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1.
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2.
Deeply subducted carbonate rocks from the Kokchetav massif (Northern Kazakhstan) recrystallised within the diamond stability field (P = 4.5–6.0 GPa; T ≈ 1000 °C) and preserve evidence for ultra high-pressure carbonate and silicate melts. The carbonate rocks consist of garnet and K-bearing clinopyroxene embedded in a dolomite or magnesian calcite matrix. Polycrystalline magnesian calcite and polyphase carbonate–silicate inclusions occurring in garnet and clinopyroxene show textural features of former melt inclusions. The trace element composition of such carbonate inclusions is enriched in Ba and light rare earth elements and depleted in heavy rare earth elements with respect to the matrix carbonates providing further evidence that the inclusions represent trapped carbonate melt. Polyphase inclusions in garnet and clinopyroxene within a magnesian calcite marble, consisting mainly of a tight intergrowth of biotite + K-feldspar and biotite + zoisite + titanite, are interpreted to represent two different types of K-rich silicate melts. Both melt types show high contents of large ion lithophile elements but contrasting contents of rare earth elements. The Ca-rich inclusions display high REE contents similar to the carbonate inclusions and show a general trace element characteristic compatible with a hydrous granitic origin. Low SiO2 content in the silicate melts indicates that they represent residual melts after extensive interaction with carbonates. These observations suggest that hydrous granitic melts derived from the adjacent metapelites reacted with dolomite at ultra high-pressure conditions to form garnet, clinopyroxene – a hydrous carbonate melt – and residual silicate melts. Silicate and carbonate melt inclusions contain diamond, providing evidence that such an interaction promotes diamond growth. The finding of carbonate melts in deeply subducted crust might have important consequences for recycling of trace elements and especially C from the slab to the mantle wedge.  相似文献   

3.
To improve our knowledge about the geochemical and environmental aftermath of Neoproterozoic global glaciations, we analyzed stable isotopes (δ13C, δ18O, δ34S) and elemental concentrations (Ca, Mg, S, Sr, Fe, and Mn) of the ～ 10-m-thick Zhamoketi cap dolostone atop the Tereeken diamictite in the Quruqtagh area, eastern Chinese Tianshan. Available chemostratigraphic data suggest that the Tereeken diamictite is probably equivalent to the Marinoan glaciation. Our new data indicate that organic and carbonate carbon isotopes of the Zhamoketi cap dolostone show little stratigraphic variations, averaging ? 28.2‰ and ? 4.6‰, respectively. In contrast, sulfur isotopes show significant stratigraphic variations. Carbonate associated sulfate (CAS) abundance decreases rapidly in the basal cap dolostone and δ34SCAS composition varies between + 9‰ and + 15‰ in the lower 2.5 m. In the overlying interval, CAS abundance remains low while δ34SCAS rises ～ 5‰ and varies more widely between + 10‰ and + 21‰. The range of δ34Spy of the cap dolostone overlaps with that of δ34SCAS, but direct comparison shows that δ34Spy is typically greater than δ34SCAS measured from the same samples. Hypotheses to explain the observations must account for both the remarkable sulfur isotope enrichment of pyrites and the inverse fractionation. We propose that CAS and pyrite were derived from two isotopically distinct reservoirs in a chemically stratified basin or a basin with a sulfate minimum zone. In this model, CAS was derived from shallow, oxic surface waters with moderate sulfate concentration and depleted in 34S due to the post-glacial influx of sulfur from continental weathering. In contrast, pyrite was derived from anoxic bottom waters (or a sulfate minimum zone) with low sulfate concentration and 34S enrichment due to long-term syn-glacial sulfate reduction. The rapid shift in CAS abundance and sulfur isotope composition within the cap dolostone is interpreted to reflect the mixing of the two reservoirs after initial deglaciation. Comparison with other post-Marinoan cap carbonates shows significant spatial heterogeneity in δ34SCAS, which together with strong temporal variation in δ34SCAS, points to generally low sulfate concentrations in post-Marinoan oceans.  相似文献   

