Measurement of partition coefficients of phenol and cresols in gas-charged crude oil/water systems

An instrument has been constructed for monitoring the partition coefficients of phenol and cresols between crude oil and water under sub-surface conditions. The device has the capacity for introducing methane gas into crude oil, thereby allowing measurements under live oil (solution gas-containing) conditions. The partition coefficients of phenol and cresols have been measured in crude oil: water substrates under “live” oil and “dead” oil (without solution gas) conditions over a temperature range 25–150 °C. Over the range investigated it is seen that the introduction of gas (crude oil saturated at 100 bar with methane) into the system resulted in an approximate doubling of partition coefficients compared to the equivalent dead oil: brine systems. The partition coefficient data obtained using the device may be employed in a number of petroleum exploration and production activities such as the determination of residual oil saturation of a water-flooded petroleum reservoir. Partition coefficient measurements may help in predicting toxic organic solute loadings in oilfield discharge waters.     

Fluorite deposits at Encantada–Buenavista, Mexico: products of Mississippi Valley type processes

Petroleum and aqueous fluid inclusions from the Encantada–Buenavista fluorite mineralized zone in northern Mexico were analyzed by microthermometry, UV fluorescence, Raman Spectroscopy, Fourier Transform Infrared Spectroscopy (FTIR) and Confocal Scanning Laser Microscopy (CSLM) to evaluate the geochemical evolution of the mineralizing fluids. Two-phase (petroleum or brine+vapor) and three-phase (petroleum+brine+vapor) inclusions are described. Aqueous and petroleum-rich inclusions commonly occur in the same plane. Vapor-decrepitated and stretched fluid inclusions are present. A low-salinity methane-saturated fluid and a high salinity-fluid with highly variable methane contents are recognized. H₂S is not quantified but is always detected in close association with methane. Petroleum inclusions are of two types: a low methane petroleum fluid (20 mol%) with low T_h (60 °C) and a petroleum fluid with a methane of content near 30 mol% and a T_h of 90 °C.Pressure and temperature diagrams for the aqueous and petroleum inclusions show three main intersects that allow P–T–X reconstruction of fluid evolution at La Encantada–Buenavista. A CH₄- and H₂S-rich low-salinity brine was mixed with oil that migrated under hydrostatic conditions with a thermal gradient of 70 °C/km. The arrival and mixing of a high-salinity aqueous fluid produced overpressure to 300 bars. A return to hydrostatic conditions was accompanied by an increase in the thermal gradient.The brine related to the fluorite orebodies appears to have a genetic relationship with the brines reported from the Jurassic petroleum basins located west of the fluorite bodies and similarities with reported fluids from Mississippi Valley type deposits. It is interpreted that the fluorine-rich fluids migrated toward the platform margins during the mid-Tertiary (30 to 32 Ma) using extension zones related to Basin and Range tectonism. Mixing of two different brines was responsible for precipitation and mineralization. Heat from magmas, related to tectonic extension, caused decrepitation and changes in the shape of fluid inclusions near the contact zones.     

Assessment of generation temperatures of crude oils

Biological marker maturity parameters were used to estimate the minimum HC generation temperatures of crude oils from Eastern Hungary. More than 50 oils and oil shows were analysed. Molecular- and homologous-ratios of biological marker compounds (triterpanes, steranes, mono- and triaromatic steroid hydrocarbons) were used as maturation parameters. The oils have at least five maturity stages, i.e. they have been generated under different thermal conditions. The highest reservoir temperature in each group was chosen as the best estimate of the groups' temperature just below the generation temperature, i.e. reservoirs of the group might be expected to be at shallower depths (lower temperatures) than those of the generation zone due to vertical migration into pools. For each maturation level, a threshold temperature range for genesis was inferred from reservoir temperatures; they are from 130–135°C for the least mature oils to 210–215°C for the most mature oils. In the least mature oils cracking was not observed, hence carbon–carbon cracking reactions had not taken place during their genesis. The most mature oils are intensively cracked oils; they are almost condensates. Two major genetic groups (families) of oils were found in the area. Both are present in each maturation level. The effects of migration were checked, and no influence on maturation was found. A number of the oils are in overpressured reservoirs within, or just above, the zone of the present-day active oil generation, hence the present-day temperatures of the pools must have been maximum temperatures. Contrary to the traditionally accepted temperature range for petroleum generation–maturation reactions (50–150°C), there is strong evidence from this study that the onset of oil generation requires temperatures higher than 130°C and is still proceeding above 215°C.     

