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Ignimbrites within calderas host intrusions with hazardous and/or economically significant hydrothermal systems. The Hvítserkur ignimbrite at Breiðuvík caldera, north-eastern Iceland, is intruded by basaltic dykes. Our data show that the ignimbrite immediately adjacent to the dyke is hard, dark-coloured, recrystallised quartz, plagioclase, and alkali feldspar with a low permeability and porosity and frequent macrofractures. At 1-2 m from the dyke, the ignimbrite is hard, dominantly glassy with pervasive perlitic microfractures, has high permeability, but low porosity and frequent macrofractures. A narrow zone of pervasive unlithified clay exists 2 m from the dyke. Beyond this, the ignimbrite is soft and zeolite-rich, has low permeability, high porosity and fewer macrofractures. The dyke intrusion promoted a narrow zone of welding, fracturing and perlitisation in the ignimbrite resulting in high permeability and focussed alteration. Our study shows how intrusions and their thermal aureoles create vertical pathways for, and horizontal barriers to, geothermal fluid flow.

The collapse of a volcanic flank can be destructive and deadly. Hydrothermal alteration is common to volcanoes worldwide and is thought to promote volcano instability by decreasing rock strength. However, some laboratory studies have shown that not all alteration reduces rock strength. Our new laboratory data for altered rhyodacites from Chaos Crags (Lassen volcanic center, California, USA) show that pore- and crack-filling mineral precipitation can reduce porosity and permeability and increase strength, Young's modulus, and cohesion. A significant reduction in permeability, by as much as four orders of magnitude, will inhibit fluid circulation and create zones of high pore fluid pressure. We explored the consequences of pore fluid pressurization on volcano stability using large-scale numerical modeling. Upscaled physical and mechanical properties for hydrothermally altered rocks were used as input parameters in our modeling. Results show that a high-pore-pressure zone within a volcano increases volcano deformation and that increasing the size of this zone increases the observed deformation. Hydrothermal alteration associated with mineral precipitation, and increases to rock strength, can therefore promote pore pressurization and volcano deformation, increasing the likelihood of volcano spreading, flank collapses, and phreatic/phreatomagmatic explosions. We conclude that porosity-decreasing alteration, explored here, and porosity-increasing alteration can both promote volcano instability and collapse, but by different mechanisms. Hydrothermal alteration should therefore be monitored at volcanoes worldwide and incorporated into hazard assessments.

International audience; The heat flux of an active volcano provides crucial information on volcanic unrest. The hydrothermal activity often responsible for volcanic unrest can be accompanied by an increase in the extent and intensity of hydrothermal alteration, which could influence the thermal properties of the volcanic edifice. Therefore, an understanding of the influence of alteration on the thermal properties of rocks is required to better interpret volcano heat flux data. We provide laboratory measurements of thermal conductivity, thermal diffusivity, and specific heat capacity for variably altered (intermediate to advanced argillic alteration) andesites from La Soufrière de Guadeloupe (Eastern Caribbean). We complement these data with previously published data for altered basaltic-andesites from Merapi (Indonesia) and new data for altered rhyodacites from Chaos Crags (USA). Our data show that thermal conductivity and thermal diffusivity decrease as a function of increasing porosity, whereas the specific heat capacity does not change systematically. Thermal conductivity decreases as a function of alteration (the percentage of secondary minerals) for the rocks from La Soufrière and Merapi (from ~1.6 to ~0.6 W·m−1·K−1 as alteration increases from ~1.5 to >75 wt%), but increases for the rocks from Chaos Crags (from ~1.1 to ~1.5 W·m−1·K−1 as alteration increases from ~6 to ~15 wt%). Although the thermal diffusivity of the rocks from Chaos Crags increases from ~0.65 to ~0.75–0.95 mm2·s−1 as alteration increases from ~6 to ~15 wt%, the thermal diffusivity of the rocks from La Soufrière and Merapi does not appear to be greatly influenced by alteration. The specific heat capacity is not significantly affected by alteration, although there is a slight trend of increasing specific heat capacity with alteration for the rocks from La Soufrière. We conclude that the decrease in thermal conductivity as a function of alteration in the rocks from La Soufrière and Merapi is the result of the low conductivity of the secondary mineral assemblage, and that a combination of the high thermal conductivity of cristobalite and the reduction in porosity as a result of the void-filling mineral precipitation can explain the increase in thermal conductivity in the rocks from Chaos Crags. Calculations show that an increase in alteration of a dome or edifice can result in decreases and increases in heat flow density, depending on the type of alteration. Therefore, alteration-induced changes in the thermal properties of dome or edifice rocks should be considered when interpreting volcano heat flux data. We conclude that it is important not only to monitor the extent and evolution of alteration at active volcanoes, but also the spatial distribution of alteration type.

