Thermodynamic data from redox reactions at high temperatures. IV. Calibration of the Re-ReO2 oxygen buffer from EMF and NiO+Ni-Pd redox sensor measurements

The chemical potential of oxygen defined by the equilibrium:

Formulation of the thermodynamic functions for mantle minerals: MgO as an example

The formulas for thermodynamic functions for minerals are presented, couched in terms of the important thermodynamic variable K_T= (P/T)_v, where is the volume thermal expansivity and K_T is the isothermal bulk modulus. Presenting the formulas in this way leads to simplification since K_T as a product varies only slightly with volume, and is close to being independent of temperature at high temperature. Using our equations, we present as examples some computed data in the form of graphs on the entropy, internal energy, Helmholtz free energy, and Gibbs free energy in the high temperature regime (up to 2000 K) and for high compression (up to 0.7), for MgO. For entropy, knowledge of the V, T dependence of K_T is sufficient. For enthalpy and internal energy, the equation of state is needed in addition.     

Mechanisms of the transformations between the α, β and γ polymorphs of Mg2SiO4 at 15 GPa

Data on the mechanisms of mantle phase transformations have come primarily from studies of analogue systems reacted experimentally at low pressures. In order to study transformation mechanisms in Mg₂SiO₄ at mantle pressures, forsterite () has been reacted in the stability field of -phase, at 15 GPa and temperatures up to 900° C, using a multianvil split-sphere apparatus. Transmission electron microscope studies of samples reacted for times ranging from 0.25–5.0 h show that forsterite transforms to -phase by an incoherent nucleation and growth mechanism involving nucleation on olivine grain boundaries. This mechanism and the resultant microstructures are very similar to those observed at much lower pressures in analogue systems (Mg₂GeO₄ and Ni₂SiO₄) as the result of the olivine to spinel () transformation. Metastable spinel () also forms from Mg₂SiO₄ olivine at 15 GPa, in addition to -phase, by the incoherent nucleation and growth mechanism. With time, the spinel progressively transforms to the stable -phase. After 1 h, spinels exhibit a highly striated microstructure along {110} and electron diffraction patterns show streaking parallel to [110] which indicates a high degree of structural disorder. High resolution imaging shows that the streaking results from thin lamellae of -phase intergrown with the spinel. The two phases have the orientation relationship [001]//[001] and [010]//[110] so that the quasi cubic-close-packed oxygen sublattices are continuous between both phases. These microstructures are similar to those observed in shocked meteorites and show that spinel transforms to -phase by a martensitic (shear) mechanism. There is also evidence that the mechanism changes to one involving diffusion-controlled growth at conditions close to equilibrium.     

Pressure-volume-temperature behavior of γ-Fe2SiO4 (spinel) based on static compression measurements at 400° C

Thirteen energy-dispersive x-ray diffraction spectra for -Fe₂SiO₄ (spinel) collected in situ at 400° C and pressures to 24 GPa constitute the basis for an elevated-temperature static compression isotherm for this important high-pressure phase. A Murnaghan regression of these molar volume measurements yields 177.3 (±17.4) GPa and 5.4(±2.5) for the 400° C, room pressure values of the isothermal bulk modulus (K _{P 0}) and its first pressure derivative (K _{P 0}), respectively. When compared to the room-Tdeterminations of K _{P 0} available in the literature, our 400° C K _{P 0} yields -4.1 (±6.2)×10^-2 GPa/degree for the average value of (K/T) _{P 0} over the temperature interval 25° C<><400°>A five-parameter V(P, T) equation for -Fe₂SiO₄ based on simultaneous regression of our data combined with the elevated P-Tdata of Yagi et al. (1987) and the extrapolated thermal expansion values from Suzuki et al. (1979) yields isochores which have very little curvature [(² T/P ²) _v 0], in marked contrast to the isochores for fayalite (Plymate and Stout 1990) which exhibit pronounced negative curvature [(T/P ²) _v <0]. along=" the=">-Fe₂SiO₄ reaction boundary V_Rvaries from a minimum of approximately 8.3% at approximately 450° C to approximately 8.9% at 1200° C. Extrapolation of the fayalite and -Fe₂SiO₄ V(P, T) relationships to the temperature and pressure of the 400 km discontinuity suggests a V _R of approximately 8.4% at that depth, approximately 10% less than the 9.3% V _R at ambient conditions.     