The petroleum generation potential and effective oil window of humic coals related to coal composition and age

A worldwide data set of more than 500 humic coals from the major coal-forming geological periods has been used to analyse the evolution in the remaining (Hydrogen Index, HI) and total (Quality Index, QI) generation potentials with increasing thermal maturity and the ‘effective oil window’ (‘oil expulsion window’). All samples describe HI and QI bands that are broad at low maturities and that gradually narrow with increasing maturity. The oil generation potential is completely exhausted at a vitrinite reflectance of 2.0–2.2%R_o or T_max of 500–510 °C. The initial large variation in the generation potential is related to the original depositional conditions, particularly the degree of marine influence and the formation of hydrogen-enriched vitrinite, as suggested by increased sulphur and hydrogen contents. During initial thermal maturation the HI increases to a maximum value, HI_max. Similarly, QI increases to a maximum value, QI_max. This increase in HI and QI is related to the formation of an additional generation potential in the coal structure. The decline in QI with further maturation is indicating onset of initial oil expulsion, which precedes efficient expulsion. Liquid petroleum generation from humic coals is thus a complex, three-phase process: (i) onset of petroleum generation, (ii) petroleum build-up in the coal, and (iii) initial oil expulsion followed by efficient oil expulsion (corresponding to the effective oil window). Efficient oil expulsion is indicated by a decline in the Bitumen Index (BI) when plotted against vitrinite reflectance or T_max. This means that in humic coals the vitrinite reflectance or T_max values at which onset of petroleum generation occurs cannot be used to establish the start of the effective oil window. The start of the effective oil window occurs within the vitrinite reflectance range 0.85–1.05%R_o or T_max range 440–455 °C and the oil window extends to 1.5–2.0%R_o or 470–510 °C. For general use, an effective oil window is proposed to occur from 0.85 to 1.7%R_o or from 440 to 490 °C. Specific ranges for HI_max and the effective oil window can be defined for Cenozoic, Jurassic, Permian, and Carboniferous coals. Cenozoic coals reach the highest HI_max values (220–370 mg HC/g TOC), and for the most oil-prone Cenozoic coals the effective oil window may possibly range from 0.65 to 2.0%R_o or 430 to 510 °C. In contrast, the most oil-prone Jurassic, Permian and Carboniferous coals reach the expulsion threshold at a vitrinite reflectance of 0.85–0.9%R_o or T_max of 440–445 °C.     

Thermal cracking history by laboratory kinetic simulation of Paleozoic oil in eastern Tarim Basin, NW China, implications for the occurrence of residual oil reservoirs

The thermal stability of Paleozoic oil in eastern Tarim Basin, NW China was investigated through laboratory kinetic simulation experiments. Laboratory cracking of a selected marine oil sample from Ordovician strata in well LG-1 of Tarim Basin was performed by confined, dry pyrolysis system at T = 300–650 °C, P = 50 MPa. Results indicated the oil required higher temperature for cracking. At laboratory heating rates, oil cracking started at 390–400 °C and the laboratory cracking was completed at around 650 °C. At geological heating rates, the onset temperature is about 148–162 °C for cracking start and was completed at 245–276 °C. The oil-cracking history was recovered using the acquired kinetic parameters and the geothermal history of TD-2, and the threshold temperature for oil cracking under geological conditions was calculated. The oil cracking started at 165 °C (R_o = 1.45%) and stopped in early Devonian (390 Ma), and the oil-cracking rates in the strata of -O₁ reached 60–70% at the end of Silurian. The calculated oil generation and oil cracking windows overlapped to some extent and were completed rapidly. The possible geological controls for the occurrence of residual oil reservoirs in Eastern Tarim basin have been discussed, including the high stability of the Paleozoic oil in Tarim Basin, the fast heating rate and longer duration time for oil cracking, the slight biodegradation in later uplift, the good preservation of the paleo-reservoirs and the moderate structural adjustment, which were critical for the exploration of residual oil and gases in this area.     