4.
In this study we performed three categories of steady- and unsteady-state core-flooding experiments to investigate capillary trapping, relative permeability, and capillary pressure, in a scCO2 + SO2/brine/limestone system at elevated temperature and pressure conditions, i.e., 60 °C and 19.16 MPa. We used a Madison limestone core sample acquired from the Rock Springs Uplift in southwest Wyoming. We carried out two sets of steady-state drainage-imbibition relative permeability experiments with different initial brine saturations to study hysteresis. We found that the final scCO2 + SO2 drainage relative permeability was very low, i.e., 0.04. We also observed a rapid reduction in the scCO2-rich phase imbibition relative permeability curve, which resulted in a high residual trapping. The results showed that between 62.8% and more than 76% of the initial scCO2 + SO2 at the end of drainage was trapped by capillary trapping mechanism (trapping efficiency). We found that at higher initial brine saturations, the trapping efficiency was higher. The maximum initial and residual scCO2-rich phase saturations at the end of primary drainage and imbibition were 0.525 and 0.329, respectively. Each drainage-imbibition cycle was followed by a dissolution process to re-establish Sw = 1. The dissolution brine relative permeabilities for both cycles were also obtained. We characterized the scCO2 + SO2/brine capillary pressure hysteresis behavior through unsteady-state primary drainage, imbibition, and secondary drainage experiments. We observed negative imbibition capillary pressure curve indicative of possible wettability alteration throughout the experiments due to contact with scCO2 + SO2/brine fluid system. The trapping results were compared to those reported in literature for other carbonate core samples. We noticed slightly more residual trapping in our sample, which might be attributed to heterogeneity, different viscosity ratio, and pore-space topologies. The impact of dynamic effects, i.e., high brine flow rate imbibition tests, on trapping of the scCO2-rich phase was also explored. We performed two imbibition experiments with relatively high brine flow rates. The residual scCO2 saturation dropped to 0.291 and 0.262 at the end of the first and second imbibition tests, i.e., 11.5% and 20.4%, respectively, compared to 0.329 under capillary-dominated regime.  相似文献   

5.
Single-crystal elasticity of stishovite was examined using a new experimental technique and an empirical macroscopic model. Employing high-frequency resonant ultrasound spectroscopy, single-crystal elastic constants of stishovite were determined: C11 = 443(3), C33 = 781(4), C12 = 193(2), C23 = 199(2), C44 = 256(2), and C33 = 316(2) GPa. The frequency range of the resonant ultrasound spectroscopy techniques was 6–20 MHz, which is much lower than the ～10 GHz range of the Brillouin scattering technique. Of the elastic constants, the shear elastic constants C44 and C66 are consistent with the average value of the previously mentioned Brillouin scattering. Conversely, the four elastic constants, C11, C33, C12, and C23, slightly deviate outside the range of previous Brillouin scattering results. The present results, except those for C12, are consistent with recent lattice dynamic analysis of inelastic X-ray scattering data. The adiabatic bulk modulus was calculated as 298 GPa, which is smaller and more consistent with the result of compression experiments than any other Brillouin scattering results (301–312 GPa). The present result shows greater P-wave velocity anisotropy (24.7%) than any preceding work. To understand the unique elastic properties of stishovite, the Gingham check model was proposed and examined. The result shows that the octahedron of 6-coordinated Si in stishovite crystal has stiffness comparable to that of diamond.  相似文献   

