Major and trace element concentration of melt inclusions from Zhupanovsky volcano, Kamchatka

The paper presents data on naturally quenched melt inclusions in olivine (Fo 69-84) from Late Pleistocene pyroclastic rocks of Zhupanovsky volcano in the frontal zone of the Eastern Volcanic Belt of Kamchatka. The composition of the melt inclusions provides insight into the latest crystallization stages (~70% crystallization) of the parental melt (~46.4 wt % SiO2, ~2.5 wt % H2O, ~0.3 wt % S), which proceeded at decompression and started at a depth of approximately 10 km from the surface. The crystallization temperature was estimated at 1100 ± 20°C at an oxygen fugacity of deltaFMQ = 0.9-1.7. The melts evolved due to the simultaneous crystallization of olivine, plagioclase, pyroxene, chromite, and magnetite (Ol: Pl: Cpx : (Crt-Mt) ~ 13 : 54 : 24 : 4) along the tholeiite evolutionary trend and became progressively enriched in FeO, SiO2, Na2O, and K2O and depleted in MgO, CaO, and Al2O3. Melt crystallization was associated with the segregation of fluid rich in S-bearing compounds and, to a lesser extent, in H2O and Cl. The primary melt of Zhupanovsky volcano (whose composition was estimated from data on the most primitive melt inclusions) had a composition of low-Si (~45 wt % SiO2) picrobasalt (~14 wt % MgO), as is typical of parental melts in Kamchatka and other island arcs, and was different from MORB. This primary melt could be derived by ~8% melting of mantle peridotite of composition close to the MORB source, under pressures of 1.5 ± 0.2 GPa and temperatures 20-30°C lower than the solidus temperature of 'dry' peridotite (1230-1240°C). Melting was induced by the interaction of the hot peridotite with a hydrous component that was brought to the mantle from the subducted slab and was also responsible for the enrichment of the Zhupanovsky magmas in LREE, LILE, B, Cl, Th, U, and Pb. The hydrous component in the magma source of Zhupanovsky volcano was produced by the partial slab melting under water-saturated conditions at temperatures of 760-810°C and pressures of ~3.5 GPa. As the depth of the subducted slab beneath Kamchatkan volcanoes varies from 100 to 125 km, the composition of the hydrous component drastically changes from relatively low-temperature H2O-rich fluid to higher temperature H2O-bearing melt. The geothermal gradient at the surface of the slab within the depth range of 100-125 km beneath Kamchatka was estimated at 4°C/km.

The stratigraphy of the Fishguard volcanic complex and associated sediments, SW Dyfed, Wales

This thesis describes the geology of a Lower Palaeozoic terrain, situated west of the town of Fishguard, SW Dyfed, Wales. The area is dominated by the Fishguard Volcanic Complex (Upper Llanvirn), and sediments that range in age from the Middle Cambrian to the Lower Llandeilo. The successions represent an insight into sedimentation and volcanism for c. 100 Ma. along the south-western margin of the Lower Palaeozoic Welsh Basin. The stratigraphy of the sedimentary sequence has been completely revised and the existing volcanostratigraphy modified. The observed complexity of the stratigraphy is primarily the consequence of Caldedonide deformation which resulted in large scale repetition. Fold-thrust tectonics dominates the structural style of the area. Caledonide trending (NE-SW) cross-faults complicate preexisting structures. Middle Cambrian (?) sedimentation is documented by shallow marine clastics and red shales deposited within tidal - subtidal environments. Upper Cambrian sedimentation was dominated by shallow marine `storm' and `fair weather' sedimentation within a muddy shelf environment. Shallow marine conglomerates and heterolithic intertidal siliciclastics mark the onset of Ordovician sedimentation during the lower Arenig transgression. Mid-Arenig sediments reflect deposits influenced by storm, fair-weather and wave related processes in various shallow marine environments, including; shoreface, inner shelf, shoaling bar, and deltaic. Graptolitic marine shales were deposited from the upper mid-Arenig through to the lower Llandeilo; during which time sediments accumulated by pelagic processes and fine grained turbidites. The varied nature of sedimentation reflects both localised change within the depositional system and the influence of larger regional eustatic events. Ordovician subaqueous volcanic activity produced thick accumulations of lavas, pyroclastics, hydroclastics, and hyaloclastics. The majority of volcanism was effusive in nature, erupted below the Pressure Compensation Level. Basaltic volcanism was characterised by pillowed lavas and tube networks, whilst sheet-flow lavas, pillow breccias and minor hyaloclastites developed locally. Silicic volcanism was dominated by rhyolitic clastics of various affinities, although coherent silicic obsidian lavas, sheet-flow lavas and pyroclastics developed. Hypabyssal intrusives of variable composition and habit occur throughout the volcanic successions. Low-grade regional metamorphism has variably affected the area, conditions of the prehnite-pumpellyite and greenschist facies having been attained. Numerous secondary phases developed in response to the conditions imposed, which collectively indicate that P-T conditions were of low-pressure facies series in the range P= 1.2-2.0 kbars and T= 230-350oC, under an elevated geothermal gradient of 40-45oC km-1. Polymineralic cataclastites associated with Caledonide deformation indicate that tectonism and metamorphism were in part contemporaneous.

