Hydrothermal silica chimney fields in the Galapagos Spreading Center at 86°W

Silica chimneys were discovered in 1985 at 86°W in the rift valley of the Galapagos Spreading Center at 2600 m depth (“Cauliflower Garden”). The inactive chimneys lack any sulfides and consist almost entirely of amorphous silica (up to 96 wt.% SiO₂, opal-A); Fe and Mn oxides are minor constituents. Oxygen isotope data show that formation of the silica chimneys took place at temperatures between 32°C (+29.9‰ δ¹⁸O) and 42°C (+27.8‰ δ¹⁸O).Th/Udating reveals a maximum age of 1440 ± 300y. Amorphous silica solubility relations indicate that the silica chimneys were formed by conductive cooling of pure hydrothermal fluids or by conductive cooling of a fluid/seawater mixture. Assuming equilibrium with quartz at 500 bars, initial fluid temperatures of more than 175°C (i.e., a concentration of > 182 ppm SiO₂) were required to achieve sufficient supersaturation for the deposition of amorphous silica at 40°C and 260 bars. If the silica chimneys originate from the same or a similar fluid as higher-temperature ( < 300°C) sulfide-silica precipitates found nearby (i.e., 2.5 km away), then subsurface deposition of sulfides may have occurred.     

Calc-alkaline and shoshonitic lavas from five Andean volcanoes (between latitudes 21° 45′ and 24°30′S) and the distribution of the Plio-Quaternary volcanism of the south-central and southern Andes

The Plio-Quaternary volcanic rocks of the south-central Andes (southward from latitude 18°S) contain two associations: calc-alkaline and shoshonitic which coincide with seismic belts as geographically distinct zones aligned parallel to the oceanic trench. There is a continuous gradation from calc-alkaline to shoshonitic associations. The shoshonitic association appears to the north of latitude 26°S; southwards, the calc-alkaline association directly abuts against the continental (Argentinian) alkaline association.Thirty-one lavas from the Plio-Quaternary calc-alkaline Socompa, Lascar, Sairecabur and Tocorpuri and shoshonitic Sierra de Lipez volcanoes were studied. The lavas are porphyric with abundant glass. The distribution and the nature of the phenocrysts vary according to the chemistry of the calc-alkaline lavas. Petrographic evidence for crystal fractionation has been observed. Occasional phenocrysts of alkali feldspars occur in the shoshonitic lavas. The K₂O and SiO₂ contents increase from calc-alkaline to shoshonitic lavas with distance away from the oceanic trench. In lavas from Socompa, Lascar, Sairecabur and Tocorpuri calc-alkaline volcanoes, K₂O, Li and Rb increase and K/Rb and Sr decrease with increasing SiO₂; Ba increases with decreasing Sr, probably as a result of plagioclase fractionation. In lavas from Sierra de Lípez shoshonitic volcano, SiO₂ is high, K₂O is high and rather constant and Li, Rb, Ba and Sr increase with increasing SiO₂. Bolivian shoshonitic lavas appear to be genetically related to the calc-alkaline suite.The calc-alkaline lavas may be derived by crystal fractionation from a parental magma of andesitic nature that originated in or above the subjacent Benioff zone.     