6.
Attenuation data extracted from full waveform sonic logs is sensitive to vuggy and matrix porosities in a carbonate aquifer. This is consistent with the synthetic attenuation (1 / Q) as a function of depth at the borehole-sonic source-peak frequency of 10 kHz. We use velocity and densities versus porosity relationships based on core and well log data to determine the matrix, secondary, and effective bulk moduli. The attenuation model requires the bulk modulus of the primary and secondary porosities. We use a double porosity model that allows us to investigate attenuation at the mesoscopic scale. Thus, the secondary and primary porosities in the aquifer should respond with different changes in fluid pressure. The results show a high permeability region with a Q that varies from 25 to 50 and correlates with the stiffer part of the carbonate formation. This pore structure permits water to flow between the interconnected vugs and the matrix. In this region the double porosity model predicts a decrease in the attenuation at lower frequencies that is associated with fluid flowing from the more compliant high-pressure regions (interconnected vug space) to the relatively stiff, low-pressure regions (matrix). The chalky limestone with a low Q of 17 is formed by a muddy porous matrix with soft pores. This low permeability region correlates with the low matrix bulk modulus. A low Q of 18 characterizes the soft sandy carbonate rock above the vuggy carbonate.This paper demonstrates the use of attenuation logs for discriminating between lithology and provides information on the pore structure when integrated with cores and other well logs. In addition, the paper demonstrates the practical application of a new double porosity model to interpret the attenuation at sonic frequencies by achieving a good match between measured and modeled attenuation.  相似文献   

7.
The Ca isotope compositions of 37 late Mesozoic skeletal carbonates, belemnites and brachiopods, from the Tethyan realm were analyzed by thermal (TIMS) and plasma (MC-ICP-MS) ionization mass spectrometry. A poor correlation between δ44/40Ca and δ18O values of belemnites suggests only a weak temperature dependency for the Ca isotope composition of belemnites, likely less than 0.02‰/°C. The δ44/40Ca record of belemnites was therefore used to reconstruct the Ca isotope composition of paleo-seawater (δ44/40CaSW), based on an experimentally determined fractionation factor between seawater Ca and belemnite calcite (αCC–SW) of ∼ 0.9986. The inferred δ44/40CaSW record, with an average stratigraphic resolution of 1 Ma, shows systematic temporal variation of ∼ 0.5‰ with the Middle/Late Jurassic (∼ 154 Ma) minimum of ∼ 1.4‰ and a subsequent general increase to the Early Cretaceous (∼ 124 Ma) maximum of ∼ 1.9‰. The global nature of the δ44/40CaSW record is supported by identical Ca isotope compositions of coeval (Kimmeridgian) belemnites collected from two distinct paleogeographic regions, the southern (New Zealand) and northern (Germany) margin of the Tethys Ocean. The observed late Mesozoic δ44/40CaSW record was simulated using a simple Ca isotope mass balance model, and the results indicate that the variation in δ44/40CaSW record can be explained by changes in oceanic input fluxes of Ca that were independent of the carbonate ion fluxes, such as the hydrothermal Ca flux or the release of Ca to the oceans via dolomitization of marine carbonates.  相似文献   

8.
Outcrops of the Cretaceous Upper sandstone formation some 375 km to the East of Addis Ababa on the motor Highway to Harar was paleomagnetically investigated. About seventy core samples were collected at various stratigraphic levels from 250–300 meters thick sedimentary formation. After standard sample preparations in the laboratory the resulting specimens were subjected to routine paleomagnetic demagnetization protocol. In the first steps of demagnetizations process the recent and viscous magnetizations were removed by heating until a temperature of level of 300 °C. Further demagnetization of the samples resulted in the isolation of the final magnetization with stable line segments that is directed towards the origin, which is interpreted as Characteristic Remanent Magnetization (ChRM). Rock – magnetic experiments have identified goethite (αFeOOH), hematite (αFe2O3), detritial hematite, and magnetite as the magnetic mineral phases carrying the remanence. The ChRM identified resulted in an average value of (Ds = 0.5°, Is = ?0.7°, α95 = 4.3°, N = 34) for the red sandstones while an average value of (Ds = 335.8°, Is = ?31.8°, α95 = 4.7°, N = 14) for the limestone intercalations. The former ChRM in the red sandstone is determined to be secondary while the latter ChRM is known to be primary. Comparison of these directional results and their pole equivalents with the African plate Apparent Polar Wander Path curve established by Besse and Courtillot (2003) give ages of between 115–130 Million years for the limestone intercalation and ages of 30 million years for red sandstone unit. These are interpreted respectively as estimates of the age of deposition and a later remagnetization respectively.  相似文献   