The recently discovered giant Huoshaoyun zinc-lead deposit in the Karakorum Range, northwestern Tibet, China, consists of a major zinc-lead carbonate and a minor lead-dominant sulfide mineralization with metal reserves of zinc and lead of over 16 million tonnes. The zinc-lead carbonate mineralization is composed of smithsonite and cerussite, with laminated, massive, veined and botryoidal textures, showing sedimentary and metasomatic structures. The lead-dominant sulfide mineralization is composed mainly of galena and minor sphalerite and pyrite, with laminated, brecciated, and veined textures. The laminated sulfide mineralized zones occur at the top of the deposit, whereas the zinc-lead carbonate mineralized bodies are located below the sulfide zones. Lead-dominant sulfide veins cut the zinc-lead carbonate ores and the host limestone. The sequence of formation of the lead-zinc ores with various mineral colors in thin sections is as follows: (1) light-colored to yellowish, fine- to coarse- and subhedral to euhedral smithsonite; (2) yellowish to reddish, fine- to coarse- and subhedral to euhedral smithsonite; (3) light-colored veined smithsonite; (4) white coarse-grained, xenomorphic cerussite; (5) colorless euhedral to sub-angular quartz crystals; (6) euhedral to anhedral lead-zinc sulfides and gypsum. The mineralization events of the Huoshaoyun deposit are: (1) early hydrothermal sedimentary smithsonite mineralization; (2) hydrothermal replacive smithsonite mineralization; (3) vein-type smithsonite mineralization; (4) open space filling and replacive cerussite mineralization; (5) lead-zinc sulfide mineralization. The fluid inclusions of cerussite indicate that the hydrothermal fluids of the cerussite ore-forming stage are characterized by a temperature range of at least 186–206 °C and low salinities (0.7–1.2 wt% NaCl eq.). The source of oxygen and carbon for the zinc-lead carbonate mineralization is possibly consistent with the involvement of marine water and a magmatic fluid, and is probably dominated by the magmatic fluid. The source of sulfur for the lead-dominant sulfide mineralization is possibly related to a magma reservoir. The zinc-lead-carbonate portion of the deposit represents a primary hypogene non-sulfide mineralization.

The nature of sub-volcanic alteration is usually only observable after erosion and exhumation at old inactive volcanoes, via geochemical changes in hydrothermal fluids sampled at the surface, via relatively low-resolution geophysical methods or can be inferred from erupted products. These methods are spatially or temporally removed from the real subsurface and thus provide only indirect information. In contrast, the ICDP deep drilling of the Mt Unzen volcano subsurface affords a snapshot into the in situ interaction between the dacitic dykes that fed dome-forming eruptions and the sub-volcanic hydrothermal system, where the most recent lava dome eruption occurred between 1990 and 1995. Here, we analyse drill core samples from hole USDP-4, constraining their degree and type of alteration. We identify and characterize two clay alteration stages: (1) an unusual argillic alteration infill of fractured or partially dissolved plagioclase and hornblende phenocryst domains with kaolinite and Reichweite 1 illite (70)-smectite and (2) propylitic alteration of amphibole and biotite phenocrysts with the fracture-hosted precipitation of chlorite, sulfide and carbonate minerals. These observations imply that the early clay-forming fluid was acidic and probably had a magmatic component, which is indicated for the fluids related to the second chlorite-carbonate stage by our stable carbon and oxygen isotope data. The porosity in the dyke samples is dominantly fracture-hosted, and fracture-filling mineralization is common, suggesting that the dykes were fractured during magma transport, emplacement and cooling, and that subsequent permeable circulation of hydrothermal fluids led to pore clogging and potential partial sealing of the pore network on a timescale of ~ 9 years from cessation of the last eruption. These observations, in concert with evidence that intermediate, crystal-bearing magmas are susceptible to fracturing during ascent and emplacement, lead us to suggest that arc volcanoes enclosed in highly fractured country rock are susceptible to rapid hydrothermal circulation and alteration, with implications for the development of fluid flow, mineralization, stress regime and volcanic edifice structural stability. We explore these possibilities in the context of alteration at other similar volcanoes., info:eu-repo/semantics/published

International audience; Volcanoes are unstable structures that deform laterally and frequently experience mass wasting events. Hydrothermal alteration is often invoked as a mechanism that contributes significantly to volcano instability. We present a study that combines laboratory experiments, geophysical data, and large-scale numerical modeling to better understand the influence of alteration on volcano stability, using La Soufrière de Guadeloupe (Eastern Caribbean) as a case study. Laboratory experiments on variably altered (advanced argillic alteration) blocks show that uniaxial compressive strength, Young's modulus, and cohesion decrease as a function of increasing alteration, but that the internal friction angle does not change systematically. Simplified volcano cross sections were prepared (a homogenous volcano, a volcano containing the alteration zone identified by a recent electrical survey, and a volcano with an artificially enlarged area of alteration) and mechanical properties were assigned to zones corresponding to unaltered and altered rock. Numerical modeling performed on these cross sections, using a hydro-thermo-mechanical modeling code, show (a) the importance of using upscaled values in large-scale models and (b) that alteration significantly increases volcano deformation and collapse volume. Finally, we combined published muon tomography data with our laboratory data to create a 3D strength map, exposing a low-strength zone beneath the southern flank of the volcano coincident with the hydrothermal system. We conclude that hydrothermal alteration decreases volcano stability and thus expedites volcano spreading and increases the likelihood of mass wasting events and associated volcanic hazards. Hydrothermal alteration, and its evolution, should therefore be monitored at active volcanoes worldwide.