Imprinting chemical remanent magnetization in claystones at 95 °C

Thermal effects related to burial and hydrothermal alteration leads to chemical remanent magnetization (CRM). We present an experimental study of CRM production by heating claystones at 95 °C. A vertical magnetic field of 2 mT was applied to the claystones during heating and the evolution of the remanence during heating in air is monitored intermittently for up to four months. Solid fragments (9 to 26 g) of claystones are included in a Teflon holder that is placed in the oven under a controlled atmosphere. Newly formed grains acquire a CRM and a thermoviscous magnetization (TVRM), both being parallel to the applied magnetic field. CRM is related to the amount of newly formed grains that pass the critical volume during the reaction. To measure the acquired remanence, the claystones are first cooled in a zero magnetic field and then measured using a 2G SQUID magnetometer.In the frame of the research programme on the feasibility of radioactive waste disposal in a deep geological formation, we investigate the magnetic transformation of Mont Terri Lower Dogger claystones (Switzerland) due to thermal imprinting at 95 °C. We simulate the dehydration that occurs in the walls of galleries after excavation when interstitial water evaporates and rehydration when the galleries are refilled allowing water to move towards dehydrated zones. During dehydration, the remanence gains one order of magnitude at the beginning of the experiment and then it follows a linear rate of 0.23 ± 0.07 mA m^− 1/day between 3 and 14 days. The magnetic susceptibility increases by a few percent. The increase of the remanence and of the magnetic susceptibility stops after 15 days. Mass monitoring indicates that interstitial water evaporates when remanence and magnetic susceptibility stabilizes. During rehydration, the remanence increases again whilst magnetic susceptibility drops by a few percent. After 20 days, the remanence during rehydration follows a rate of 0.42 ± 0.15 mA m^− 1/day. By contrast, when rehydration takes place later, after 66 days, the rate is much lower (0.09 ± 0.04 mA m^− 1/day). Low temperature investigation of magnetic properties indicates an initial magnetic assemblage of magnetite and pyrrhotite. Newly formed magnetite and hematite carry the remanence. We propose that magnetite is formed at the expense of pyrite. Hematite results from the progressive oxidation of newly formed magnetite. Our results suggest the possibility that any claystones that pass the oil window can be remagnetized due to the unique action of temperature.     

Petrology and Fe–Ti oxide reequilibration of the 1991 Mount Unzen mixed magma

A dacitic magma (64.5 wt.% SiO₂), a mixture of phenocryst-rich rhyodacite and an aphyric mafic magma, was erupted during the recent 1991–1995 Mount Unzen eruptive cycle. The experimental and analytical results of this study reveal additional details about conditions in the premixing and postmixing magmas, and the nature of the mixing process. The preeruption rhyodacitic magma was at a temperature of 790±20°C according to Fe–Ti oxide phenocryst cores, and at a depth of 6 to 7 km (160 MPa) according to Al-in-hornblende geobarometry. The mafic magma that mixed with the rhyodacite is found as andesitic (54 to 62 wt.% SiO₂) enclaves in the erupted magma and was essentially aphyric when intruded. Phase equilibria indicate that an aphyric andesite at 160 MPa is >1030°C (H₂O-saturated) and possibly as high as 1130°C (2 wt.% H₂O). The composition of the rhyodacite which was mixed with the andesite is estimated to lie between 67 and 69 wt.% SiO₂. Using these compositions and temperatures, the temperature of the Unzen magma after mixing is estimated to be at least 850° to 870°C. The groundmass Fe–Ti oxide microphenocrysts and those in pargasite-bearing reaction zones around biotite phenocrysts both give 890±20°C temperatures; the oxide–oxide contacts give temperatures of 910±20°C. The 900±30°C postmixing temperatures are consistent with phase-equilibria experiments which show that the magma was not above 930°C at 160 MPa. Our Fe–Ti oxide reequilibration experiments suggest that the mixing of the two magmas began within a few weeks of the eruption, which is a shorter time than is calculated using available diffusion data. There is also evidence that some mixing took place much closer to the time of extrusion based on the presence of unrimmed biotite phenocrysts in the magma.     

SrNdPb geochemical morphology between 10° and 17°N on the Mid-Atlantic Ridge: A new MORB isotope signature

Basalts dredged along the Mid-Atlantic Ridge axis between 10°N and 17°N have been studied for their trace element characteristics [1]. To give complementary information on mantle source history and magma genesis, these samples have been analysed for their SrNdPb isotopic compositions. There is a good correlation between the structure of the ridge axis which shows a topographic anomaly centered around 14°N and hygromagmaphile element ratios such as Rb/Sr, (Nb/Zr)_N or Sm/Nd as well as isotopic ratios plotted as a function of latitude. The samples coming from the 14°N topographic high show new MORB SrNd isotopic characteristics which pictured in a classical mantle array diagram, put their representative points close to HIMU sources of ocean islands such as St. Helena, Tubuaïand Mangaia. The 14°N mantle source presents geochemical characteristics which indicate mantle differentiation processes and a mantle history that are more distinct than so far envisaged from typical MORB data. Pb data indicates that the 14°N mantle source cannot be the result of binary mixing between a depleted mantle and a HIMU-type source. Rather, the enriched endmember could itself be a mixture of Walvis-like and HIMU-like materials. The geochimical observations presented favour the model of an incipient ridge-centered plume, in agreement with [1].     