9.
SHRIMP zircon U–Pb dating, mineral chemical, element geochemical and Sr–Nd–Pb–Hf isotopic data have been determined for the Yulong monzogranite-porphyry in the eastern Tibet, China. The Yulong porphyry was emplaced into Triassic strata at about 39 Ma. The rocks are weakly peraluminous and show shoshonitic affinity, i.e., alkalis-rich, high K2O contents with high K2O / Na2O ratios, enrichment in LREE and LILE. They also show some affinities with the adakite, e.g., high SiO2 and Al2O3, and low MgO contents, depleted in Y and Yb, and enrichment in Sr with high Sr / Y and La / Yb ratios, and no Eu anomalies. The Yulong porphyry has radiogenic 87Sr / 86Sr (0.7063–0.7070) and unradiogenic 143Nd / 144Nd (εNd = − 2.0 to − 3.0) ratios. The Pb isotopic compositions of feldspar phenocrysts separated from the Yulong porphyry show a narrow range of 206Pb / 204Pb ratios (18.71–18.82) and unusually radiogenic 207Pb / 204Pb (15.65–15.67) and 208Pb / 204Pb (38.87–39.00) ratios. In situ Hf isotopic composition of zircons that have been SHRIMP U–Pb dated is characterized by clearly positive initial εHf values, ranging from + 3.1 to + 5.9, most between + 4 and + 5. Phenocryst clinopyroxene geothermometry of the Yulong porphyry indicates that the primary magmas had anomalously high temperature (> 1200 °C). The source depth for the Yulong porphyry is at least 100 km inferred by the metasomatic volatile phase (phlogopite–carbonate) relations. Detailed geochemical and Sr–Nd–Pb–Hf isotopic compositions not only rule out fractional crystallization or assimilation-fractional crystallization processes, but also deny the possibility of partial melting of subducted oceanic crust or basaltic lower crust. Instead, low degree (1–5%) partial melting of a metasomatized lithosphere (phlogopite–garnet clinopyroxenite) is compatible with the data. This example gives a case study that granite can be derived directly by partial melting of an enriched lithospheric mantle, which is important to understand the source and origin of diverse granites.  相似文献   

10.
Serpentinization of the mantle wedge is an important process that influences the seismic and mechanical properties in subduction zones. Seismic detection of serpentines relies on the knowledge of elastic properties of serpentinites, which thus far has not been possible in the absence of single-crystal elastic properties of antigorite. The elastic constants of antigorite, the dominant serpentine at high-pressure in subduction zones, were measured using Brillouin spectroscopy under ambient conditions. In addition, antigorite lattice preferred orientations (LPO) were determined using an electron back-scattering diffraction (EBSD) technique. Isotropic aggregate velocities are significantly lower than those of peridotites to allow seismic detection of serpentinites from tomography. The isotropic VP/VS ratio is 1.76 in the Voigt–Reuss–Hill average, not very different from that of 1.73 in peridotite, but may vary between 1.70 and 1.86 between the Voigt and Reuss bonds. Antigorite and deformed serpentinites have a very high seismic anisotropy and remarkably low velocities along particular directions. VP varies between 8.9 km s? 1 and 5.6 km s? 1 (46% anisotropy), and 8.3 km s? 1 and 5.8 km s? 1 (37%), and VS between 5.1 km s? 1 and 2.5 km s? 1 (66%), and 4.7 km s? 1 and 2.9 km s? 1 (50%) for the single-crystal and aggregate, respectively. The VP/VS ratio and shear wave splitting also vary with orientation between 1.2 and 3.4, and 1.3 and 2.8 for the single-crystal and aggregate, respectively. Thus deformed serpentinites can present seismic velocities similar to peridotites for wave propagation parallel to the foliation or lower than crustal rocks for wave propagation perpendicular to the foliation. These properties can be used to detect serpentinite, quantify the amount of serpentinization, and to discuss relationships between seismic anisotropy and deformation in the mantle wedge. Regions of high VP/VS ratios and extremely low velocities in the mantle wedge of subduction zones (down to about 6 and 3 km.s?1 for VP and VS, respectively) are difficult to explain without strong preferred orientation of serpentine. Local variations of anisotropy may result from kilometer-scale folding of serpentinites. Shear wave splittings up to 1–1.5 s can be explained with moderately thick (10–20 km) serpentinite bodies.  相似文献   