A review of Antarctic granulite-facies rocks

Precambrian granulite-facies rocks occur in significant proportion in the East Antarctic Precambrian shield. Ages of metamorphic and deformational events range from 2500 m.y. to about 500 m.y., but some rocks are much older, notably the approximately 3500 m.y. ages for crust formation in Enderby Land. Mineral assemblages over most of the area are typical of the hornblende granulite facies, and sparse temperature pressure estimates indicate metamorphism at 700–800°C and 5–8 kbar at reduced water pressures. A terrane of exceptional interest is the Napier complex of Enderby Land, where sapphirine-quartz ± garnet, sillimanite-orthopyroxene, osumilite, and inverted pigeonite are associated with pyroxene-granulite-facies rocks. Metamorphic conditions are estimated to have reached 900°–980°C, 7–9 kbar, and p_H2O < 0.5 kbar. Metamorphism in the Napier complex, and possibly in other parts of East Antarctica, may be associated with large loss of fluid rather than massive influx of CO₂.     

An experimental study of the solubility and speciation of the Rare Earth Elements (III) in fluoride- and chloride-bearing aqueous solutions at temperatures up to 300 °C

The solubility of REE(III) fluoride solids was determined in fluoride- and chloride-bearing solutions at 150, 200 and 250 °C and saturated water vapor pressure. These experimental data, together with experimental data from previously published studies, were used to evaluate formation constants for chloride- and fluoride-bearing aqueous species of the entire REE(III) group at temperatures up to 300 °C. The data show that the stability of these species differs significantly from that predicted theoretically. For example, contrary to the theoretical predictions, LREEF²⁺ species are more stable than HREEF²⁺ species at elevated temperature. The behavior of the chloride-bearing species is similar. Parameters for the Helgeson–Kirkham–Flowers (HKF) equation of state were determined for REEF²⁺, REECl²⁺ and REECl₂⁺ complexes using these experimental data and permit calculation of formation constants of these species at conditions not investigated experimentally. These data now permit the mobility of all REE in fluoride- and chloride-bearing hydrothermal systems to be reliably evaluated at intermediate temperatures and pressures.     

Mineral assemblages of the Francisco I. Madero Zn–Cu–Pb–(Ag) deposit, Zacatecas, Mexico: Implications for ore deposit genesis

The Francisco I. Madero deposit, central Mexico, occurs in the Mesozoic Guerrero Terrane, which hosts many ore deposits, both Cretaceous (volcanogenic massive sulfides) and Tertiary (epithermal and skarn deposits). It is hosted by a 600 m-thick calcareous-pelitic unit, of Lower Cretaceous age, crosscut by porphyritic dikes that strike NW–SE. A thick felsic volcanic Tertiary sequence, consisting of andesites and rhyolitic ignimbrites, unconformably overlies the Cretaceous series. At the base, the mineralization consists of several mantos developed within calcareous beds. They are dominantly composed of sphalerite, pyrrhotite and pyrite with minor chalcopyrite, arsenopyrite and galena. At the top of the orebody, there are calcic skarns formed through prograde and retrograde stages. The resulting mineral assemblages are rich in manganoan hedenbergite (Hd_75–28Di_40–4Jh_40–20), andraditic garnets (Adr_100–62Grs_38–0), epidote (Ep_95–36Czo_60–5Pie_8–0), chamosite, calcite and quartz. The temperature of ore deposition, estimated by chlorite and arsenopyrite geothermometry, ranges from 243° to 277 °C and from 300° to 340 °C, respectively. The pressure estimated from sphalerite geobarometry averages 2.1 kbar. This value corresponds to a moderately deep skarn and agrees with the high Cu content of the deposit. Paragenesis, P–T conditions and geological characteristics are compatible with a distal, dike-related, Zn skarn deposit. Its style of mineralization is similar to that of many high-temperature carbonate replacement skarn deposits in the Southern Cordillera.     