Mössbauer study of a California desert celadonite and its pedogenically-related smectite

Celadonite from the northwestern Mojave Desert area of California was examined by detailed Mössbauer spectroscopy at temperatures from 10 K to 400 K. In addition to the predominant Fe³⁺ doublet with isomer shift 0.4 mm s^–1 and quadrupole splitting 0.4 mm s^–1, another Fe³⁺ doublet with 0.4, 1.2 mm/s and two Fe²⁺ doublets with 1.1, 1.7, 2.7 mm s^–1 at 300 K were distinguished. The minor Fe³⁺ component is ascribed to dehydroxylated surface sites. Most of the remaining Fe(90%) is M2 cis-OH octahedral in an ordered M⁺–M²⁺ array. However, about 10% is M1 trans-OH Fe²⁺. Isomer shift vs. T gives Debye temperatures of 570 K for Fe³⁺ in M2 and 380 K for both Fe²⁺ sites, indicating greater vibrational freedom for Fe²⁺. Quadrupole splitting vs. T for Fe²⁺ gives a valence electronic energy splitting of 760 cm^–1 between the ground and first excited state for M2. The M1 sites have a more drastic variation in vs. T which indicates not only a lower first excited state but a rhombic distortion at these sites. A proposed explanation is a neighboring M2 site vacancy. The soil clay formed from this celadonite, which is mostly Fe-rich smectite, was also studied by Mössbauer spectroscopy. About half the Fe²⁺ has been oxidized in the clay, but the isomer shifts and quadrupole splittings are essentially the same as in the original celadonite. A texture orientation in the clay absorber was detected by measuring the absorber at 55° to the source radiation. This texture effect produces asymmetric doublets in the usual 90° measurement.     

Grossular activity-composition relationships in ternary garnets determined by reversed displaced-equilibrium experiments

Activity-composition relationships of Ca₃Al₂Si₃O₁₂ (grs) in ternary Ca-Mg-Fe garnets of various compositions have been determined by reversed displaced equilibrium experiments at 1000° C and 900° C and pressures of 8 to 17 kbar. The mixing of grs in garnet is nearly ideal at 30 mol% grs, with positive deviations from ideality at lower grs contents. Models of garnet mixing currently in the literature do not predict this trend. Analysis of the present reversals, in conjunction with a garnet mixing model based solely on calorimetry measurements on the binary joins, indicates that a ternary interaction constant for a ternary asymmetric Margules model (Wohl 1953) cannot be constrained. Apparently, some aspects of the garnet binary joins are still not well-known. An alternative asymmetric empirical model, based on analysis of pseudobinary joins of constant Mg/Mg + Fe(Mg #), reproduces the data well and is able to predict grs activity coefficients for garnets with grs contents between 3 and 40 mol% and Mg numbers between 0 and 0.60. The grossular activity coefficient, _grs, is given by:

Mössbauer study of the thermal decomposition of lepidocrocite and characterization of the decomposition products

The lepidocrocite (-FeOOH) to maghemite (-Fe₂O₃), and the maghemite to hematite (-Fe₂O₃) transition temperatures have been monitored by TGA and DSC measurements for four initial -FeOOH samples with different particle sizes. The transition temperature of -FeOOH to -Fe₂O₃ and the size of the resulting particles were not affected by the particle size of the parent lepidocrocite. In contrast, the -Fe₂O₃ to -Fe₂O₃ transition temperature seems to depend on the amount of excess water molecules present in the parent lepidocrocite. Thirteen products obtained by heating for one hour at selected temperatures, were considered. Powder X-ray diffraction was used to qualify their composition and to determine their mean crystallite diameters. Transmission electron micrographs revealed the particle morphology. The Mössbauer spectra at 80 K and room temperature of the mixed and pure decomposition products generally had to be analyzed with a distribution of hyperfine fields and, where appropriate, with an additional quadrupole-splitting distribution. The Mössbauer spectra at variable temperature between 4.2 and 400 K of two single-phase -Fe₂O₃ samples with extremely small particles show the effect of superparamagnetism over a very broad temperature range. Only at the lowest temperatures (T55 K), two distributed components were resolved from the magnetically split spectra. In the external-field spectra the m_I=0 transitions have not vanished. This effect is an intrinsic property of the maghemite particles, indicating a strong spin canting with respect to the applied-field direction. The spectra are successfully reproduced using a bidimensional-distribution approach in which both the canting angle and the magnetic hyperfine field vary within certain intervals. The observed distributions are ascribed to the defect structure of the maghemites (unordered vacancy distribution on B-sites, large surface-to-bulk ratio, presence of OH^- groups). An important new finding is the correlation between the magnitude of the hyperfine field and the average canting angle for A-site ferric ions, whereas the B-site spins show a more uniform canting. The Mössbauer parameters of the two hematite samples with MCD₁₀₄ values of respectively 61.0 and 26.5 nm display a temperature variation which is very similar to that of small-particle hematites obtained from thermal decomposition of goethite. However, for a given MCD the Morin transition temperature for the latter samples is about 30 K lower. This has tentatively been ascribed to the different mechanisms of formation, presumably resulting in slightly larger lattice parameters for the hematite particles formed from goethite, thus shifting the Morin transition to lower temperatures.Senior Research Associate, National Fund for Scientific Research (Belgium)     