Two-phase separation and fracturing in mid-ocean ridge gabbros at temperatures greater than 700°C

Microthermometric analyses of fluid inclusions on a suite of hydrothermally altered gabbros recovered just south of the eastern intersection of the Kane Fracture Zone and the Mid-Atlantic Ridge, record the highest homogenization temperatures yet reported for mid-ocean ridge hydrothermal systems. Fluid salinities in the high temperature inclusions are more than ten times that of seawater. Multiple generations of fluid inclusions entrapped along healed microfractures exhibit three distinct temperature-compositional groups. We interpret these populations as having been trapped during three separate fracturing events.The earliest episode of brittle failure in the gabbros is represented by coplanar, conjugate vapor-dominated and brine-dominated fluid inclusion arrays in primary apatite. Vapor-dominated inclusions exhibit apparent homogenization temperatures of 400°C and contain equivalent salinities of 1–2 wt.% NaCl. These inclusions are interspersed with liquid-dominated, sulfide-bearing inclusions containing salinities of 50 wt.% NaCl equivalent. These high salinity inclusions remain unhomogenized at temperatures greater than 700°C.Compositional and phase relationships of the fluid inclusions may be accounted for by two-phase separation of a fluid under 1000–1200 bars pressure. These pressures require that fluid entrapment occurred under a significant lithostatic component and indicate a minimum entrapmentdepth of 2 km below the axial valley floor. This depth corresponds to a minimum tectonic uplift of 3 km, in order to emplace the samples at the 3100 m recovery depth. The microfracture networks within magmatic apatites represent fluid flow paths for either highly modified, deeply penetrating seawater or a late stage magmatic aqueous fluid. The inclusions may have formed close to the brittle-ductile transition zone adjacent to an active magma chamber.Following collapse of the high temperature front, lower temperature fluids of definite seawater origin circulated through the open fracture networks, pervasively altering portions of the gabbros. This stage is represented by low-to-moderate (1–7 wt.% NaCl equivalent) salinity inclusions in plagioclase, apatite, epidote, and augite, which homogenize at temperatures of approximately 200–300°C and 400°C. Formation of hydrous mineral assemblages, under greenschist to lower amphibolite facies conditions, resulted in sealing of the vein system and may have resulted in modification of seawater salinities by as much as a factor of two. During or following these later stages of hydrothermal activity the gabbros were emplaced high on the axial walls by differential uplift attending formation of the flanking mountains.     

Chemical and optical studies of glass shards in Pleistocene and Pliocene ash layers from DSDP site 192, Northwest Pacific Ocean

Thirty-four ash layers of Pleistocene and Pliocene age from DSDP Site 192, northwestern Pacific Ocean, have been subjected to detailed chemical and optical study to evaluate: (1) the chemical and optical variability in glass shards from deep-sea ash layers, and (2) secondary changes brought about by prolonged exposure to seawater. Glass shards from approximately half of the ash layers studied were found to have uniform compositions which approach the precision of the microprobe chemical analyses, whereas the remainder are compositionally diverse (e.g., SiO₂, variations of 5–15% among shards from the same ash layer) and appear to be the eruptive products of compositionally zoned magma chambers. Optical studies of glass shards confirm the absence of devitrification or the formation of pervasive secondary alteration products. By contrast, chemical studies suggest that the glass shards have experienced progressive hydration with possible minor ion exchange of K, Mg, Ca and Si. The hydration occurs rapidly and leads to a rather uniform water content of 4.5–5% after several hundred thousands of years exposure to seawater. Step-wise heating dehydration experiments, optical effects, and published'oxygen isotope studies indicate that the water of hydration is incorporated uniformly within the glass. Systematic chemical differences between electron microprobe analyses of glass shard interiors and corresponding bulk chemical study by atomic absorption lead us to postulate that glass shard margins have undergone a minor chemical exchange with major cations in seawater. They have gained 0.10–0.20 wt. % K₂0, MgO, and CaO while losing a corresponding amount of Si₂O. Although the glass shards from DSDP Site 192 are hydrated and may have experienced subtle, surficial ion exchange, we stress that they are the most chemically representative samples available of magmas that were explosively erupted from volcanic arcs.     