Compressional and shear wave velocities of igneous rocks and volcanic glasses to 900° C and 20 kbar

Simultaneous measurements of compressional and shear wave velocities, V_p and V_s, in acidic and basic igneous rocks and volcanic glasses, were made up to 900°C and at 10–20 kbar.The effects of pressure and temperature on V_p and V_s in glasses and glassy rocks change at about 600°C, presumably the glass transition temperature. These effects are directly related to the silica content in the samples. and for obsidian are negative at room temperature and 245°C, but are positive at 655°C. The velocity—pressure relations for obsidian display an obvious hysteresis phenomena. for basalt glass is slightly negative, but is positive for usual substances at room temperature, and for obsidian and glassy andesite are positive up to about 600°C but are negative above that temperature. However, for basalt glass as well as other crystalline rocks, and are negative at all temperatures. Glass once heated above the glass transition temperature T_g under pressure P₁ retains the memory of pressure P₁ after it is cooled down below T_g and while subjected to another pressure P₂. An abrupt shift of the velocities correlating to pressure P₂ occurs when the glass is again heated to T_g. V_p−T and V_s−T relations for obsidian, glassy andesite, and basalt glass clearly exhibit this pressure memory.     

Solution mechanisms of silicate in aqueous fluid and H2O in coexisting silicate melts determined in-situ at high pressure and high temperature

The structure of H₂O-saturated silicate melts, coexisting silicate-saturated aqueous solutions, and supercritical silicate liquids in the system Na₂O·4SiO₂–H₂O has been characterized with the sample at high temperature and pressure in a hydrothermal diamond anvil cell (HDAC). Structural information was obtained with confocal microRaman and with FTIR microscopy. Fluids and melts were examined along pressure-temperature trajectories defined by the isochores of H₂O at nominal densities, ρ_fluid, (from EOS of pure H₂O) of 0.90 and 0.78 g/cm³. With ρ_fluid = 0.78 g/cm³, water-saturated melt and silicate-saturated aqueous fluid coexist to the highest temperature (800 °C) and pressure (677 MPa), whereas with ρ_fluid = 0.90 g/cm³, a homogeneous single-phase liquid phase exists through the temperature and pressure range (25–800 °C, 0.1–1033 MPa). Less than 5 vol% quartz precipitates near 650 °C in both experimental series, thus driving Na/Si-ratios of melt + fluid phase assemblages to higher values than that of the Na₂O·4SiO₂ starting material.Molecular H₂O (H₂O°) and structurally bonded OH groups were observed in coexisting melts and fluids as well as in supercritical liquids. Their OH/(H₂O)-ratio is positively correlated with temperature. The OH/(H₂O)° in melts is greater than in coexisting fluids. Structural units of Q³, Q², Q¹, and Q⁰ type are observed in all phases under all conditions. An expression of the form, 12Q³ + 13H₂O2Q² + 6Q¹ + 4Q⁰, describes the equilibrium among those structural units. This equilibrium shifts to the right with increasing pressure and temperature with a ΔH of the reaction near 425 kJ/mol.     

Genetic significance of fluid inclusions in the CSA Cu–Pb–Zn deposit, Cobar, Australia