Carbon isotopic thermometry and geobarometry of sillimanite isograd in thermal aureoles: the depth of emplacement of upper crustal granitic bodies

Carbon isotope fractionation between coexisting calcite and graphite (C ) has been studied in metamorphosed limestones from three thermal aureoles around Cretaceous granitic bodies (i.e., Tanohata, Tono, and Senmaya aureoles) in the Kitakami Mountains, Northeast Japan. C in each aureole decreases toward the granitic bodies, and becomes virtually uniform near the sillimanite isograd for metapelites, although calcite has variable isotopic ratios reflecting the original sedimentary compositions. The relationships indicate that isotopic equilibrium has been attained in metamorphosed limestone of sillimanite grade. Estimated C at the sillimanite isograd is similar in the Tanohata and Tono aureoles, but different in the Senmaya aureole with smaller carbon isotopic fractionations. From the temperature dependence of C and the negative dP/dT of andalusite–sillimanite equilibrium, we conclude that the sillimanite isograd in the Senmaya aureole was under higher temperature and lower pressure than in the other two localities. Temperatures at the sillimanite isograd are estimated by using existing calibrations of carbon isotopic exchange between calcite and graphite, whereas pressures are estimated from carbon isotopic temperatures and the andalusite–sillimanite equilibrium (Holdaway and Mukhopadhyay 1993a). Consistency of the P–T estimates is examined in the light of phase equilibria in the pelitic system. The estimated pressures at the sillimanite isograd are at about 2.1–2.7(±0.2) kbar for the Tanohata and Tono aureoles and less than 1 kbar for the Senmaya aureole, respectively. Geobarometry of sillimanite isograd in thermal aureoles indicates a marked difference in the depth of solidification of upper crustal granitoids: the Senmaya pluton has intruded and solidified at a very shallow level of less than 4 km whereas the Tanohata and Tono plutons are more deep-seated (ca. 8–10 km). The method can also be an effective tool in studying low-pressure type metamorphism in which geothermobarometry using garnet is not always applicable.Editorial responsibility: J. Hoefs     

Carbon and hydrogen isotopic composition and generation pathway of biogenic gas in China