Structural changes in trend parameters of the MLT winds based on wind measurements at Obninsk (55°N, 37°E) and Collm (52°N, 15°E)

Recent analysis of the long-term behavior of different geophysical data has demonstrated that trend parameters can change during a period of observation. Sophisticated general methods for an objective analysis of structural changes in linear trends have been developed during the last 10 years. Such methods are applied for an analysis of changes in trend parameters of the mesosphere/lower thermosphere wind observed over Obninsk (55°N, 37°E) from 1964 to 2007 and Collm (52°N, 15°E) from 1979 to 2008, respectively. We found that trend models with breakpoints are generally preferred against straight lines. At Obninsk, there are break-years in trends of the winter prevailing winds close to 1977, when a climatic regime shift was observed. The break-years in trends of the semidiurnal tides for both stations are close to years of possible changes in stratospheric ozone. Correlations of the Obninsk and Collm winds with atmospheric indices are also considered.     

Andean evolution at the Guañacos and Chos Malal fold and thrust belts (36°30′–37°s)

The Andes between 36°30′ and 37°S represent a Cretaceous fold and thrust belt strongly reactivated in the late Miocene. Most of the features that absorbed Neogene shortening were already uplifted in the late Cretaceous, as revealed by field mapping and confirmed by previous fission track analysis. This Andean section is formed by two sectors: a western-inner sector generated by the closure of the upper Oligocene-lower Miocene intra-arc Cura Mallín basin between the middle and late Miocene (Guañacos fold and thrust belt), and an eastern-outer sector, where late Triassic-early Jurassic extensional depocenters were exhumed in two discrete phases of contraction, in the latest early Cretaceous and late Miocene to the Present, respectively (Chos Malal fold and thrust belt). Late Miocene deformation has not homogeneously reactivated Cretaceous compressive structures, being minimal south of 37°30′S through the eastern-outer sector (southern continuation of the Chos Malal fold and thrust belt). The reason for such an inhomogeneous deformational evolution seems to be related to the development of a late Miocene shallow subduction regime between 34°30′ and 37°45′S, as it was proposed in previous studies. This shallow subduction zone is evidenced by the eastward expansion of the arc that was accompanied by the eastern displacement of the orogenic front at these latitudes. As a result, the Cretaceous fold and thrust belt were strongly reactivated north of 37°30′S producing the major topographic break along the Southern Central Andes.     

GEOSECS AtlanticSi profiles

Measurements of five cosmogenic³²Si vertical profiles in Atlantic waters (27°N to 60°S) are presented. The amounts of dissolved SiO₂ extracted range from 2 to 54 g; the amounts of water from which SiO₂ was extracted range between 540 kg and 270, 000 kg. In additon, SiO₂ recovered from four surface particulate composites (64°N to 61°S) were also analyzed for³²Si.³²Si measurements were made by milking and counting the daughter activity, ³²P. The net³²P activities range from 0.7 to 6.8 cph; typical errors in measurements of the³²P activities are 20–30%.The³²Si concentrations vary from 0.6 dpm/10⁶ kg of water in the North Atlantic surface waters to 235 dpm/10⁶ kg at 400 m depth in the circumpolar waters. The vertical profiles of³²Si at the five Atlantic stations approximately follow the Si profiles but the depth gradients are different. This would be expected also considering the in-situ release mechanisms due to dissolution and advection/diffusion from the bottom waters. Except for the circumpolar station 89, where the Si and³²Si profiles show the effect of marked vertical mixing (nearly depth independent profiles), the profiles show the following features: (1) specific activities of³²Si (³²Si/SiO₂ ratios) are lowest at intermediate depths, and (2) on an average the surface specific activities are higher, by 2–4 times, than the bottom water values. These data are consistent with generation of the highest specific activity³²Si waters at the surface, where Si concentrations are lowest and precipitation adds cosmogenic³²Si scavenged from the troposphere. Rapid removal of biogenic silica to the water-sediment interface, without much dissolution during transit, leads to the second regime of high³²Si specific activities.The³²Si inventories in the water column in the latitude belt 27°N-27°S are in the range (1–1.4) × 10⁻² dpm³²Si/cm², which is consistent with the expected fallout of cosmogenic³²Si. However, the³²Si column inventories south of 40°S are higher by a factor of 5–7, whereas the corresponding Si inventories increase by only a factor of 3. This excess³²Si in the Southern Ocean cannot be explained by direct fallout from the stratosphere or by melting of Antarctic snow and ice. Instead, this excess is maintained primarily by the southward deep-water transport of³²Si dissolved from sinking particulates.     