Mapeamento da isoterma de Curie na Bacia do Parnaíba estimada através da profundidade da base das fontes magnéticas

Located on the western edge of the Brazilian northeast, the Parnaíba Basin is an intra cratonic basin with oil production. This study aims at understanding its genesis and evolution, using aeromagnetic and gravity data. We used the spectral analysis of aeromagnetic data to map the depth to the bottom of the magnetic sources in order to assimilate this depth with the depth of the Curie isotherm, and infer the geothermal gradient. Using the spectral analysis technique, we succeeded in mapping the surface of the depth to the bottom of magnetic sources (SBFM), which marks the depth that occur magnetization. In the Parnaíba Basin the SBFM presented depths around -20,5 and -28,5 , which was consistent with an inversion of the same dataset using the technique of Magnetization Vector Inversion (MVI). Furthermore, SBFM topography correlates well with Moho depth, which was estimated from satellite gravimetric data from the GOCE mission (Gravity Field and Steady-State Ocean Circulation Explorer). Assuming that SBFM coincides with the Curie isotherm of magnetite (ICM), defined as the surface at which magnetite ( ) looses its ferromagnetic properties, it was possible to estimate the geothermal gradient. The geothermal gradient in the basin showed values between 19.2 and 26.5 , allowing to estimate the heat flow for the Parnaíba basin after assuming a conductivity of 2.69 . The resulting heat flow values ranged between 51.6 and 71.3 , which is consistent with values found in other works throughout the South American continent. Lithospheric thickness using an empirical relationship, finding values between -65.8 and -89.2 . We propose that thermal structure of Parnaíba basin is influenced by a deep thermal anomaly. This anomaly has heated the lithosphere beneath the basin and has resulted in relatively thin values for the lithospheric thickness and relatively high surface heat flow values. The origin of the anomaly is not clear, but the correlation between Curie depth and Moho topography, suggests that tectonic extension processes could have played a role.

Gas hydrates of nonpressurized (GC) and pressurized (DAPC) sediment cores from the Hakon Mosby Mud Volcano, SW Barents Sea

The occurrence of gas hydrates at submarine mud volcanoes (MVs) located within the gas hydrate stability zone (GHSZ) is controlled by upward fluid and heat flux associated with MV activity. Determining the spatial distribution of gas hydrates at MVs is crucial to evaluate their sensitivity to known episodic changes in volcanic activity. We determined the hydrocarbon inventory and spatial distribution of hydrates at an individual MV structure. The Håkon Mosby Mud Volcano (HMMV), located at 1,250 m water depth on the Barents Sea slope, was investigated by combined pressure core sampling, heat flow measurements, and pore water chemical analysis. Quantitative pressure core degassing revealed gas-sediment ratios between 3.1 and 25.7, corresponding to hydrate concentrations of up to 21.3% of the pore volume. Hydrocarbon compositions and physicochemical conditions imply that gas hydrates incipiently crystallize as structure I hydrate, with a dissociation temperature of around 13.8°C at this water depth. Based on numerous in situ measurements of the geothermal gradient in the seabed, pore water sulfate profiles and microbathymetric data, we show that the thickness of the GHSZ increases from less than 1 m at the warm center to around 47 m in the outer parts of the HMMV. We estimate the total mass of hydrate-bound methane stored at the HMMV to be about 102.5 kt, of which 2.8 kt are located within the morphological Unit I around the center and thus are likely to be dissociated in the course of a large eruption.