CSA mine exploits a ‘Cobar-type’ Cu–Pb–Zn±Au±Ag deposit within a cleaved and metamorphosed portion of the Cobar Supergroup, central New South Wales. The deposit comprises systems of ‘lenses’ that encompass veins, disseminations and semi-massive to massive Cu–Pb–Zn ores. The systems and contained lenses truncate bedding, are approximately coplanar with regional cleavage and similarly oriented shear zones and plunge parallel to the elongation lineation. Systems have extreme vertical continuity (>1000 m), short strike length (400 m) and narrow width (100 m), exhibit vertical and lateral ore-type variation and have alteration haloes. Models of ore formation include classical hydrothermalism, structurally controlled remobilisation and polymodal concepts; syntectonic emplacement now holds sway.Fluid inclusions were examined from quartz±sulphide veins adjacent to now-extracted ore, from coexisting quartz–sulphide within ore, and from vughs in barren quartz veins. Lack of early primary inclusions precluded direct determination of fluids associated with D₂–D₃ ore and vein emplacement. Similarly, decrepitation (by near-isobaric heating) of the two oldest secondary populations precluded direct determination of fluid phases immediately following D₂–D₃ ore and vein emplacement. Post-decrepitation outflow (late D₃ to early post-D₃) is recorded by monophase CH₄ inclusions. Entrained outflow of deeply circulated meteoric fluid modified the CH₄ system; modification is recorded by H₂O+CH₄ and H₂O+(trace CH₄) secondary populations and by an H₂O+(trace CH₄) primary population. The contractional tectonics (D₂–D₃) of ore emplacement was superseded by relaxational tectonics (D_4P) that facilitated meteoric water penetration and return flow.Under D₂ prograde metamorphism, entrapment temperatures (Tt) and pressures (Pt) for pre-decrepitation secondary inclusions are estimated as Tt300–330 °C and Pt1.5–2 kbar≈Plith (the lithostatic pressure). Decrepitation accompanied peak metamorphism (T350–380 °C) in mid- to late-D₃, while in late-D₃ to early post-D₃, essentially monophase CH₄ secondary inclusions were entrapped at Tt350 °C and Pt=1.5–2 kbar≈Plith. Subsequently, abundant CH₄ and entrained meteoric water were entrapped as H₂O+CH₄ secondaries under slowly decreasing temperature (Tt330–350 °C) and constant pressure (Pt1.5–2 kbar). Finally, with increasingly dominant meteoric outflow, H₂O+(trace CH₄) populations record decreasing temperatures (Tt>300 to <350 down to 275–300 °C) at pressures of Phydrostatic<Pt (1 kbar) <Plith (1.5 kbar).The populations of inclusions provide insight into fluid types, flow regimes and P–T conditions during parts of the deposit's evolution. They indirectly support the role of basin-derived CH₄ fluids in ore formation, but provide no insight into a basement-sourced ore-forming fluid. They fully support post-ore involvement of meteoric water. The poorly constrained entrapment history is believed to span 10 Ma from 395 to 385 Ma.     

As–(Ag) sulphide veins in the Spanish Central System: further evidence for a hydrothermal event of Permian age

The Spanish Central System (SCS) has been subjected to repeated deformation and fluid flow events which have produced both sulphide-bearing and barren vein systems. Although several hydrothermal episodes took place between 300 and 100 Ma, fluid circulation during the Permian was especially important, giving rise to a range of different types of deposits. This study presents a multidisciplinary approach leading to the characterisation of the chemistry and age of the hydrothermal fluids that produced the As–(Ag) mineralised stockwork of Mónica mine (Bustaviejo, Madrid). Fluid inclusion data indicate the presence of two different fluids. An initial ore stage (I) formed from a low- to moderate salinity (3–8 wt.% eq. NaCl) H₂O–NaCl–CO₂–CH₄ fluid, at minimum trapping temperature of 350±15 °C and 0.3 kbar. A second H₂O–NaCl fluid is found in three types of fluid inclusions: a high temperature and low salinity type (340±20 °C; 0.8–3.1 wt.% eq. NaCl) also associated to ore stage I, a moderate temperature and very low salinity type (160–255 °C; 0–1.5 wt.% eq. NaCl) represented in ore stage III, and a very low temperature and hypersaline type (60–70 °C; 30–35 wt.% NaCl), unrelated to the mineralising stages and clearly postdating the previous types. ⁴⁰Ar–³⁹Ar dating on muscovite from the early As–Fe stage (I) has provided an age of 286±4 Ma, synchronous with the late emplacement phases of La Cabrera plutonic massif (288±5 Ma) and with other Permian hydrothermal events like Sn–W skarns and W–(Sn) sulphide veins. δ¹⁸O of water in equilibrium with stage I quartz (5.3–7.7‰), δD of water in equilibrium with coexisting muscovite (−16.0‰ to −2.0‰), and sulphide δ³⁴S (1.5–3.6‰) values are compatible with waters that leached metamorphic rocks. The dominant mechanism of the As–(Ag) deposition was mixing and dilution processes between aqueous–carbonic and aqueous fluids for stage I (As–Fe), and nearly isobaric cooling processes for stages II (Zn–Cu–Sn) and III (Pb–Ag). The origin and hydrothermal evolution of As–(Ag) veins is comparable to other hydrothermal Permian events in the Spanish Central System.     