The carbon and hydrogen isotopic composition of biogenic gas is of great importance for the study of its generation pathway and reservoiring characteristics. In this paper, the formation pathways and reservoiring characteristics of biogenic gas reservoirs in China are described in terms of the carbon and hydrogen isotopic compositions of 31 gas samples from 10 biogenic gas reservoirs. The study shows that the hydrogen isotopic compositions of these biogenic gas reservoirs can be divided into three intervals: δ>−200‰, −250‰<δ<-−200‰ and δ<−250‰. The forerunners believed that the main generation pathway of biogenic gas under the condition of continental fresh water is acetic fermentation. Our research results showed that the generation pathway of biogenic gas under the condition of marine facies is typical CO₂- reduction, the biogenic gas has heavy hydrogen isotopic composition: its δ values are higher than −200‰; that the biogenic gas under the condition of continental facies also was generated by the same way, but its hydrogen isotopic composition is lighter than that of biogenetic gas generated under typical marine facies condition: −250‰<δ<−200‰, the δ values may be related to the salinity of the water medium in ancient lakes. From the relevant data of the Qaidam Basin, it can be seen that the hydrogen isotopic composition of biogenic methane has the same variation trend with increasing salinity of water medium. There are biogenic gas reservoirs formed in transitional regions under the condition of continental facies. These gas reservoirs resulted from both CO₂-reduction and acetic fermentation, the formation of which may be related to the non-variant salinity of ancient water medium and the relatively high geothermal gradient, as is the case encountered in the Baoshan Basin. The biogenic gas generating in these regions has light hydrogen isotopic composition: δ<−250‰, and relatively heavy carbon isotopic composition. There is a fairly strong negative correlation between the carbon isotopic composition and the hydrogen isotopic composition. The generation mechanism and pathway of carbon, and the hydrogen isotopic composition of biogenic gas may be used to ascertain whether biogenic gas samples from the natural world are of industrial utilization value. In general, the biogenic gas formed by way of acetic fermentation is not propitious to the formation of gas reservoirs.     

Low-temperature gas from marine shales

Thermal cracking of kerogens and bitumens is widely accepted as the major source of natural gas (thermal gas). Decomposition is believed to occur at high temperatures, between 100 and 200°C in the subsurface and generally above 300°C in the laboratory. Although there are examples of gas deposits possibly generated at lower temperatures, and reports of gas generation over long periods of time at 100°C, robust gas generation below 100°C under ordinary laboratory conditions is unprecedented. Here we report gas generation under anoxic helium flow at temperatures 300° below thermal cracking temperatures. Gas is generated discontinuously, in distinct aperiodic episodes of near equal intensity. In one three-hour episode at 50°C, six percent of the hydrocarbons (kerogen & bitumen) in a Mississippian marine shale decomposed to gas (C₁–C₅). The same shale generated 72% less gas with helium flow containing 10 ppm O₂ and the two gases were compositionally distinct. In sequential isothermal heating cycles (~1 hour), nearly five times more gas was generated at 50°C (57.4 μg C₁–C₅/g rock) than at 350°C by thermal cracking (12 μg C₁–C₅/g rock). The position that natural gas forms only at high temperatures over geologic time is based largely on pyrolysis experiments under oxic conditions and temperatures where low-temperature gas generation could be suppressed. Our results indicate two paths to gas, a high-temperature thermal path, and a low-temperature catalytic path proceeding 300° below the thermal path. It redefines the time-temperature dimensions of gas habitats and opens the possibility of gas generation at subsurface temperatures previously thought impossible.     

Al-O--Al paramagnetic defects in kaolinite

Trapped holes located on Al-O-Al bonds in kaolinite were studied by electron paramagnetic resonance spectroscopy (EPR) at 9.3 and 35 GHz applied to well-crystallized, X-ray irradiated and oriented samples. The Q-band EPR spectrum is characterized by three clearly separated groups of 11 quasi-equidistant superhyperfine lines centered at g_xx=2.040±0.0005, g_yy=2.020±0.0005 and g_zz=2.002±0.001. In each of these groups, the 11 superhyperfine lines exhibit intensities according to the ratios 12345654321. An angular dependence of the Q-band EPR spectrum with respect to the magnetic field is demonstrated by measurements on oriented films of kaolinite. An appropriate numerical treatment of the EPR spectra is described, which allowed extraction of the SuperHyperfine Structures (SHFS). X-and Q-band spectra have also been simulated. It is concluded from these experiments that only one type of center is present. This center, labelled the B-center in the literature, is very probably a hole trapped on oxygen (O^- center) atoms coupled to two octahedral aluminium.     