11.
With transmission electron microscopy (TEM) we observed nanometer-sized pores in four ultracataclastic and fractured core samples recovered from different depths of the main bore hole of the San Andreas Fault Observatory at Depth (SAFOD). Cutting of foils with a focused ion beam technique (FIB) allowed identifying porosity down to the nm scale. Between 40 and 50% of all pores could be identified as in-situ pores without any damage related to sample preparation. The total porosity estimated from TEM micrographs (1–5%) is comparable to the connected fault rock porosity (2.8–6.7%) estimated by pressure-induced injection of mercury. Permeability estimates for cataclastic fault rocks are 10? 21–10? 19 m2 and 10? 17 m2 for the fractured fault rock. Porosity and permeability are independent of sample depth. TEM images reveal that the porosity is intimately linked to fault rock composition and associated with deformation. The TEM-estimated porosity of the samples increases with increasing clay content. The highest porosity was estimated in the vicinity of an active fault trace. The largest pores with an equivalent radius > 200 nm occur around large quartz and feldspar grains or grain-fragments while the smallest pores (equivalent radius < 50 nm) are typically observed in the extremely fine-grained matrix (grain size < 1 μm). Based on pore morphology we distinguish different pore types varying with fault rock fabric and alteration. The pores were probably filled with formation water and/or hydrothermal fluids at elevated pore fluid pressure, preventing pore collapse. The pore geometry derived from TEM observations and BET (Brunauer, Emmett and Teller) gas adsorption/desorption hysteresis curves indicates pore blocking effects in the fine-grained matrix. Observations of isolated pores in TEM micrographs and high pore body to pore throat ratios inferred from mercury injection suggest elevated pore fluid pressure in the low permeability cataclasites, reducing shear strength of the fault.  相似文献   

12.
Shallow carbonates are of utmost importance as potential sources of groundwater in karstified semi-arid terrains. Ground-Penetrating Radar (GPR) is being increasingly used as a prominent mapping tool in such environments. However, its potential in exploring and identifying shallow water-saturated zones (WSZs) in carbonates is constrained by the geoelectrical properties of carbonate soils as a function of moisture content. We report results of a case study that includes laboratory geoelectrical characterization and their comparison to in situ GPR attenuation measurements performed on Cretaceous Edwards Formation rudist mounds in central Texas, which we hypothesize as analogs for water-bearing formations in semi-arid karstified carbonate terrains. Dielectric measurements on field-collected rock samples carried out in the laboratory under controlled conditions of moisture saturation suggest that real and imaginary parts of dielectric constants of rocks with higher porosity and/or permeability have steeper dependence on pore moisture content; they produce better dielectric contrasts but allow shallower penetration. Our analyses suggest that within carbonates, dielectric contrasts improve with decrease in sounding frequency and/or increase in moisture content; and the relationship between dielectric permittivity and moisture content may be represented by 3rd order polynomial equations. GPR surveys using a wide-band 400 MHz antenna reveal subsurface mound morphologies with heights of ～ 1–2 m and basal diameters of ～ 8–10 m resembling outcrop analogs. Each mound appears to be composed of smaller amalgamated lithounits that seem geoelectrically similar. Amplitudes decays of the backscattered radar signal correlate to moisture distribution. Measuring the differences in signal attenuation allows differentiation between saturated and non-saturated zones. Velocity analyses of GPR profiles enable estimation of moisture distribution in the vicinity of the mounds. Optimal delineation and production of high-resolution GPR data up to a depth of ～ 10 m were observed for a sounding frequency of ～ 250 MHz with moisture content of ～ 5% by weight. Below this moisture level, the dielectric contrast is insufficient to uniquely identify water-saturated zones from the surrounding geoelectrical context, and above it, the radar signal is substantially attenuated leading to a total inefficiency of the method.  相似文献   