The physical properties and mechanical behaviour of impactites are an important parameter in fluid flow models and slope stability and landscape evolution assessments for heavily impacted planetary bodies. We first present porosity, permeability, Young's modulus, and uniaxial compressive strength measurements for three suevites from the Ries impact crater (Germany). Porosity ranges from 0.18 to 0.43, permeability from 5.8 × 10−16 to 5.1 × 10−14 m2, Young's modulus from 1.4 to 8.1 GPa, and uniaxial compressive strength from 7.3 to 48.6 MPa. To explore their mechanical behaviour, we performed triaxial deformation experiments on these samples at a range of confining pressures. The brittle–ductile transition for the lowest (0.25) and highest (0.38) porosity suevite samples was at a confining pressure of ~30 and ~10 MPa, respectively (corresponding to, for example, depths of ~1 and ~4 km on Mars, respectively). Microstructural observations show that the dominant deformation micromechanism during brittle deformation is microcracking, and during ductile deformation is distributed cataclastic pore collapse. We show that a theoretically grounded permeability model for welded granular media accurately captures the permeability of the studied suevites, and we use micromechanical models to glean insight as to their mechanical behaviour. Finally, we upscale our laboratory measurements to provide physical property values for length scales more relevant for large-scale models, and we compare these data with those for basalt (a lithology representative of the surface of the inner Solar System bodies). These analyses show how macroscopic fractures serve to increase the permeability and decrease the strength and Young's modulus of suevite and basalt. We also find, for example, that basalt can be a factor of 2–5 stronger than suevite in the shallow crust. Our study suggests, therefore, that the rock masses comprising older, bombarded crusts are substantially weaker and more porous and permeable than the younger plains material on these bodies. These findings should be considered in large-scale fluid flow modelling and when providing crustal strength estimates or slope stability assessments for planetary bodies on which protracted records of impact bombardment are preserved.

An asteroid impact in southwest Germany ca. 15 Ma left a > 20 km-diameter blanket of poorly sorted clastic rock, called suevite. In the 15th century, the suevite was used to construct a Gothic church (St. George's church, Nordlingen). Visual inspection of the church highlights its strong weathering susceptibility. We investigate whether the suevite used to construct the church and the rocks used in its restoration (suevite and sandstone) are weaker when saturated with water, important for conservation strategies. We additionally assess, by comparing their physical properties, the suitability of the replacement stones. We show that the strength of the suevite used to build the church is reduced by half when water-saturated, considered here a consequence of its high smectite content. This helps explain the prevalent weathering of the stones forming the outer walls of the church. The replacement suevite has a higher wet/dry strength ratio than the original suevite and is therefore more resistant to weathering. Not only does the replacement sandstone have a low ratio of wet/dry strength, but also its physical properties are different from the original suevite, which has almost identical physical properties to those of the replacement suevite. Based on these results, and the appearance of the stones, we recommend that, where possible, natural suevite stones be used to replace the weathered blocks of suevite at St. George's church and at buildings built using suevite within the region.

Dome-forming volcanoes are among the most hazardous volcanoes on Earth. Magmatic outgassing can be hindered if the permeability of a lava dome is reduced, promoting pore pressure augmentation and explosive behaviour. Laboratory data show that acid-sulphate alteration, common to volcanoes worldwide, can reduce the permeability on the sample lengthscale by up to four orders of magnitude and is the result of pore- and microfracture-filling mineral precipitation. Calculations using these data demonstrate that intense alteration can reduce the equivalent permeability of a dome by two orders of magnitude, which we show using numerical modelling to be sufficient to increase pore pressure. The fragmentation criterion shows that the predicted pore pressure increase is capable of fragmenting the majority of dome-forming materials, thus promoting explosive volcanism. It is crucial that hydrothermal alteration, which develops over months to years, is monitored at dome-forming volcanoes and is incorporated into real-time hazard assessments., The permeability of a dome exerts a control on the outgassing efficiency of the underlying magma. The authors investigate the role of hydrothermal alteration on this process in the laboratory and use these data to model whether the overpressures generated are capable of promoting explosive behaviour.

International audience; Hydrothermal fluids can alter the chemical and physical properties of the materials through which they pass and can therefore modify the efficiency of fluid circulation. The role of hydrothermal alteration in the development of geothermal and epithermal mineral resources, systems that require the efficient hydrothermal circulation provided by fracture networks, is investigated here from a petrophysical standpoint using samples collected from a well exposed and variably altered palaeo-hydrothermal system hosted in the Ohakuri ignimbrite deposit in the Taupō Volcanic Zone (New Zealand). Our new laboratory data show that, although quartz and adularia precipitation reduces matrix porosity and permeability, it increases the uniaxial compressive strength, Young’s modulus, and propensity for brittle behaviour. The fractures formed in highly altered rocks containing quartz and adularia are also more planar than those formed in their less altered counterparts. All of these factors combine to enhance the likelihood that a silicified rock-mass will host permeability-enhancing fractures. Indeed, the highly altered silicified rocks of the Ohakuri ignimbrite deposit are much more fractured than less altered outcrops. By contrast, smectite alteration at the margins of the hydrothermal system does not significantly increase strength or Young’s modulus, or significantly decrease permeability, and creates a relatively unfractured rock-mass. Using our new laboratory data, we provide permeability modelling that shows that the equivalent permeability of a silicified rock-mass will be higher than that of a less altered rock-mass or a rock-mass characterised by smectite alteration, the latter of which provides a low-permeability cap required for an economically viable hydrothermal resource. Our new data show, using a petrophysical approach, how hydrothermal alteration can produce rock-masses that are both suitable for geothermal energy exploitation (high-permeability reservoir and low-permeability cap) and more likely to host high-grade epithermal mineral veins, such as gold and silver (localised fluid flow).