Iron-Titanium Oxide Geothermometry and Petrogenesis of Lava Flows and Dykes from Mandla Lobe of the Eastern Deccan Volcanic Province, India

Compositional studies on different forms of magnetite, ulvospinel, ilmenite and hematite mineral phases occurring in 37 lava flows and 6 dykes of the Mandla lobe are presented in this paper. Ilmenite (0001) in equilibrium with titanomanetite show high values of temperature of equilibration, ranging from 1172–974°C, for high alumina quartz normative tholeiitic lava flows of Chemical Type - A; 1129–1229°C for low alumina quartz normative tholeiitic lava flows of Chemical Type - B; 1283–1124°C for tholeiitic lava flows of Chemical Type - F and 1243°C and 99O°C for two diopside olivine normative tholeiite flows of Chemical Type D. High olivine normative flows of Chemical Type - G and H show 1095°C and 1092°C respectively. Whereas, high hypersthene normative tholeiite flow of Chemical me C shows temperature of 1187°C. Data plots disposition over iron-titanium oxide equilibration temperature vs – logfo₂, diagram for Mandla lava flows and other parts of the Deccan (Igatpuri, Mahabaleshwer, Nagpur and Sagar areas) revealed that tholeiitic (evolved) basalt of the eastern Deccan volcanic province formed at high temperatures whereas, picritic (primitive) lavas of Igatpuri and tholeiitic basalt of Mahabaleshwar areas were formed at low temperatures. Mahabaleshwer basalts follow FMQ (fayalite-magnetite-quartz) buffer curve but, plots of the Mandla basalts lie above this curve indicating higher temperatures of crystallisation of ilmenite-titanomagnetite than that of the lava flows from other parts of Deccan 'Raps. The eastern Deccan Traps are most evolved types of lava as characterised by its low Mg-number and Ni content whereas, Igatpuri lava flows are picritic (primitive), having high Mg-number and Ni contents. Temperature vs FeO + Fe₂O₃ / FeO + Fe₂O₃ + MgO ratio data plots for Mandla and other Deccan lava flows and liquidus data for Hawaiian tholeiites, indicated that Igatpuri basalts lie parallel to the liquidus line of Hawaiian tholeiite but at lower temperatures. Large data plots of Mandla lava flows lie along the liquidus line of the Hawaiian lava. The highly vesicular nature of compound lava flows having large amount of volatile is responsible for low temperature values whereas, lava flows represented by high temperatures show high modal values of glass and opaque minerals.     

The shift of the α-β transition temperature of quartz associated with the thermal expansion of granite at high pressure

Measurements are presented of volume changes in granite during room-temperature compression to 100, 200 and 300 MPa confining pressure followed by temperature increase to 900°C. Comparison with thermal expansion and compressibility data for the constituent minerals allows changes in porosity to be estimated. Under confining pressure, porosity is found to decrease with heating to 200°C through expansion of the minerals into cracks which are thought to be related to the geological cooling history of the rock. Between 200°C and 840°C porosity increases as a result of differential thermal expansion of the constituent minerals, but crack opening is increasingly suppressed at higher confining pressures. Extrapolation of the results indicates that differential thermal expansion can no longer cause crack opening in dry granite at confining pressures in excess of 450 MPa. The quartz α-β transition temperature in granite is marked by a kink in the thermal expansion curve of the rock, and it is found to increase by 60°C–70°C per 100 MPa confining pressure, as opposed to the published value of 26°C per 100 MPa for single crystals of quartz. Equations are presented which allow calculation of the effects of confining pressure and temperature on the stresses and displacements in and around a spherical inclusion embedded in a matrix of different elasticity and thermal expansion. The theory, together with a simple self-consistent model for granite, accounts semiquantitatively for the observations of thermal expansion and the effect of confining pressure thereon, and for the observed α-β transition temperatures for quartz in granite.     

Variations in the carbon isotope composition and production yield of various pyrolysis products under open and closed system conditions

Production rates and carbon isotopic compositions of various pyrolysis products were investigated for three sediments from the Williston Basin under open and closed pyrolysis conditions in the temperature range of 300–600°C.Both parameters do not show any significant differences for kerogens and carbon dioxides with the analytical procedure. Contrary to open system pyrolysis, however, decreasing yields of pyrolysates and higher amounts of gaseous hydrocarbons (C_2–4 compounds) at temperatures of 500 and 600°C, point to their decomposition to give ultimately methane.Moreover, these pyrolysis products display distinct carbon isotopic variations under open and closed pyrolysis conditions. They are due to a kinetic isotope effect, i.e. the preferential cleavage of ¹²C-¹²C over ¹³C-¹²C bonds, but the extent of the shift in isotopic composition seems to depend primarily on the reservoir size and the type of source material.     