13.
The single backscattering model was used to estimate total attenuation of coda waves (Qc) of local earthquakes recorded on eight seismological stations in the complex area of the western continental Croatia. We estimated Q0 and n, parameters of the frequency dependent coda-Q using the relation Qc = Q0fn. Lapse time dependence of these parameters was studied using a constant 30 s long time window that was slid along the coda of seismograms. Obtained Qc were distributed into classes according to their lapse time, tL. For tL = 20–50 s we estimated Q0 = 45–184 and n = 0.49–0.94, and for tL = 60–100 s we obtained Q0 = 119–316 and n = 0.37–0.82. There is a tendency of decrease of parameter n with increasing Q0, and vice versa. The rates of change of both Q0 and n seem to decrease for lapse times larger than 50–80 s, indicating an alteration in rock properties controlling coda attenuation at depths of about 100–160 km. A very good correlation was found between the frequency dependence parameter n and the Moho depths for lapse times of 50, 60 and 70 s.  相似文献   

14.
At the appropriate times, silica diffusion in clay is possibly the rate determining process for the dissolution of vitrified waste disposed of in a clay layer. For testing this hypothesis, combined glass dissolution/silica diffusion experiment are performed. SON68 glass coupons doped with the radioactive tracer 32Si are sandwiched between two cores of humid Boom Clay, heated to 30 °C. Due to glass dissolution, 32Si is released and diffuses into the clay. At the end of an experiment, the mass loss of the glass coupon is measured and the clay core is sliced to determine the diffusion profile of the 32Si released from the glass in the clay.Both mass loss and the 32Si diffusion profile in the clay are described well by a model combining glass dissolution according to a linear rate law with silica diffusion in the clay. Fitting the experiments to this model leads to an apparent silica diffusion coefficient in the clay between 7 × 10−13 m2/s and 1.2 × 10−12 m2/s. Previously determined values from diffusion experiments at 25 °C are around 6 × 10−13 m2/s (In-Diffusion experiments) and 2 × 10−13 m2/s (percolation experiments). The maximal glass dissolution rate for glass next to clay is around 1.6 × 10−7 g glass/m2 s (i.e. 0.014 g glass/m2 day). In undisturbed clay, the measured silica concentration is around 5 mg/L. Combining these values with the previously measured (In-Diffusion experiments) product of accessible porosity and retardation factor, leads in two ways to a silica glass saturation concentration in clay between 8 and 10 mg Si/L.Another candidate for the rate determining process of the dissolution of vitrified waste disposed in a clay layer is silica precipitation. Although silica precipitation due to glass dissolution has been shown experimentally at 90 °C, extending the model with silica precipitation does not lead to much better fits, nor could meaningful values of a possible precipitation rate be obtained.  相似文献   

15.
《Marine pollution bulletin》2012,64(5-12):201-208
Flow cytometry was used to examine immune responses in haemocytes of the green-lipped mussel Perna viridis under six combinations of oxygen level (1.5 mg O2 l−1, 6.0 mg O2 l−1) and temperature (20 °C, 25 °C and 30 °C) at 24 h, 48 h, 96 h and 168 h. The mussels were then transferred to normoxic condition (6.0 mg O2 l−1) at 20 °C for further 24 h to study their recovery from the combined hypoxic and temperature stress. Esterase (Est), reactive oxygen species (ROS), lysosome content (Lyso) and phagocytosis (Pha) were reduced at high temperatures, whereas hypoxia resulted in higher haemocyte mortality (HM) and reduced phagocytosis. For HM and Pha, changes were observed after being exposed to the stresses for 96 h, whereas only a 24 h period was required for ROS and Lyso, and a 48 h one for Est. Recovery from the stresses was observed for HM and Pha but not other immune responses.  相似文献   