The Middle Miocene Upper Freshwater Molasse sediments represent the last cycle of clastic sedimentation during the evolution of the North Alpine Foreland Basin. They are characterized by small-scale lateral and temporal facies changes that make intra-basin stratigraphic correlations at regional scale difficult. This study provides new U–Pb zircon ages as well as revised 40Ar/ 39Ar data of volcanic ash horizons in the Upper Freshwater Molasse sediments from southern Germany and Switzerland. In a first and preliminary attempt, we propose their possible correlation to other European tephra deposits. The U–Pb zircon data of one Swiss (Bischofszell) and seven southern German (Zahling, Hachelstuhl, Laimering, Unterneul, Krumbad, Ponholz) tuff horizons indicate eruption ages between roughly 13.0 and 15.5 Ma. The stratigraphic position of the Unterneul and Laimering tuffs, bracketing the ejecta of the Ries impact (Brockhorizon), suggests that the Ries impact occurred between 14.93 and 15.00 Ma, thus assigning the event to the reversed chron C5Bn1r (15.032–14.870 Ma) which is in accordance with paleomagnetic evidence. We combine our data with published ages of tuff horizons from Italy, Switzerland, Bavaria, Styria, Hungary, and Romania to derive a preliminary tephrochronological scheme for the Middle Miocene in Central Europe in the age window from 13.2 to 15.5 Ma. The scheme is based on the current state of knowledge that the Carpathian–Pannonian volcanic field was the only area in the region producing explosive calc-alkaline felsic volcanism. This preliminary scheme will require verification by more high-quality ages complemented by isotopic, geochemical and paleomagnetic data.

International audience; Geothermal projects in the Upper Rhine Graben aim to harness thermal anomalies that have arisen due to hydrothermal circulation within the granitic basement and the overlying Permo-Triassic sedimentary units. We present here a systematic microstructural, mineralogical, and petrophysical characterisation of the lowermost unit of this Permo-Triassic sedimentary succession—the Buntsandstein—sampled from exploration well EPS-1 at the Soultz-sous-Forêts geothermal site (France). Twelve depths were sampled (from 1008 to 1414 m) and cylindrical cores were prepared perpendicular and parallel to bedding. These cores were described in terms of their microstructure, grain size and shape, specific surface area, pore size and pore throat size distribution, mineral content, porosity, P-wave velocity, and permeability. The Buntsandstein sandstones are predominantly feldspathic sandstones, often characterised by pores filled or partially filled (with clays (R3 illite–smectite), dolomite, siderite, and barite) as a consequence of diagenesis, tectonics, and the circulation of hydrothermal fluids. The porosity, dry P-wave velocity, and permeability of these sandstones vary from ~ 0.03 to 0.2, ~ 2.5 to 4.5 km s−1, and ~ 10−18 to 10−13 m2, respectively. Our data show that P-wave velocity decreases and permeability increases as porosity increases. P-wave velocities are significantly higher when measured parallel to bedding (by about 10 to 25%), and that saturation with water increases P-wave velocity (by about 5 to 50%, depending on sample orientation). The pervasive pore-filling precipitation has significantly reduced the permeabilities of the Buntsandstein sandstones, which are orders of magnitude less permeable than similarly porous unaltered sandstone. We also find that their permeability can be up to an order of magnitude more permeable when measured parallel to bedding than perpendicular to bedding. Although Buntsandstein units with low matrix permeabilities (as low as ~ 10−18 m2) require macroscopic fractures to attain the high permeability required to sustain regional hydrothermal circulation, matrix permeability is important for units with low fracture densities and high matrix permeabilities. We anticipate that these data will aid future fluid flow modelling and seismic investigations at geothermal sites within the Upper Rhine Graben.

The Ediacaran continental flood basalts and associated tuffs were studied to identify and quantify alteration processes by means of XRD and chemistry, supplemented by Mossbauer and FTIR spectroscopies, petrography, oxygen and iron isotopes, K-Ar dating, and organic geochemistry. Two superimposed alteration processes were identified: the Ediacaran hydrothermal alteration, induced by meteoric waters, heated and put in motion by the cooling basalt, and the Caledonian and/or Variscan potassic alteration. The degree of basalt alteration was quantified using as an index the sum of primary minerals in the bulk rock. The sequence of minerals dissolved and crystallized during the hydrothermal alteration was established. The alteration resulted in the loss of Ca (dissolution of plagioclases), compensated by the gain of water and Mg (crystallization of clays), and proceeded from the edges of the basalt flows in an oxidizing environment, evidenced by the increasing amount of hematite and Fe3+/Fe2+ ratio of the bulk rock. Cyanobacteria were active in the hydrothermal system, most probably responsible for the measured negative δ56Fe values and more reducing conditions at the stage of intense alteration. Chlorophaeite (palagonite), following quartz as the earliest petrographically identifiable basalt alteration product was found to vary systematically from fully isotropic to birefringent. The chlorophaeite was identified as a mixture of Fe-montmorillonite and Fe-saponite, identical with griffithite and oxysmectites, probably preceded by a finer-grained ferrosaponite at the isotropic stage. REE content of chlorophaeite indicates basaltic volcanic glass (sideromelane) as the major source of material. REE in clays are contained mostly in the dioctahedral smectite, while in the bulk rock mostly in phosphates. The smectite characteristics and Mg enrichment are indicative of the hydrothermal basalt alteration process, which perhaps was dominant also on Mars. Both mineral and chemical composition of tuffs vary continuously from basaltic to felsic, the latter close to the measured rhyodacite composition, dominated by quartz and feldspars. The basaltic tuffs resemble the most altered basalts but contain also abundant albite and chlorite, indicative of higher alteration temperatures, up to 220 °C. Tuff composition indicates stronger component of felsic volcanism in the trap formation than evidenced by the preserved bodies of effusive rocks.