Al-Si ordering in Sr-feldspar SrAl2Si2O8: IR,TEM and single-crystal XRD evidences

Al-Si ordering in Sr-feldspar has been followed by isothermal annealing, starting from a disordered metastable configuration. Ordering could not be followed by changes in the spontaneous strain as cell parameters did not show significant changes with thermal treatment from 0.016 h to 452 h at T=1350° C, while, on the contrary, significant changes in IR spectra are observed. A single crystal obtained from melt (Q _od 0) has been progressively heated up to 678 h at T=1350° C and the relevant structural refinements enabled to monitor changes in degree of Al-Si order up to Q_od = 0.86. In isothermal treatment for Sr-feldspar it is observed a significantly lower Q _od than in anorthite after the same annealing time. TEM observation has shown in Sr-feldspar, also for shortest annealing, b type reflections, while in anorthite, in the same conditions, e type reflections have been observed (Carpenter 1991a). In the first stages of ordering b APDs sized 100 Å (at T=1350° C, 0.33 h) have been observed in Sr-feldspar; APD coarsening occurs with an activation energy of 120±7 kcal mol^-1, not significantly different from anorthite. The ordering process seems to be a slower process in Sr-feldspar than in anorthite, even though data from longer annealing suggest that the Q _od close to the equilibrium is the same in Sr and Ca-feldspar (Q _od = 0.86 at T=1350° C).     

The α-β phase transition in cristobalite,SiO2

Cristobalite, a high temperature phase of silica, SiO₂, undergoes a (metastable) first-order phase transition from a cubic, , to a tetragonal, P4₃2₁2 (or P4₁2₁2), structure at around 220° C. The cubic C9-type structure for -cristobalite (Wyckoff 1925) is improbable because of two stereochemically unfavorable features: a 180° Si-O-Si angle and an Si-O bond length of 1.54 Å, whereas the corresponding values in tetragonal -cristobalite are 146° and 1.609 Å respectively. The structure of the -phase is still controversial. To resolve this problem, a symmetry analysis of the (or P4₁2₁2) transition in cristobalite has been carried out based on the Landau formalism and projection operator methods. The starting point is the ideal cubic ( ) C9-type structure with the unit cell dimension a (7.432 Å) slightly larger than the known a dimension (7.195 Å at 205° C) of -cristobalite, such that the Si-O-Si angle is still 180°, but the Si-O bond length is 1.609 Å. The six-component order parameter driving the phase transition transforms according to the X₄ representation. The transition mechanism essentially involves a simultaneous translation and rotation of the silicate tetrahedra coupled along 110. A Landau free-energy expression is given as well as a listing of the three types of domains expected in -cristobalite from the transition. These domains are: (i) transformation twins from a loss of 3-fold axes, (ii) enantiomorphous twins from a loss of the inversion center, and (iii) antiphase domains from a loss of translation vectors 1/2 110 (FP). These domains are macroscopic and static in -cristobalite, and microscopic and dynamic in -cristobalite. The order parameter , couples with the strain components as ², which initiates the structural fluctuations, thereby causing the domain configurations to dynamically interchange in the -phase. Hence, the - cristobalite transition is a fluctuation-induced first-order transition and the -phase is a dynamic average of -type domains.     

Fluid venting activity on the Costa Rica margin: new results from authigenic carbonates

Carbonate precipitates on mounds and along tectonic scarps off the Costa Rica margin are manifestations of subduction-induced dewatering. The long-term dewatering history is recorded in mineralogical, petrological and isotope signals of carbonates recovered from these sites. The carbonates are strongly depleted in ¹³C (–11 to –53 PDB) and enriched in ¹⁸O (+4 to +8 PDB). Thermogenic methane and biogenic methane were identified as sources of the carbon. Chemoherm carbonates and seepage-associated carbonates formed in a focused flow regime have lighter ¹³C values, while others formed in a more diffusive flow regime have slightly enriched C isotope values. Three fluid components were inferred based on the calculation of equilibrium ¹⁸O: clay dehydration water, gas hydrate water and seawater. Calculated equilibrium ¹⁸O values of carbonates from different down-core depths as well as from different precipitation stages show that the ¹⁸O of the precipitating fluid is progressively depleted with time. Dolostones showing a methane-C source and a well constrained O-isotope signature are thought to have formed at depth in the sediment and subsequently became exhumed. Glauconitic sandstones cemented by methane-derived carbonate provide evidence that fluid and solid material have been expelled by the mud volcano.     

U.S. Geological Survey probabilistic methodology for oil and gas resource appraisal of the United States

Probabilistic methodology used by the U.S. Geological Survey is described for estimating the quantity of undiscovered recoverable conventional resources of oil and gas in the United States. A judgmental probability distribution of the quantity of resource and its properties is determined for a geologic province or basin. From this distribution, point and interval estimates of the quantity of undiscovered resource are obtained. Distributions and their properties are established for each of the following resources: (1) oil and nonassociated gas from estimates of the probability of the resource being present and the conditional probability distribution of the quantity of resource given that the resource is present, (2) associated-dissolved gas from its corresponding oil distribution, (3) total gas, (4) oil and total gas in two or more provinces. Computer graphics routines are illustrated with examples from the U.S. Geological Survey Circular 860.     