Chronology of cenozoic igneous and tectonic events in the central Chilean Andes — latitudes 35° 30′ to 36°S

Sixty-six K---Ar dates from igneous rocks in the central Chilean Andes between 33° and 38°S are reported in this study. From these results and observed field relations, major Cenozoic volcanic and intrusive rock units are divided into chronologic groups representing igneous events.Volcanic units of Oligocene (33.3–27.9 m.y.) and Early Miocene (20.2 m.y.) age have been dated west of the present range at 33°S but neither the magnitude nor extent of these volcanic events has yet been established. Extensive Middle to Late Miocene volcanism (15.3–6.4 m.y.) followed by regional folding is recognized in the map area between 35° 20′ and 36°S. Partly contemporaneous Middle Miocene volcanism (18.4–13.7 m.y.) also followed by regional folding is recorded in the Andes between 37° 30′ and 38°S. General volcanic quiescence from 6.4 to 2.5 m.y. is observed in the map area but whether this volcanic hiatus is of regional significance is not known.The majority of the K---Ar dates document a history of nearly continuous volcanism throughout the last 2.5 m.y. in the map area. The abundant and diverse sequences of volcanic strata formed during this time, have been divided into four successive age groups which as map units show the evolution and distribution of latest volcanic activity.Landforms preserved by this volcanic series show that topographic relief similar to the present has prevailed during this time. Deep incision of rivers into young volcanic terrain, estimated to be on the order of 1–2 m/1000 years, has produced a complex volcanic and morphologic record.Four plutons dated in this study give ages of 62.0, 41.3, 19.5, and 7.0 m.y. No spatial pattern of emplacement is observed in the map area where three of these plutons are represented.Similarities in structural style, orientation and degree of deformation of Miocene and Mesozoic strata suggest that Late Miocene regional folding may have accounted for a significant part of the observed deformation in older basement strata previously ascribed to earlier orogenies.A regional comparison of ages of recognized igneous and tectonic event at different latitudes in the central and southern Andes shows the gross chronology of Cenozoic events which can be correlated with sea-floor spreading and subduction events.     

Dissolved carbon dioxide in basaltic glasses: concentrations and speciation

Carbon dioxide dissolved in both synthetic Ca±Mg-bearing silicate glasses and natural basaltic glasses has been characterized using infrared spectroscopy. CO₂ is inferred to be dissolved in these glasses as distorted Ca or Mg carbonate ionic complexes that result in unique infrared absorption bands at 1515 cm⁻¹ and 1435 cm⁻¹. This speciation contrasts with the case of CO₂-bearing sodium aluminosilicate glasses, which contain both dissolved molecular CO₂ and dissolved Na-carbonate ionic-complexes. The difference in speciation in Ca±Mg-bearing melts may result in part from a higher activity of oxygens that react with CO₂ molecules to produce carbonate.Dissolved CO₂ contents of natural basaltic glasses can be determined from the intensities of the carbonate absorption bands at 1515 cm⁻¹ and 1435 cm⁻¹. The uncertainty of the method is estimated to be ± 15% of the amount present. The infrared technique is a powerful tool for the measurement of dissolved CO₂ contents in natural basaltic glasses since it is non-destructive, can be aimed at regions of glass a few tens of microns in size, and can discriminate between dissolved carbonate and carbon present as carbonate alteration, contained in fluid inclusions, or adsorbed on the glass.A set of submarine basaltic glasses dredged from a variety of locations contain 0–400 ppm dissolved CO₂, measured using the infrared technique. These concentrations are lower than most previous reports for similar basaltic glasses. No general relationship is observed between dissolved CO₂ content and depth of magmatic eruption, although some correlation might be present in restricted geographic locales.     