International audience; Geothermal energy exploitation in the Upper Rhine Graben currently targets high-temperature anomalies in the crystalline Paleozoic basement at depths up to 5 km. However, at certain locations (e.g. Rittershoffen, France), geothermal installations are actively targeting resources at shallower depths where the Paleozoic granite transitions into the overlying Permo-Triassic sandstones. We here investigate the variation in physical properties—including porosity, P-wave velocity, permeability, uniaxial compressive strength, and thermal properties—in rocks that locally extend across the Paleozoic–Permo-Triassic boundary in four locations to the west of the Upper Rhine Graben. The lithologies investigated include sandstones, breccia, granites, metagranites, dolomite, and altered and unaltered volcanic rocks and represent the variety of lithologies at this transition. We note that while the porosity, permeability, thermal conductivity, and P-wave velocity of the Permo-Triassic sedimentary cover and Paleozoic crystalline basement rocks are consistent with values determined for rocks from exploratory and production boreholes at Soultz-sous-Forêts (France), the other lithologies (belonging to neither the sedimentary nor basement sequences) are conspicuously lower in porosity and permeability. Further, the attendant strength of these other lithologies could make them relatively unamenable to fracturing, reducing the possibility of fracture-controlled permeability in these units. Indeed, we conclude that in areas where these low-permeability and high-strength rocks act to cap the crystalline basement, hydrothermal convection may be curtailed and geothermal exploitation may be rendered untenable.

Neapolitan Yellow Tuff (NYT) has been used in construction in Naples (Italy) since the Greeks founded the city—then called Neapolis—in the sixth century BCE. We investigate here whether this popular building stone is weaker when saturated with water, an issue important for assessments of weathering damage and monument preservation. To this end, we performed 28 uniaxial compressive strength measurements on dry and water-saturated samples cored from a block of the lithified Upper Member of the NYT. Our experiments show that the strength of the zeolite-rich NYT is systematically reduced when saturated with water (the ratio of wet to dry strength is 0.63). Complementary experiments show that two other common Neapolitan building stones—Piperno Tuff and the grey Campanian Ignimbrite (both facies of the Campanian Ignimbrite deposit devoid of zeolites)—do not weaken when wet. From these data, and previously published data for tuffs around the globe, we conclude that the water-weakening in NYT is a consequence of the presence of abundant zeolites (the block tested herein contains 46 wt.% of zeolites). These data may help explain weathering damage in NYT building stones (due to rainfall, rising damp, and proximity to the sea or water table) and the observed link between rainfall and landslides, rock falls, and sinkhole formation in Naples, and the weathering of other buildings built from zeolite-rich tuffs worldwide.

The use of Mt. Epomeo Green Tuff (MEGT) as a building stone is widespread on Ischia Island (Italy). We assess here the fire resistance of MEGT by thermally stressing samples to temperatures up to 1000 °C. Porosity and uniaxial compressive strength increase and decrease from 44% and 4.5 MPa at ambient temperature to 48% and 1.5 MPa following exposure to 1000 °C, respectively. Complementary thermogravimetric and X-ray powder diffraction analyses, experiments that monitor acoustic emissions during heating/cooling, and microstructural observations highlight that these changes are the result of thermal microcracks, formed due to the breakdown of zeolites and clays (MEGT contains 35 wt.% analcime, 15 wt.% smectite, and 3 wt.% illite) at high temperature. Although the stability of structures built from MEGT will be jeopardised at high temperature, a very low thermal diffusivity requires that fires must burn for many hours to compromise the strength of a typical dimension stone: tuffs are tough in the event of fire.