The effects of sub-blocking temperature metamorphism on the K/Ar systematics of hornblendes: 40Ar/39Ar dating of polymetamorphic garnet amphibolite from the Franciscan Complex,California

The effects of sub-blocking temperature metamorphism on the K/Ar system in hornblende, as revealed by ⁴⁰Ar/³⁹Ar release spectra, have been studied in a polymetamorphic knocker from the Franciscan Complex (FC), California. A primary amphibolite assemblage of horn-blende +rutile+epidote+apatite±garnet±sphene is variably overprinted by a blueschist facies assemblage of blue amphibole +lawsonite+chlorite+white mica+pumpellyite±sphene. The secondary assemblage formed at a temperature of 370° C, below that at which rapid Ar diffusion is expected in hornblende. Hornblendes from three, variably-altered samples of garnet amphibolite yield total gas ages of 147 to 161 Ma, but the corresponding plateau ages of 163.0±2.8, 160.6±2.2, and 161.8±2.2 Ma are identical within error. Hornblende separates with lower total gas ages come from more highly overprinted rocks, have excess K compared to that expected on the basis of electron probe analyses, and exhibit anomalously high K/Ca ratios in the low-temperature fractions of their incremental heating spectra. The reduced total gas ages result from the presence of thin (2 m) sheets of younger white mica in hornblendes from the moderately and highly altered amphibolites. The secondary micas are difficult to detect because of their small size and low abundance (2%), but because their K content is 50 to 100 times that of the host hornblende, they contribute significantly to the K and Ar budgets of the sample. The mica intergrowths are not removed by normal sample preparation, but because the mica inclusions degas at lower temperatures than hornblende during vacuum extraction, incremental heating analyses can provide precise cooling ages for the hornblendes as well as useful estimates of the age of the mica inclusions. The hornblende separate from the most altered sample contained 20±10% younger blue amphibole replacing hornblende, but its plateau age was not significantly affected. This is consistent with a replacement process in which K and Ar loss from the hornblende are coupled, leaving the K/Ar system undisturbed in relict primary grains. The K and Ar budgets of the sample are not strongly affected by the blue amphibole because of its very low K content. Because partial replacement of primary amphibole by high-K phyllosilicates occurs in many geological environments, effects like those described here could be widespread.     

Carbon isotope fractionation between calcite,graphite and CO2: an experimental study

The partitioning of stable carbon isotopes between calcite, graphite and CO₂ was experimentally determined at temperatures from 500 to 1200 °C and 1 to 15 kbar pressure. Attainment of carbon isotope equilibrium in CO₂-calcite runs was proven by achieving the same fractionation from isotopically opposite directions. The resultant CO₂-calcite fractionation curve for carbon differs from Bottinga's calculation by 1.2 and confirms recent experiments of Chacko et al. and Mattey et al. In CO₂-graphite experiments equilibrium fractions were extrapolated by applying the partial-exchange technique of Northrop and Clayton and by optimizing the contribution of surface reaction in graphite. CO₂-graphite fractionations at temperatures up to 800 °C are in fair agreement with Bottinga's calculation, but yield a surprisingly high fractionation of 5 at upper mantle temperatures. The combination of CO₂-calcite (carbon) and CO₂-graphite fractionation results in a new experimentally determined calcite-grapite fractionation curve, expressed by the equation:

The Enåsen gold deposit,central Sweden

Stable isotope analyses of quartz, sulphides, and magnetite were conducted to provide information on thermal history and source of hydrothermal fluids in the Palaeoproterozoic Enåsen gold deposit. Reequilibration and homogenization of oxygen isotopes throughout the rock have apparently not occurred despite the upper amphibolite to granulite facies regional metamorphism that has affected the rocks. However, oxygen isotope geothermometry on a coexisting quartz-magnetite pair gave a minimum temperature for peak metamorphism of around 650 °C which agrees with Fe-Mg geothermometry. This suggests that grain-scale equilibrium is achieved. The variation in oxygen isotope ratios (¹⁸O = 7.3 – 10.5) on quartz from the metamorphosed acid sulphate alteration zone is suggested to represent a cooling trend in the fossil hydrothermal system with higher ¹⁸O-values in more superficial parts. Temperatures of alteration and silicification and isotopic composition of hydrothermal fluids could not be defined from the present data but it was recognized that the data is compatible with a epithermal genesis for the deposit. It is suggested that alteration, silicification, and mineralization at the Enåsen gold deposit took place in a high sulphidation epithermal environment at temperatures of around 200–250 °C and that the hydrothermal fluids consisted of meteoric and magmatic water. A tentative reconstruction of the fossil hydrothermal system is presented. Sulphur isotope ratios of sulphides from the fold-bearing quartz-sillimanite gneiss gave ³⁴S-values close to zero indicating a magmatic source of the sulphur.     

Natural groundwater of a gas field utilizable for a bioremediation of trichloroethylene-contamination

Groundwater from a shallow aquifer in Mobara, a city in a natural gas field in Chiba Prefecture, Japan, was found to contain a significant amount of dissolved methane (<3.1 mM) along with nitrate, phosphate and methane-oxidizing bacteria (methanotrophs, <9.9×10⁶ MPN ml^–1) which can degrade trichloroethylene (TCE). This water exhibited high methanotroph growth activity and rapid degradation of TCE. This water was introduced into a TCE-contaminated aquifer. The concentration of TCE at the monitoring well 2 m down-gradient of the injection pit decreased from 128 g L^–1 before the injection to less than the lower detection limit of 12.5 g L^–1 after the injection, while it decreased only slightly (to 86 g L^–1) when control water was injected. These results demonstrate the feasibility of utilizing a natural groundwater resource containing methane and methanotrophs without any additives for bioremediation of a TCE-contaminated site.     

Wetting behavior of partial melts during crustal anatexis: the distribution of hydrous silicic melts in polycrystalline aggregates of quartz

The equilibrium distribution of hydrous silicic melts in polycrystalline aggregates of quartz was characterized in a series of partial melting and melt distribution experiments in the systems quartz-albite-orthoclase-H₂O and quartz-anorthite-H₂O, at 650 to 1000 MPa and 800 to 900° C. Near-equilibrium textures in these experiments are characterized by very low quartz-quartz-melt wetting angles, and by a substantial number of thin melt films along grain boundaries. Wetting angles in the H₂O-saturated experiments are as follows: 18° at 800° C-1000 MPa, and 12° at 900° C-1000 MPa in the granitic system; 18° at 850° C-650 MPa, 15° at 900° C-650 MPa, and 15° at 900° C-1000 MPa in the quartzanorthite system. In the granitic system at 900° C-1000 MPa, a decrease of H₂O content in melt from 17 wt% (at saturation) to 6 wt%, results in a slight increase of wetting angle from 12° to 16°. These low wetting angles — and the observation that many grain boundaries are wetted by melt films-indicate that the ratio of quartz-quartz to quartz-melt interfacial energies (_ss/_s1) is high: 2. Secondary electron imaging of fracture surfaces of melt-poor samples provided a three-dimensional insight into the geometry of melt; at low melt fraction, melt forms an interconnected network of channels along grain edges, as predicted for isotropic systems with wetting angles below 60°. This high-permeability geometry suggests that the segregation of granitic melts is not as sluggish as previously anticipated; simple compaction calculations for a permeability range of 10^-12 to 10^-9 m² indicate that segregation may operate at low to moderate melt fractions (below 30 vol. %), within relatively short time-scales, i.e., 10⁵ to 10⁶ years. Quartzmelt textures show significant deviations from the equilibrium geometries predicted for isotropic partially molten systems. The most consistent deviation is the pervasive development of crystallographically-controlled, planar faces of quartz; these faces provide definitive evidence for non-isotropic quartz-melt surface energy. For most silicates other than quartz, the grain-scale distribution of partial melts deviates even more significantly from equilibrium distributions in isotropic systems; accordingly, in order to describe adequately melt distributions in most natural source regions, the equilibrium model should be modified to account for anisotropy of solid-liquid interfacial energy.Contribution CNRS-INSU-DBT n^o 651