Chemical geothermometry and fluid–mineral equilibria for the Ömer–Gecek thermal waters, Afyon area, Turkey

Thermal waters of the Ömer–Gecek geothermal field, Turkey, with temperatures ranging from 32 to 92°C vary in chemical composition and TDS contents. They are generally enriched in Na–Cl–HCO₃ and suggest deep water circulation. Silica and cation geothermometers applied to the Ömer–Gecek thermal waters yield reservoir temperatures of 75–155°C. The enthalpy–chloride mixing model, which approximates a reservoir temperature of 125°C for the Ömer–Gecek field, accounts for the diversity in the chemical composition and temperature of the waters by a combination of processes including boiling and conductive cooling of deep thermal water and mixing of the deep thermal water with cold water. It is also determined that the solubility of silica in most of the waters is controlled by the chalcedony phase. Equilibrium states of the Ömer–Gecek thermal waters studied by means of the Na–K–Mg triangular diagram, Na–K–Mg–Ca diagram, K–Mg–Ca geoindicator diagram, activity diagrams in the systems composed of Na₂O–CaO–K₂O–Al₂O₃–SiO₂–CO₂–H₂O phases, log SI diagrams, and finally the alteration mineralogy indicate that most of the spring and low-temperature well waters in the area can be classified as shallow or mixed waters which are likely to be equilibrated with calcite, chalcedony and kaolinite at predicted temperature ranges similar to those calculated from the chemical geothermometers. It was also observed that mineral equilibrium in the Ömer–Gecek waters is largely controlled by CO₂ concentrations.     

CO2-filled vesicles in mid-ocean basalt

Volatile-filled vesicles are present in minor amounts in all samples of mid-ocean basalt yet collected (and presumably erupted) down to depths of 4.8 km. When such vesicles are pierced in liquid under standard conditions, the volume expansion of the gas is 0.2 ± 0.05 times the eruption pressure in bars or 20 ± 5 times the eruption depth in km. Such expansion could be used as a measure of eruption depth.A variety of techniques: (1) vacuum crushing and gas chromatographic, freezing separation, and mass spectrographic analyses; (2) measurements of phase changes on a freezing microscope stage; (3) microscopic chemical and solubility observations; and (4) volume change measurements, all indicate that CO₂ comprises more than 95% by volume of the vesicle gas in several submarine basalt samples from the Atlantic and Pacific. The CO₂ held in vesicles is present in quantities about equal to or greater than that presumed to be dissolved in the glass (melt) and amounts to 400–900 ppm of the rock. The rigid temperature of the glass is 800–1000°C and increases for shallower samples. A sulfur gas was originally present in subordinate amounts in the vesicles, but has largely reacted with iron in the vesicle walls to produce sulfide spherules.     

An experimental investigation of the quartz, Na-K, Na-K-Ca geothermometers and the effects of fluid composition

To test the possible effect of different fluid compositions on some standard geothermometry techniques, experiments were conducted in which a rhyolite from the Presidio Bolson area of West Texas was interacted with fluids of two different compositions (0.1 M NaCl and 0.01 M NaHCO₃). The temperature range was 100–500°C, pressure was 1000 bars, water/rock mass ratios were 6:1 and 5:1, and the duration of the experiments ranged from 12 to 130 days.Results showed that the quartz geothermometer worked well in the experimental system up to temperatures of 400°C. The results were not affected by differences in the major anionic species.The Na-K geothermometer gave temperatures an average of 76°C lower than the experimental temperatures, regardless of fluid type. The experimental data from this study agree well with previous experimental work in feldsparquartz systems.The Na-K-Ca geothermometer did not work well for experiments using 0.01 M NaHCO₃ but did work well for experiments using 0.1 M NaCl. Benjamin et al. (1983) concluded that the Na-K-Ca geothermometer is based on alteration reactions rather than feldspar exchange; however, no evidence for alteration reactions was observed in this study.     

Deep sea explosive activity on the Mid-Atlantic Ridge near 34°50′N: Magma composition, vesicularity and volatile content