Chemical and isotopic composition of carbonate veins from ODP Leg 209

Carbonate veins hosted in ultramafic basement drilled at two sites in the Mid Atlantic Ridge 15°N area record two different stages of fluid-basement interaction. A first generation of carbonate veins consists of calcite and dolomite that formed syn- to postkinematically in tremolite-chlorite schists and serpentine schists that represent gently dipping large-offset faults. These veins formed at temperatures between 90 and 170 °C (oxygen isotope thermometry) and from fluids that show intense exchange of Sr and Li with the basement (87Sr/86Sr = 0.70387 to 0.70641, d7Li L-SVEC = + 3.3 to + 8.6 per mil). Carbon isotopic compositions range to high d13C PDB values (+ 8.7 per mil), indicating that methanogenesis took place at depth. The Sr-Li-C isotopic composition suggests temperatures of fluid-rock interaction that are much higher (T > 350-400 °C) than the temperatures of vein mineral precipitation inferred from oxygen isotopes. A possible explanation for this discrepancy is that fluids cooled conductively during upflow within the presumed detachment fault. Aragonite veins were formed during the last 130 kyrs at low-temperatures within the uplifted serpentinized peridotites. Chemical and isotopic data suggest that the aragonites precipitated from cold seawater, which underwent overall little exchange with the basement. Oxygen isotope compositions indicate an increase in formation temperature of the veins by 8-12 °C within the uppermost ~ 80 m of the subseafloor. This increase corresponds to a high regional geothermal gradient of 100-150 °C/km, characteristic of young lithosphere undergoing rapid uplift.

(Table 1) Peak intensities and stable carbon and oxygen isotope ratios of various diagenetic carbonates of ODP Site 128-799

Abundant and various diagenetic carbonates were recovered from a 1084-m-thick, Quaternary to lower Miocene section at ODP Site 799 in the Japan Sea. Petrographic, XRD, SEM, EDS-chemical, and isotopic analyses revealed wide variations in occurrence and textural relations and complex mineralogy and chemistry. Diagenetic carbonates include calcite, calcium-rich rhodochrosite, iron- and manganese-rich magnesite, iron- and manganese-rich dolomite and ankerite, and iron- and manganeserich lansfordite (hydrous Mg-carbonate). Rhodochrosite commonly occurs as small, solid nodules and semi-indurated, thin layers in bioturbated, mottled sediments of Units I and II (late Miocene to Quaternary). Lansfordite occurs as unindurated nodules and layers in Unit II (late Miocene and Pliocene), whereas magnesite forms indurated beds a few centimeters thick in slightly bioturbated-to-faintly laminated sediments of Unit III (middle and late Miocene). Some rhodochrosite nodules have dark-colored, pyritic cores, and some pyrite-rhodochrosite nodules are overgrown by and included within magnesite beds. Dolomite and ankerite tend to form thick beds (>10 cm) in bedded to laminated sediments of Units III, IV, and V (early to late Miocene). Calcite occurs sporadically throughout the Site 799 sediments. The d18O values of carbonates and the interstitial waters, and the measured geothermal gradient indicate that almost all of the Site 799 carbonates are not in isotopic equilibrium with the ambient waters, but were precipitated in the past when the sediments were at shallower depths. Depths of precipitation obtained from the d18O of carbonates span from 310 to 510 mbsf for magnesite and from 60 to 580 mbsf for dolomite-ankerite. Rhodochrosite and calcite are estimated to have formed within sediments at depths shallower than 80 mbsf. Diagenetic history in the Site 799 sediments have been determined primarily by the environment of deposition; in particular, by the oxidation-reduction state of the bottom waters and the alkalinity level of the interstitial waters. Under the well-oxygenated bottom-water conditions in the late Miocene and Pliocene, manganese initially accumulated on the seafloor as hydrogenous oxides and subsequently was mobilized and reprecipitated as rhodochrosite within the shallow sulfate-reduction, sub-oxic zone. Precipitation of lansfordite occurred in the near-surface sediments with abundant organic carbon and an extremely high alkalinity during the latest Miocene and Pliocene. The lansfordite was transformed to magnesite upon burial in the depth interval 310 to 510 mbsf. Dolomite first precipitated at shallow depths in Mn-poor, anoxic, moderately biocalcareous sediments of early to late Miocene. With increasing temperature and depth, the dolomite recrystallized and reequilibrated with ambient waters at depths below about 400 mbsf.