Compressional wave velocity of granite and amphibolite up to melting temperatures at 1 GPa

Compressional wave velocities (V_P) at above-solidus temperatures and at 1 GPa were obtained for a granite and amphibolite, which are considered to be major constituents of the continental crust. The temperature variation of velocities showed that the V_P values of granite decreased with rising temperature, but substantially increased beyond the melting temperature (850–900 °C). Such an increase may be caused by the α–β transition of quartz. The velocities of amphibolite decreased linearly with increasing temperature and dropped sharply at temperatures above the solidus (700 °C), indicating that partial melting of amphibolite acts to significantly lower the seismic velocities.     

HP–LT Variscan metamorphism in the Cubito-Moura schists (Ossa-Morena Zone, southern Iberia)

Multi-equilibrium thermobarometry shows that low-grade metapelites (Cubito-Moura schists) from the Ossa–Morena Zone underwent HP–LT metamorphism from 340–370 °C at 1.0–0.9 GPa to 400–450 °C at 0.8–0.7 GPa. These HP–LT equilibriums were reached by parageneses including white K mica, chlorite and chloritoid, which define the earliest schistosity (S₁) in these rocks. The main foliation in the schists is a crenulation cleavage (S₂), which developed during decompression from 0.8–0.7 to 0.4–0.3 GPa at increasing temperatures from 400–450 °C to 440–465 °C. Fe³⁺ in chlorite decreased greatly during prograde metamorphism from molar fractions of 0.4 determined in syn-S₁ chlorites down to 0.1 in syn-S₂ chlorites. These new data add to previous findings of eclogites in the Moura schists indicating that a pile of allochtonous rocks situated next to the Beja-Acebuches oceanic amphibolites underwent HP–LT metamorphism during the Variscan orogeny. To cite this article: G. Booth-Rea et al., C. R. Geoscience 338 (2006).     

Solubility of Pt and Pd sulfides and Au metal in aqueous bisulfide solutions

An experimental study of the solubility of Pt and Pd sulfides and Au metal in aqueous bisulfide solutions was conducted at temperatures from 200° to 350 °C and at saturated vapor pressure. A 500-mL Bridgemantype pressure vessel constructed of titanium, and equipped with a motor-driven magnetic stirrer was employed. The pH and the oxidation state were buffered by the coexistence of H₂S/HS^–/SO _inf4 ^sup2– . The pH at temperature was calculated to be in the range 5.91–9.43, and S was 0.3–2.2 m. Under the experimental conditions, the measured solubility of gold is about two to three orders of magnitude greater than that of either platinum and palladium, and the measured solubility of platinum is, in general, approximately equal to that of palladium, in molal units. The solubilities are found to be in the range: platinum 4–800 ppb, palladium 1–400 ppb, and gold 2–300 ppm. The solubility data can be modeled adequately using the following reactions: Au+H₂S+HH^–=Au(HS) ₂ ^– +1/2H₂ (K₁₄); PtS+HS^–+H⁺=Pt (HS) ₂ ⁰ (K₁₅); PdS+HS^–+H⁺=Pd (HS) ₂ ⁰ (K₁₆); PtS₂+H₂=Pt (HS) ₂ ⁰ (K₂₁).With equilibrium constants determined as follows (errors represent two standard deviations): Preliminary measurements of the solubilities of metallic Pt, Pd and Au as hydroxide complexes were also conducted using a second titanium pressure vessel, at temperatures of 200° to 350 °C and vapor saturation pressure, with pH and the oxidation state controlled or buffered by adding known amounts of NaOH and H₂ gas. The concentration of NaOH was in the range 0.01–1.3 m, and the partial pressure of H₂ at 200 °C was 62–275 bars, initially. Under the temperature and pressure conditions of these experiments, the solubility of platinum in 1 m NaOH solution is less than 100 ppb, that of palladium is less than 10 ppb and that of gold is less than 0.2 ppm; and in 0.01 m NaOH solutions, both Pt and Pd solubilities are less than 1 ppb. These data indicate that the contributions of hydroxide complexes to the total solubilities in the bisulfide runs, where the pH was in the range of 5.9–9.4, are negligible. The concentrations of both Pt and Pd as bisulfide complexes in the Salton Sea geothermal system predicted using the stability constants determined in this work agree very well with those values measured by McKibben et al. (1990). This calculation strongly suggests that the PGE are transported in moderately reducing, near neutral hydrothermal fluids as bisulfide complexes, as is gold. However, the much lower maximum solubility of the PGE relative to gold severely constrains models of re genesis, and may explain the relative rarity of hydrothermal PGE deposits compared to the relative abundance of hydrothermal Au deposits.     