Fluid inclusion studies in combination with hydrogen oxygen and sulphur isotope data provide novel insights into the genesis of giant amethyst bearing geodes in Early Cretaceous Paraná continental flood basalts at Amestita do Sul Brazil. Monophase liquid inclusions in colourless quartz amethyst calcite barite and gypsum were analysed by microthermometry after stimulating bubble nucleation using single femtosecond laser pulses. The salinity of the fluid inclusions was determined from ice melting temperatures and a combination of prograde and retrograde homogenisation temperatures via the density maximum of the aqueous solutions. Four mineralisation stages are distinguished. In stage I celadonite chalcedony and pyrite formed under reducing conditions in a thermally stable environment. Low d34SV CDT values of pyrite ( 25 to 32 ‰) suggest biogenic sulphate reduction by organotrophic bacteria. During the subsequent stages II (amethyst goethite and anhydrite) III (early subhedral calcite) and IV (barite late subhedral calcite and gypsum) the oxidation state of the fluid changed towards more oxidising conditions and microbial sulphate reduction ceased. Three distinct modes of fluid salinities around 5.3 3.4 and 0.3 wt NaCl equivalent characterise the mineralisation stages II III and IV respectively. The salinity of the stage I fluid is unknown due to lack of fluid inclusions. Variation in homogenisation temperatures and in d18O values of amethyst show evidence of repeated pulses of ascending hydrothermal fluids of up to 80 90 °C infiltrating a basaltic host rock of less than 45 °C. Colourless quartz and amethyst formed at temperatures between 40 and 80 °C while the different calcite generations and late gypsum precipitated at temperatures below 45 °C. Calculated oxygen isotope composition of the amethyst precipitating fluid in combination with dD values of amethyst hosted fluid inclusions ( 59 to 51 ‰) show a significant 18O shift from the meteoric water line. This 18O shift high salinities of the fluid inclusions with chloride sulphate composition and high d34S values of anhydrite and barite (7.5 to 9.9 ‰) suggest that sedimentary brines from deeper parts of the Guaraní aquifer system must have been responsible for the amethyst mineralisation. © 2014 Springer Verlag Berlin Heidelberg.

Mineralogical and geochemical variations among the Carboniferous and Cretaceous sedimentary kaolin deposits from Sinai provided an opportunity to examine the effect of the source area on compositions of the deposits. The Carboniferous kaolin deposits are mineralogically and geochemically heterogeneous. The Khaboba and Hasbar deposits consist of kaolinite, quartz, anatase, illite, chlorite, zircon, and leucoxene. The shale-normalized rare earth element (REE) patterns of the Khaboba deposit showed a slight LREE over HREE enrichment ((La/Yb)SN = 1.19–1.51) with a MREE depletion (Gd/Gd*SN = 0.51–0.75), while the Hasbar kaolin had a MREE enrichment. The Abu Natash kaolin deposit consisted of kaolinite, anatase, and a little quartz with larger TiO2, Cr, and V and smaller Zr and Nb contents compared to other Carboniferous deposits. The shale-normalized REE patterns of the Abu Natash deposit exhibited a positive Eu anomaly (Eu/Eu*SN = 1.28–1.40) and a MREE enrichment (Gd/Gd*SN = 1.41–2.05). The Cretaceous deposits were relatively homogeneous in terms of mineralogical composition and geochemistry and are composed of kaolinite, quartz, anatase, rutile, zircon, and leucoxene. The Cretaceous kaolin deposits showed mostly flat shale-normalized REE patterns with a variable LREE depletion. The presence of illite and chlorite, the absence of rutile, large Zr and Nb contents, and the REE patterns suggested a component of weathered low-grade metasediments as a source for the Carboniferous deposits in the Khaboba and Hasbar areas, while the large Ti, Cr, and V, and small quartz contents indicated mafic source rocks for the Abu Natash deposit. The abundance of high-Cr rutile and the absence of illite and chlorite, and large Zr, Ti, Cr, and V contents suggested a mixture of medium- to high-grade metamafic and granitic rocks as source rocks for the Cretaceous kaolin deposits. The occurrence of alkaline rocks in the source of the deposits studied was identified by high-Nb contents and the presence of bastnaesite. The mineralogical and geochemical heterogeneity and lesser maturity of the Carboniferous deposits suggested local sources for each deposit and their deposition in basins close to the sources. The mineralogical and geochemical homogeneity and maturity of the Cretaceous deposits, on the other hand, indicated common sources for all deposits and their deposition in relatively remote basins.

Understanding the physicochemical conditions extant and mechanisms operative during explosive volcanism is essential for reliable forecasting and mitigation of volcanic events. Rhyolitic pumices reflect highly vesiculated magma whose bubbles can serve as a strain indicator for inferring the state of stress operative immediately prior to eruptive fragmentation. Obtaining the full kinematic picture reflected in bubble population geometry has been extremely difficult, involving dissection of a small number of delicate samples. The advent of reliable high-resolution tomography has changed this situation radically. Here we demonstrate via the use of tomography how a statistically powerful picture of the shapes and connectivity of thousands of individual bubbles within a single sample of tube pumice emerges. The strain record of tube pumice is modelled using empirical models of bubble geometry and liquid rheology, reliant on a constraint of magmatic water concentration. FTIR analysis reveals an imbalance in water speciation, suggesting post-eruption hydration, further supported by hydrogen and oxygen isotope measurements. Our work demonstrates that the strain recorded in the tube pumice dominated by simple shear (not pure shear) in the late deformational history of vesicular magma before eruption. This constraint in turn implies that magma ascent is conditioned by a velocity gradient (across the conduit) at the point of origin of tube pumice. Magma ascent accompanied by simple shear should enhance high eruption rates inferred independently for these highly viscous systems. © Author(s) 2016., Financial support was provided by the Deutsche Forschungsgemeinschaft (DFG) – International Continental Drilling Program (ICDP) grant HE 4565-2-1 as well as the DFG grants LA 2651-1-1 and LA 2651 3-1. Yan Lavallée acknowledges support from the European Research Council (ERC) for the Starting Grant on Strain Localisation in Magmas (SLiM, no. 306488). Donald B. Dingwell acknowledges a Research Professorship in Experimental Volcanology of the Bundesexzellenzinitiative (LMUexcellent) as well as an ERC Advanced Grant on Explosive Volcanism in the Earth System (EVOKES, no. 247076).