16.
Equivalent dose (De) values were measured by using medium aliquots of different grain size quartz fractions of five lakeshore sediments from the arid region of north China. There are two different relationships between De values and grain sizes of these five samples. The first relationship is that the De values obtained from various grain sizes are in agreement within 1 delta errors. The second relationship is that De values are similar to each other for fractions between 125 and 300 μm, while the De value of the 63–90 μm fraction is 40～55% smaller than others. For example, the De values obtained for sample #3 are 20.15 ± 1.19 Gy, 19.80 ± 0.83 Gy and 20.93 ± 1.06 Gy for fractions of 90–125, 125–150 and 250–300 μm respectively, but are 10.79 ± 0.84 Gy for the 63–90 μm fraction. The second relationship can't be interpreted by previous studies of both dosimetry and heterogeneous bleaching. It is deduced for sample #2, #3 and #6 that fine particles (<90 μm) intruded after the dominant sedimentation. Comparison of OSL ages from different grain size fractions of sample #2 with a radiocarbon age from the same lithologic layer supports that fractions coarser than 125 μm yield more reliable burial ages, while the fraction finer than 90 μm yields underestimated ages for some lakeshore sediments from this arid region.  相似文献   

17.
This study is undertaken to understand how calcite precipitation and dissolution contributes to depth-related changes in porosity and permeability of gas-bearing sandstone reservoirs in the Kela 2 gas field of the Tarim Basin, Northwestern China. Sandstone samples and pore water samples are col-lected from well KL201 in the Tarim Basin. Vertical profiles of porosity, permeability, pore water chem-istry, and the relative volume abundance of calcite/dolomite are constructed from 3600 to 4000 m below the ground surface within major oil and gas reservoir rocks. Porosity and permeability values are in-versely correlated with the calcite abundance, indicating that calcite dissolution and precipitation may be controlling porosity and permeability of the reservoir rocks. Pore water chemistry exhibits a sys-tematic variation from the Na2SO4 type at the shallow depth (3600-3630 m), to the NaHCO3 type at the intermediate depth (3630―3695 m),and to the CaCl2 type at the greater depth (3728―3938 m). The geochemical factors that control the calcite solubility include pH, temperature, pressure, Ca2 concen-tration, the total inorganic carbon concentration (ΣCO2), and the type of pore water. Thermodynamic phase equilibrium and mass conservation laws are applied to calculate the calcite saturation state as a function of a few key parameters. The model calculation illustrates that the calcite solubility is strongly dependent on the chemical composition of pore water, mainly the concentration difference between the total dissolved inorganic carbon and dissolved calcium concentration (i.e., [ΣCO2] -[Ca2 ]). In the Na2SO4 water at the shallow depth, this index is close to 0, pore water is near the calcite solubility. Calcite does not dissolve or precipitate in significant quantities. In the NaHCO3 water at the intermedi-ate depth, this index is greater than 0, and pore water is supersaturated with respect to calcite. Massive calcite precipitation was observed at this depth interval and this intensive cementation is responsible for decreased porosity and permeability. In the CaCl2 water at the greater depth, pore water is un-der-saturated with respect to calcite, resulting in dissolution of calcite cements, as consistent with microscopic dissolution features of the samples from this depth interval. Calcite dissolution results in formation of high secondary porosity and permeability, and is responsible for the superior quality of the reservoir rocks at this depth interval. These results illustrate the importance of pore water chemis-try in controlling carbonate precipitation/dissolution, which in turn controls porosity and permeability of oil and gas reservoir rocks in major sedimentary basins.  相似文献   

18.
Silica alteration zones and cherts are a conspicuous feature of Archaean greenstone belts worldwide and provide evidence of extensive mobilisation of silica in the marine environment of the early Earth. In order to understand the process(es) of silicification we measured the silicon and oxygen isotope composition of sections of variably silicified basalts and overlying bedded cherts from the Theespruit, Hooggenoeg and Kromberg Formations of the Barberton Greenstone Belt, South Africa.The δ30Si and δ18O values of bulk rock increase with increasing amount of silicification from unsilicified basalts (?0.64‰ < δ30Si < ?0.01‰ and + 8.6‰ < δ18O < + 11.9‰) to silicified basalts (δ30Si and δ18O values as high as + 0.81‰ and + 15.6‰, respectively). Cherts generally have positive isotope ratios (+ 0.21‰ < δ30Si < + 1.05‰ and + 10.9 < δ18O < + 17.1), except two cherts, which have negative δ30Si values, but high δ18O (up to + 19.5‰).The pronounced positive correlations between δ30Si, δ18O and SiO2 imply that the isotope variation is driven by the silicification process which coevally introduced both 18O and 30Si into the basalts. The oxygen isotope variation in the basalts from about 8.6‰ to 15.6‰ is likely to represent temperature-dependent isotope fractionation during alteration. Our proposed model for the observed silicon isotope variation relies on a temperature-controlled basalt dissolution vs. silica deposition process.  相似文献   