Granulitic metamorphism in the Laouni terrane (Central Hoggar, Tuareg Shield, Algeria)

In the Laouni terrane, which belongs to the polycyclic Central Hoggar domain, various areas contain outcrops of formations showing granulite-facies parageneses. This high-temperature metamorphism was accompanied by migmatization and the emplacement of two types of magmatic suite, one of continental affinity (garnet pyroxenites and granulites with orthoferrossilite–fayalite–quartz), and the other of arc affinity (layered metanorites). Paragenetic, thermobarometric and fluid-inclusion studies of the migmatitic metapelites and metabasites make it possible to reconstruct the P–T–aH₂O path undergone by these formations. This path is clockwise in the three studied areas, being characterized by a major decompression (Tamanrasset: 10.5 kbar at 825 °C to 6 kbar at 700 °C; Tidjenouine: 7.5 kbar at 875 °C; to 3.5 kbar at 700 °C; Tin Begane: 13.5 kbar at 850 °C; to 5 kbar at 720 °C), followed by amphibolitization that corresponds to a fall of temperature (from 700 to 600 °C) and an increase in water activity (from 0.2–0.4 to almost 1).The main observed features are in favour of petrogenesis and exhumation related to the Eburnean orogeny. However, the lacks of good-quality dating work and a comparison with juvenile Pan-African formations having undergone high-pressure metamorphism, in some cases reaching the eclogite facies, do not rule out the possibility that high-temperature parageneses are locally due to Pan-African events.     

Thermobarometric data from a fossil zircon partial annealing zone in high pressure–low temperature rocks of eastern and central Crete, Greece

A fossil partial annealing zone of fission tracks in zircon is described from high pressure–low temperature (HP–LT) rocks of the Phyllite–Quartzite Unit (PQ) on the island of Crete, Greece. Correlation of regional trends in fission track age populations with independent thermobarometric and microstructural data, and with new experimental annealing results, allows a calibration of this low temperature thermochronological method to a degree hitherto not available from other field examples.The zircon fission track (FT) ages of samples from the PQ across Crete range from original detrital signature through reduced to completely reset. The annealing is the result of a single heating period related to the HP–LT metamorphism with near-peak temperatures lasting for only a few million years some time between 24±1 and 20±1 Ma. In eastern Crete, where rocks have experienced temperatures of 300±50 °C and pressures of 0.8±0.3 GPa, zircon FT ages range from 414±24 to 145±10 Ma. Ages above 300 Ma occur mostly near the east coast of the island in rocks which have not been heated to above ca. 280 °C and probably represent a pre-Variscan source. Track lengths are already indicative of a substantial annealing at this temperature. Most of the zircon FT ages from eastern Crete scatter within error around the stratigraphic age. Samples with apparent zircon FT ages significantly younger than the depositional age are only observed in areas where temperatures exceeded ca. 320 °C. Towards the west, a sudden decrease to very young ages ranging from 17±2 to 18±1 Ma reflects a complete resetting at ca. 350 °C. Short tracks, however, are still observed. Throughout the central and western part of the island, ages are consistently below 22 Ma. Thermobarometric data for this area indicate maximum temperatures of 400±50 °C and pressures of 1±0.3 GPa. Only samples from western Crete, which have been exposed to 400±50 °C, show exclusively long tracks. Consequently, the high temperature limit of the zircon partial annealing zone (ZPAZ) appears to be between 350 and 400 °C.A significant influence of elevated confining pressure on the stability of fission tracks in zircon is ruled out by the results of annealing experiments at 0.5 GPa and at different temperatures, which fit the curves previously obtained by other authors at ambient pressure.