The Belgian nonsulfide Zn deposits represent the historical basis for the zinc mining and smelting industry in Europe. The zinc ores were called "calamines" and consist of a mixture of Zn carbonates (smithsonite, hydrozincite) and Zn silicates (hemimorphite, willemite and Zn clays), with a variable content of Pb minerals. The "calamines" are considered to be oxidation products of primary sulfide ores. The most important was the La Calamine orebody (more than 600,000 tons of Zn metal) that was continuously exploited for several centuries. Nonsulfide ores were also exploited at Schmalgraf, Engis, Dickenbusch, Fossey, Rocheux-Oneux, Welkenraedt and in other smaller deposits (all no longer accessible for study), where the "calamines" extended from the surface to an average depth of 40 to 50 m. The primary Zn-Pb sulfide mineralization consists of post-Variscan hydrothermal veins and replacement bodies, mostly occurring in the Dinantian (Visean) limestones. The sulfides intersect the Paleozoic rocks and are truncated and unconformably covered by Late Cretaceous sediments (Santonian Aachen Fm.). The same setting has been observed for the nonsulfide ores, Suggesting an Early to Mid-Cretaceous weathering, consistent with other geological and geochronological data on paleoweathering in Europe. The extensive occurrence of willemite, that appears to be the first deposited nonsulfide mineral, is a striking particularity of the Belgian "calamines". Most fluid inclusions in willemite (80%) and all inclusions in smithsonite are monophase (aqueous). Ice melting temperatures suggest salinities between 0 and 5 wt.% NaCl equiv. Homogenization temperatures of rare two-phase inclusions (liquid+vapor) in willemite display a large variation between 80 and 190 degrees, an interval matching the temperature ranges of other willemite ores throughout the world, so far considered of hydrothermal origin. The stable isotope variation of Belgian smithsonites and cerussites is very similar to the range measured in other supergene nonsulfide deposits similar to those of SW Sardinia. Belgian smithsonites exhibit a limited range of delta O-18 values from 27.1 to 30.6 parts per thousand, averaging 28.4 parts per thousand +/- 0.8 parts per thousand V-SMOW. This limited range points to a relatively uniform isotope composition of the oxidizing waters and constant temperatures of smithsonite crystallization. Carbon isotope values, even from the same mine, show a considerable range from -11.6 to -1.6 parts per thousand. This extensive range indicates at least two carbon sources: 13 C-depleted carbon derived from the organic matter in the soils and 13 C-enriched carbon originating from marine carbonate host rocks. Cerussites have oxygen isotope values ranging from 16.8 to 19.3 parts per thousand, averaging 17.8 +/- 1.0 parts per thousand and carbon isotope values of -18.4 to -14.7 parts per thousand. The metallic deposits of Eastern Belgium have undergone a polyphase history, which started with a possibly Jurassic sulfide mineralization, followed by oxidation under high silica activities and consequently by supergene weathering. Owing to structure and mineralogical association, we do not consider the high homogenization temperatures as reliable minimum temperature estimates of willemite formation. However, it is possible that the willemite concentrations could have been derived from low-temperature, localized hydrothermal processes caused by deeply reaching oxidizing fluids. Smithsonite and hemimorphite, often developed at the expenses of willemite, have all the characteristics of supergene oxidation products.

The O-18/O-16 and C-13/C-12 ratios of carbonate minerals formed by supergene oxidation of Zn-Pb deposits and submarine alteration of ancient slags were studied in order to constrain isotope fractionation factors for smithsonite, cerussite, and phosgenite, and to characterize conditions of nonsulfide ore formation. We present new isotope data of carbonate-hosted ores from the lglesiente district (Sardinia, Italy) and Vila Ruiva (Portugal), as well as from the silicate-hosted ores of the Broken Hill district, New South Wales (Australia) and Freihung (Germany) and review previously published isotope data. The temperature dependence of oxygen isotope fractionation between Pb and Zn carbonate minerals and water below 240 degrees C for cerussite and below 100 degrees C for smithsonite and phosgenite can be expressed as 10001n alpha(cerussite-water) = 2.29(10(6)/T-2)-3.56 10001n alpha(smithsonite-water) = 3.10(10(6)/T-2)-3.50 10001n alpha(phosgenite-water) = 2.55(10(6)/T-2)-3.50 with Tin Kelvin. The carbon isotope fractionation between smithsonite, phosgenite, hydrozincite and calcite is less than about 2 parts per thousand, while cerussites are strongly depleted in C-13 by about 10 parts per thousand as compared to the former minerals. Oxygen isotope variations of individual carbonate minerals within a deposit are relatively small indicating constant formation temperatures and a single, meteoric fluid source. Average formation temperatures of the studied deposits are calculated at 20 +/- 5 degrees C using the estimated isotope compositions of local paleometeoric waters. We observe a linear relationship between the isotope values of estimated paleometcoric waters and supergene carbonates. Thus, base metal carbonate minerals from supergene deposits may provide paleoclimatic information. The carbon isotope values are in most carbonate-hosted deposits highly variable (more than 10 parts per thousand) suggesting at least two isotopically distinct carbon sources. The isotopically light component can be related to oxidation of C3 plants (soil-derived carbon) and/or microbes that take active part in sulfide oxidation, while the isotopically heavy component originates from carbonate carbon from wall rocks and/or atmospheric carbon. The C-13-enriched component is less dominant in silicate-hosted deposits.