Amino acid racemization for several DSDP samples (Table 1)

Kinetic parameters for the epimerization of isoleucine in multispecific foraminiferal asemblages were used to establish the effects of burial depth and the geothermal gradient on the extent of reaction. It was observed that with a little as thirty meters of burial in a normal thermal regime there were differences between the extent of epimerization measured and that which would have been predicted for thermal equilibrium with bottom water temperatures. As would be expected, these differences are greatest when the heat flow (the geothermal gradient) and/or the sedimentation rates are highest. These effects were observed in most of the DSDP samples studied, and have been used to estimate the average heat flux since the time of sample deposition. Occasional anomalous effects were observed which could not be related to past or present heat flux. These were determined to be due to such geologic occurrences as slumping and reworking or to recent sample contamination. Other problems emerged related to bottom water temperatures including changes over geologic time which are unknown and could not be deduced. Thus, the presence of epimerization anomalies in DSDP cores as noted above limits the effectiveness of amino acid geochronology in such cores, unless these anomalies can be recognized as ab initio.

Quantifying uplift and denudation of a thermally heterogeneous crust: a detailed multi-thermochronometeric study of central west Britain

Topography is often thought as exclusively linked to mountain ranges formed by plates collision. It is now, however, known that apart from compression, uplift and denudation of rocks may be triggered by rifting, like it happens at elevated passive margins, and away from plate boundaries by both intra-plate stress causing reactivation of older structures, and by epeirogenic movements driven by mantle dynamics and initiating long-wavelength uplift. In the Cenozoic, central west Britain and other parts of the North Atlantic margins experienced multiple episodes of rock uplift and denudation that have been variable both at spatial and temporal scales. The origin of topography in central west Britain is enigmatic, and because of its location, it may be related to any of the processes mentioned above. In this study, three low temperature thermochronometers, the apatite fission track (AFT) and apatite and zircon (U-Th-Sm)/He (AHe and ZHe, respectively) methods were used to establish the rock cooling history from 200◦C to 30◦C. The samples were collected from the intrusive rocks in the high elevation, high relief regions of the Lake District (NW England), southern Scotland and northern Wales. AFT ages from the region are youngest (55–70 Ma) in the Lake District and increase northwards into southern Scotland and southwards in north Wales (>200 Ma). AHe and ZHe ages show no systematic pattern; the former range from 50 to 80 Ma and the latter tend to record the post-emplacement cooling of the intrusions (200–400 Ma). The complex, multi-thermochronometric inverse modelling suggests a ubiquitous, rapid Late Cretaceous/early Palaeogene cooling event that is particularly marked in Lake District and Criffell. The timing and rate of cooling in southern Scotland and in northern Wales is poorly resolved as the amount of cooling was less than 60◦C. The Lake District plutons were at >110◦C prior to the early Palaeogene; cooling due to a combined effect of high heat flow, from the heat producing granite batholith, and the blanketing effect of the overlying low conductivity Late Mesozoic limestones and mudstones. Modelling of the heat transfer suggests that this combination produced an elevated geothermal gradient within the sedimentary rocks (50–70◦C/km) that was about two times higher than at the present day. Inverse modelling of the AFT and AHe data taking the crustal structure into consideration suggests that denudation was the highest, 2.0–2.5 km, in the coastal areas of the Lake District and southern Scotland, gradually decreasing to less than 1 km in the northern Southern Uplands and northern Wales. Both the rift-related uplift and the intra-plate compression poorly correlate with the timing, location and spatial distribution of the early Palaeogene denudation. The pattern of early Palaeogene denudation correlates with the thickness of magmatic underplating, if the changes of mean topography, Late Cretaceous water depth and eroded rock density are taken into consideration. However, the uplift due to underplating alone cannot fully justify the total early Palaeogene denudation. The amount that is not ex- plained by underplating is, however, roughly spatially constant across the study area and can be referred to the transient thermal uplift induced by the mantle plume arrival. No other mechanisms are required to explain the observed pattern of denudation. The onset of denudation across the region is not uniform. Denudation started at 70–75 Ma in the central part of the Lake District whereas the coastal areas the rapid erosion appears to have initiated later (65–60 Ma). This is ~10 Ma earlier than the first vol- canic manifestation of the proto-Iceland plume and favours the hypothesis of the short period of plume incubation below the lithosphere before the volcanism. In most of the localities, the rocks had cooled to temperatures lower than 30◦C by the end of the Palaeogene, suggesting that the total Neogene denudation was, at a maximum, several hundreds of metres. Rapid cooling in the last 3 million years is resolved in some places in southern Scotland, where it could be explained by glacial erosion and post-glacial isostatic uplift.

