flow conditions, in particular in those regions of a system at or near quartz equilibrium, so that the aqueous silica concentration is buffered by quartz and correlated with the temperature distribution.     

Oscillatory zoning and trace element incorporation in hydrothermal minerals: insights from calcite growth experiments

Oscillatory zoning and fine‐scale variations in trace element chemistry are commonly observed in hydrothermal minerals. It has been suggested that fine‐scale chemical variations are caused by extrinsic changes in the parent hydrothermal system, such as varying fluid composition, pressure or temperature, as well as changes in mineral growth rate. In this study, LA–ICP–MS (laser ablation, inductively coupled plasma mass spectrometer) analyses were carried out on calcite crystals grown in Ca–NH₃–Cl solutions doped with rare earth elements (REE). The variety of crystal morphologies observed (euhedral to acicular), likely relate to variations in trace element abundance and calcite supersaturation state. Crystals display oscillatory and sector zoning, with significant variations in REE concentrations among zones. Cyclic variations in REE concentrations (exceeding 10‐fold) occur over distances of <1 mm along the growth direction of acicular calcite crystals. In general, trace element concentrations decrease during progressive crystal growth, implying that the concentration of trace and REEs within crystals reflects the overall composition of the growth solution. However, bulk changes in crystal composition are modulated by fine‐scale (<1 mm) variations, which are inferred to be caused by growth‐rate‐controlled incorporation of trace elements. These results have important implications for using hydrothermal minerals to infer fluctuations in fluid compositions in ancient, exhumed hydrothermal systems.     

Thermoluminescence age of quartz xenocrysts in basaltic lava from Oninomi monogenetic volcano, northern Kyushu, Japan

We determined the eruption age of basaltic rocks by application of thermoluminescence (TL) method, which is often used for TL dating, to quartz. Mafic magma only rarely includes quartz because of their mutual disequilibration. The basaltic lavas reported herein include quartz as xenocrysts, as corroborated by their rounded or anhedral shape. The basaltic lava used for this study is from the Oninomi monogenetic volcano in northern Kyushu, Japan. The volcano eruption was estimated as occurring 7.3–29 ka because the lava exists between two widespread tephras: Aira-Tanzawa ash (26–29 ka) and Kikai-Akahoya ash (7.3 ka). We succeed-ed in collecting ca. 200 mg of quartz by decomposition of 30 kg of the lava samples. TL measurements for the lava indicate the eruption age as 15.8 ± 2.5 ka, which is fairly consistent with the stratigraphical estimation. Although the TL method has played a considerable part in constraining the timescale of Quaternary events, its application has been limited to silicic samples. The present result demonstrates the availability of quartz for dating even of mafic rock.