Submersible observations and sampling were carried out in the rift valley of the Mid-Atlantic Ridge (MAR) near 34°40′N–35°N. The 4-km-wide rift valley consists of a Neo Volcanic Zone (NVZ) (<1 km wide) bounded at the west by a Median Ridge (MR) (5 km wide and 20 km long) and at the east by the first scarps of the eastern wall. The MR and the eastern wall are characterized by volcanic cones about 200–300 m height culminating at depths of 1500–1900 m which are made up of volcaniclastic deposits (pyroclasts and hyaloclasts) suggestive of explosive volcanism. Based on their surface morphology, degree of vesicularity, and composition, the erupted deposits are classified into four groups: (1) poorly vesicular (<15% vesicles) N- and T-MORBs (K/Ti <0.25, Na₂O+K₂O<2.9%) consisting of sheet flows and pillows formed during fissure eruptions in the NVZ at 2000–2300 m depths; (2) vesicular (15–30% vesicles) E-MORBs (K/Ti=0.25−0.45,Na₂O+K₂O>2.8−3.2%) and alkali basalts (K/Ti=0.45−0.70,Na₂O+K₂O>3.3−4) made up mainly of pillows; (3) highly vesicular (>35% vesicles) pillow lava and pyroclastic (scoria-like) alkali basalts (K/Ti>0.45−0.80,Na₂O+K₂O>3−4%); and (4) hyaloclastites consisting of glassy shards of alkali basalt composition. The total water and carbon contents of the deposits increase with the incompatible element concentrations. The estimated initial H₂O content for the N- and T-MORBs is less than 3500 ppm, whereas for the E-MORBs and alkali basalts the H₂O content is near 4000 and 7000 ppm, respectively. While the H₂O is mainly in the melt, the carbon is in the form of CO₂ filling vesicles. The vesicles are formed from magma with an initial carbon content of 1000–3000 for the N- and T-MORBs, 3000–6500 ppm for the E-MORBs and higher than 1 wt% for the alkali basalts.The various lava types were derived from a heterogeneous mantle source composed of enriched and depleted components during sequential eruptions of N-, T- and E-MORBs and alkali basalts (K/Ti>0.7). The amount of CO₂ and H₂O in equilibrium with the dissolved species present in the vesicles indicates that CO₂ (XCO₂=1−0.84) was the main exsolved compound responsible for bubble nucleation. The increase in the degree of vesicularity and pressure of the volatile phases is mainly due to the early exsolution of CO₂ from an alkali melt. The exsolution of significant amounts of dissolved water occurred only for the alkali basalt a few hundred meters beneath the seafloor and contributed to late bubble expansion. This subsequent addition of magmatic water to the vesicles increased the gas pressure and triggered explosions. An alternative hypothesis for the explosive volcanism is based on field observations. During crater collapsed, seawater could have been trapped in fractured volcanic conduits and later sealed by hydrothermal fluid circulation and precipitation. In such an environment, this seawater will be heated and vaporized during renewed magmatic upwelling. Both scenarios give rise to fragmented debris (hyaloclasts and pyroclasts) and the explosive events create turbulent flows followed by differential gravity settling of the particles (shards versus lapilli) through the seawater.     

Hydrothermal vent waters at 13°N on the East Pacific Rise: isotopic composition and gas concentration

Gas concentrations and isotopic compositions of water have been measured in hydrothermal waters from 13°N on the East Pacific Rise. In the most Mg-depleted samples ( 5 × 10⁻³ moles/kg) the gas concentrations are: 3–4.5 × 10⁻⁵ cm³ STP/kg helium, 0.62–1.24 cm³ STP/kg CH₄, 10.80–16.71 × 10⁻³ moles/kg CO₂. The samples contain large quantities (95–126 cm³/kg) of H₂ and some carbon monoxide (0.26–0.36 cm³/kg) which result from reaction with the titanium sampling bottles. δ¹³C in methane and CO₂ (−16.6 to −19.5 and −4.1 to −5.5 respectively) indicate temperatures between 475 and 550°C, whereas δ¹³C_CO is compatible with formation by reduction of CO₂ on Ti at 350°C close to the sampling temperature.³He/⁴He are very homogeneous at (7.5 ± 0.1)R_A(³He/⁴He = 1.0 × 10⁻⁵) and very similar to already published data as well as CH₄/³He ratios between 1.4 and 2.1 × 10⁶.¹⁸O and D in water show enrichments from 0.39 to 0.69‰ and from 0.62 to 1.49‰ respectively. These values correspond to W/R ratios of 0.4–7. The distinct¹⁸O enrichments indicate that the isotopic composition of the oceans is not completely buffered by the hydrothermal circulations. The³He-enthalpy relationship is discussed in terms of both hydrothermal heat flux and³He mantle flux.     