19.
The Toarcian Oceanic Anoxic Event (OAE) in the Early Jurassic (∼ 183 Ma ago) was characterized by widespread near-synchronous deposition of organic-rich shales in marine settings, as well as perturbations to several isotopic systems. Characteristically, two positive carbon-isotope excursions in a range of materials are separated by an abrupt negative shift. Carbon-isotope profiles from Toarcian fossil wood collected in England and Denmark have previously been shown to exhibit this large drop (∼ − 7‰) in δ13C values, interpreted as due to an injection of isotopically light CO2 into the ocean–atmosphere system. However, the global nature of this excursion has been challenged on the basis of carbon-isotope data from nektonic marine molluscs (belemnites), which exhibit heavier than expected carbon-isotope values. Here we present new data, principally from fossil wood and bulk carbonate collected at centimetre scale from a hemipelagic section at Peniche, coastal Portugal. This section is low in organic carbon (average TOC = ∼ 0.5%), and the samples should not have suffered significant diagenetic contamination by organic carbon of marine origin. The carbon-isotope profile based on wood shows two positive excursions separated by a large and abrupt negative excursion, which parallels exactly the profile based on bulk carbonate samples from the same section, albeit with approximately twice the amplitude (∼ − 8‰ in wood versus ∼ − 3.5‰ in carbonate). These data indicate that the negative carbon-isotope excursion affected the atmosphere and, by implication, the global ocean as well. The difference in amplitude between terrestrial organic and marine carbonate curves can be explained by greater water availability in the terrestrial environment during the negative excursion, for which there is independent evidence from marine osmium-isotope records and, plausibly, changes in atmospheric CO2 content, for which independent evidence is also available. The Peniche succession is also notable for the occurrence of re-deposited sediments: their lowest occurrence coincides with the base of the negative excursion and their highest occurrence coincides with its top. Thus, slope instability and sediment supply could have been strongly linked to the global environmental perturbation, an association that may misleadingly simulate the effects of sea-level fall.  相似文献   

20.
Drinking water wells indiscriminatingly placed adjacent to fecal contaminated surface water represents a significant but difficult to quantify health risk. Here we seek to understand mechanisms that limit the contamination extent by scaling up bacterial transport results from the laboratory to the field in a well constrained setting. Three pulses of Escherichia coli originating during the early monsoon from a freshly excavated pond receiving latrine effluent in Bangladesh were monitored in 6 wells and modeled with a two-dimensional (2-D) flow and transport model conditioned with measured hydraulic heads. The modeling was performed assuming three different modes of interaction of E. coli with aquifer sands: (1) irreversible attachment only (best-fit ki = 7.6 day−1); (2) reversible attachment only (ka = 10.5 and kd = 0.2 day−1); and (3) a combination of reversible and irreversible modes of attachment (ka = 60, kd = 7.6, ki = 5.2 day−1). Only the third approach adequately reproduced the observed temporal and spatial distribution of E. coli, including a 4-log10 lateral removal distance of ∼9 m. In saturated column experiments, carried out using aquifer sand from the field site, a combination of reversible and irreversible attachment was also required to reproduce the observed breakthrough curves and E. coli retention profiles within the laboratory columns. Applying the laboratory-measured kinetic parameters to the 2-D calibrated flow model of the field site underestimates the observed 4-log10 lateral removal distance by less than a factor of two. This is promising for predicting field scale transport from laboratory experiments.  相似文献   

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