International audience; Volcanic hydrothermal systems host a prodigious variety of physico-chemical conditions. The physico-chemical state and mechanical behaviour of rocks within is correspondingly complex and often characterised by vast heterogeneity. Here, we present uniaxial and triaxial compression experiments designed to investigate the breadth of mechanical behaviour and failure modes (dilatant or compactant) for hydrothermally-altered lava and ash tuff deposits from Whakaari (White Island volcano) in New Zealand, a volcano with a well-documented and very active hydrothermal system. Our deformation experiments show that the failure mode of low porosity lava remains dilatant over a range of depths (up to pressures corresponding to depths of about 2 km). Upon failure, shear fractures, the result of the coalescence of dilatational microcracks, are universally present. The high porosity ash tuffs switch however from a dilatant to a compactant failure mode (driven by progressive distributed pore collapse) at relatively low pressure (corresponding to a depth of about 250 m). We capture the salient features of the dynamic conditions (e.g., differential stress, effective pressure) in a schematic cross section for the Whakaari hydrothermal system and map, for the different lithologies, areas susceptible to either dilatant vs. compactive modes of failure. The failure mode will impact, for example, the evolution of rock physical properties (e.g., porosity, permeability, and elastic wave velocity) and the nature of the seismicity accompanying periods of unrest. We outline accordingly the potential implications for the interpretation of seismic signals, outgassing, ground deformation, and the volcanic structural stability for Whakaari and similar hydrothermally-active volcanoes worldwide.

Deposition of quartz–molybdenite–pyrite–topaz–muscovite–fluorite and subsequent hubnerite and sulfide–fluorite–rhodochrosite mineralization at the Sweet Home Mine occurred coeval with the final stage of magmatic activity and ore formation at the nearby world-class Climax molybdenum deposit about 26 to 25 m.y. ago. The mineralization occurred at depths of about 3,000 m and is related to at least two major fluid systems: (1) one dominated by magmatic fluids, and (2) another dominated by meteoric water. The sulfur isotopic composition of pyrite, strontium isotopes and REY distribution in fluorite suggest that the early-stage quartz–molybdenite–pyrite–topaz–muscovite–fluorite mineral assemblage was deposited from magmatic fluids under a fluctuating pressure regime at temperatures of about 400°C as indicated by CO2-bearing, moderately saline (7.5–12.5 wt.% NaCl equiv.) fluid inclusions. LA-ICPMS analyses of fluid inclusions in quartz demonstrate that fluids from the Sweet Home Mine are enriched in incompatible elements but have considerably lower metal contents than those reported from porphyry–Cu–Au–Mo or Climax-type deposits. The ore-forming fluid exsolved from a highly differentiated magma possibly related to the deep-seated Alma Batholith or distal porphyry stock(s). Sulfide mineralization, marking the periphery of Climax-type porphyry systems, with fluorite and rhodochrosite as gangue minerals was deposited under a hydrostatic pressure regime from low-salinity ± CO2-bearing fluids with low metal content at temperatures below 400°C. The sulfide mineralization is characterized by mostly negative δ34S values for sphalerite, galena, chalcopyrite, and tetrahedrite, highly variable δ18O values for rhodochrosite, and low REE contents in fluorite. The Pb isotopic composition of galena as well as the highly variable 87Sr/86Sr ratios of fluorite, rhodochrosite, and apatite indicates that at least part of the Pb and Sr originated from a much more radiogenic source than Climax-type granites. It is suggested that the sulfide mineralization at the Sweet Home Mine formed from magmatic fluids that mixed with variable amounts of externally derived fluids. The migration of the latter fluids, that were major components during late-stage mineralization at the Sweet Home Mine, was probably driven by a buried magmatic intrusion.

International audience; Vigorous hydrothermal activity interspersed by sequences of phreatic and phreatomagmatic eruptions occur at Whakaari (White Island volcano), New Zealand. Here, we investigate the influence of sample type (hydrothermally altered cemented ash tuffs and unconsolidated ash/lapilli) and fragmentation mechanism (steam flashing versus gas expansion) on fragmentation and ejection velocities as well as on particle-size and shape. Our rapid decompression experiments show that fragmentation and ejection speeds of two ash tuffs, cemented by alunite and amorphous opal, increase with increasing porosity and that both are significantly enhanced in the presence of steam flashing. Ejection speeds of unconsolidated samples are higher than ejection speeds of cemented tuffs, as less energy is consumed by fragmentation. Fragmentation dominated by steam flashing results in increased fragmentation energy and a higher proportion of fine particles. Particle shape analyses before and after fragmentation reveal that both steam flashing and pure gas expansion produce platy or bladed particles from fracturing parallel to the decompression front. Neither fragmentation mechanisms nor sample type show a significant influence on the shape. Our results emphasize that, under identical pressure and temperature conditions, eruptions accompanied by the process of liquid water flashing to steam are significantly more violent than those driven simply by gas expansion. Therefore, phase changes during decompression and cementation are both important considerations for hazard assessment and modeling of eruptions in hydrothermally active environments.