Oxygen diffusion rates in quartz exchanged with CO2

Oxygen self diffusion rates were determined in quartz samples exchanged with¹⁸O-enriched CO₂ between 745 and 900°C and various pressures, and the diffusion profiles were measured using an ion microprobe. The activation energy (Q) and preexponential factor (D₀) at P(CO₂) = P(tot) = 100 bar, for diffusion parallel to the c-axis are 159 ( ± 13) kJ/g atom and 2.10 (+0.75/ −0.55) × 10⁻⁸ cm²/s. This rate is approximately 100 times slower than that obtained from hydrothermal experiments and 100 times faster than a previous 1-bar quartz-O₂ exchange experiment. The oxygen diffusion rate measured at 0.6 bar, 888°C, and at 900°C in vacuum is in agreement with the previous 1-bar exchange experiments with¹⁸O₂. The effect of higher CO₂ pressures is small. At 900°C, the diffusion rate exchanged with CO₂ is = 2.35 × 10⁻¹⁵ cm²/s at 100 bar, 2.24 × 10⁻¹⁵ cm²/s at 3.45 kbar and 8.13 × 10⁻¹⁵ cm²/s at 7.2 kbar.There is probably a diffusing species, other than oxygen, that enhances the oxygen diffusion rate in these quartz-CO₂ systems, relative to that occurring at very low pressures or in a vacuum. The effect of this diffusing species, however, is not as strong as that associated with H₂O. Preserved oxygen isotope fractionations between coexisting minerals in a slowly cooled, high-grade metamorphic terrane will vary depending upon whether a water-rich phase was present or not. Closure temperatures will be approximately 100°C higher in rocks where no water-rich phase was present during cooling. The measured fractionations between coexisting minerals in metamorphic rocks may potentially be used as a sensor of water presence during retrogression.     

Stability relation of (Mg,Fe)SiO3 garnets, major constituents in the Earth's interior

High-pressure and high temperature experiments at 20 GPa on (Mg,Fe)SiO₃ have revealed stability fields of two types of aluminium-free ferromagnesian garnets; non-cubic garnet and cubic garnet (majorite). Majorite garnet is stable only within a limited compositional variation, 0.2 < Fe/(Mg + Fe)< 0.4, and in the narrow temperature interval of 200°C around 2000°C, while the stability of non-cubic garnet with more iron-deficient compositions persists up to higher temperatures. These two garnets show fractional melting into iron-deficient garnet and iron-rich liquid, and the crystallization field of cubic garnet extends over Fe/(Mg + Fe)= 0.5. The assemblage silicate spinel and stishovite is a low-temperature phase, which also occurs in the iron-rich portion of the MgSiO₃—FeSiO₃ system. The sequence as given by the Fe/(Mg + Fe) value for the coexisting phases with the two garnets at 2000°C and 20 GPa is: silicate modified spinel aluminium-free garnets silicate spinel.Natural majorite in shock-metamorphosed chondrites is clarified to be produced at pressures above 20 GPa and temperatures around 2000°C. Similar shock events may cause the occurrence of non-cubic garnet in iron-deficient meteorites. Non-cubic garnet could be a stable phase in the Earth's mantle if a sufficiently low concentration of aluminium is present in the layer corresponding to the stable pressure range of non-cubic garnet. The chemical differentiation by melting in the deep mantle is also discussed on the basis of the present experimental results and the observed coexistence of majorite garnet with magnesiowüstite in chondrites.     

Presence of native gold and tellurium in the active high-sulfidation hydrothermal system of the La Fossa volcano (Vulcano, Italy)

Grains of native gold and tellurium were found in siliceous hydrothermally altered rocks in the high-temperature (170–540°C) fumarolic field of the La Fossa volcano (Island of Vulcano). In addition to Au and Te, Pb–Bi sulfides (cannizzarite) and Tl-bromide chloride were found as sublimates in the hottest fumarolic vents of the crater rim. The chemical composition of altered rocks associated with sublimate deposition indicate the presence of a significant concentration of Te (up to 75 ppm), while gold concentrations are very low (<9 ppb). Pb, Bi and Tl are strongly enriched in the hottest and less oxidized fumarolic vents, reaching concentrations of 2186, 146 and 282 ppm, respectively. These elements are transported (generally as chloride complexes) to the surface by volcanic gases, and several of these (Bi, Te, Tl) are originated from magma degassing. The silicic alteration is produced by the flow of fluids with pH<2. High acidity results from introduction of magmatic gases such as SO₂, HCl and HF released by the shallow magmatic reservoir of La Fossa volcano. The silicic alteration found at Vulcano may represent an early stage of the `vuggy silica' facies which characterizes the high-sulfidation epithermal ore deposits, confirming the analogies existing between this type of ore deposit and magmatic-hydrothermal systems associated with island-arc volcanoes.