Influência da adição de cinza do bagaço de cana calcinada em sistemas de pastas para cimentação de poços petrolíferos

Cementing operation is one of the most important stages in the oil well drilling processes and has main function to form hydraulic seal between the various permeable zones traversed by the well. However, several problems may occur with the cement sheath, either during primary cementing or during the well production period. Cements low resistance can cause fissures in the cement sheath and compromise the mechanical integrity of the annular, resulting in contamination of groundwater and producing zones. Several researches show that biomass ash, in particular, those generated by the sugarcane industry have pozzolanic activity and can be added in the composition of the cementing slurries in diverse applications, providing improvements in mechanical properties, revenue and cement durability. Due to the importance of a low cost additive that increases the mechanical properties in a well cementing operations, this study aimed to potentiate the use of sugarcane bagasse ash as pozzolanic material, evaluate the mechanisms of action of this one on cement pastes properties and apply this material in systems slurries aimed to cementing a well with 800 m depth and geothermal gradient of 1.7 °F/100 ft, as much primary cementing operations as squeeze. To do this, the ash beneficiation methods were realized through the processes of grinding, sifting and reburning (calcination) and then characterization by X-ray fluorescence, XRD, TG / DTG, specific surface area, particle size distribution by laser diffraction and mass specific. Moreover, the ash pozzolanic activity added to the cement at concentrations of 0%, 20% and 40% BWOC was evaluated by pozzolanic activity index with lime and with Portland cement. The evaluation of the pozzolanic activity by XRD, TG / DTG and compressive strength confirmed the ash reactivity and indicated that the addition of 20% in the composition of cement slurries produces improvement 34% in the mechanical properties of the slurry cured. Cement slurries properties evaluated by rheological measurements, fluid loss, free fluid, slurry sedimentation, thickening time and sonic strength (UCA) were satisfactory and showed the viability of using the sugarcane ash in cement slurries composition for well cementing

Geothermal measurements at ODP Leg 127 and 128 sites

Downhole temperature and thermal conductivity measurements in core samples recovered during Legs 127 and 128 in the Japan Sea resulted in five accurate determinations of heat flow through the seafloor and accurate estimates of temperature vs. depth over the drilled sections. The heat flows measured at these sites are in excellent agreement with nearby seafloor measurements. Drilling sampled basaltic rocks that form the acoustic basement in the Yamato and Japan basins and provided biostratigraphic and isotopic estimates of the age of these basins. The preliminary age estimates are compared with predicted heat flow values for two different thermal models of the lithosphere. A heat flow determination from the crest of the Okushiri Ridge yielded an anomalously high heat flow of 156 mW/m**2. This excessive heat flow value may have resulted from frictional heating on an active reverse fault that bounds the eastern side of the Ridge. Accurate estimates of sedimentation rates and temperatures in the sedimentary section combined with models of basin formation provide an opportunity to test thermochemical models of silica diagenesis. The current location of the opal-A/opal CT transition in the sedimentary section is determined primarily by the thermal history of the layer in which the transition is now found. Comparison of the ages and temperatures of the layer where the opal-A/opal-CT is found today is compatible with an activation energy of 14 to 17 kcal/mole.

(Table 1) Results of geothermal measurements in the Black Sea 2000 and 2001 expeditions

According to the World Ocean Program in the northeastern part of the continental slope of the Black Sea geothermal, seismologic and seismic studies were carried out. An analysis of heat flow distribution allowed to distinguish a negative geothermal anomaly near the Dzhubga area, where the Russia-Turkey pipeline was being constructed. During seismological observations (August-September 1999, September 2001) more than 1200 seismic events were recorded. They proved high tectonic activity of the region under study, which stimulates gravitational sediment transport on the continental slope. The seismo-acoustic survey carried out in the area of the geothermal anomaly revealed no reflecting horizons within the sedimentary cover. This may be related to turbidite-landsliding processes. Results of modeling of the heat flow anomaly showed that it had originated approximately 1000 years ago due to a powerful landslide. This also suggests a possibility of an avalanche displacement of sedimentary masses in the area of the pipeline at present.

Geothermal measurements in the Tyrrhenian Sea

Geothermal data obtained during Cruise 12 of the R/V Vityaz-II and published data on heat flux of the Tyrrhenian Sea are analyzed. The thermal field is related to principal tectonic structures of the basin. Distribution of heat flux indicates that the initial stage of rifting occurs in the central basin of the Tyrrhenian Sea.