Atmospheric dimethyl sulfide (DMS) and sulfur dioxide (SO2) concentrations were measured at Baring Head, New Zealandduring February and March 2000. Anti-correlated DMS and SO2 diurnalcycles, consistent with the photochemical production of SO2 from DMS, were observed in clean southerly air off the ocean. The data is used to infer a yield of SO2 from DMS oxidation. The estimated yields are highly dependent on assumptions about the DMS oxidation rate. Fitting the measured data in a photochemical box model using model-generated OH levels and the Hynes et al. (1986) DMS + OH rate constant suggests that theSO2 yield is 50–100%, similar to current estimates for the tropical Pacific.However, the observed amplitude of the DMS diurnal cycle suggests that the oxidation rate is higher than that used by the model, and therefore, that theSO2 yield is lower in the range of 20–40%. 相似文献
Apatite fission track analysis was performed on 56 samples from central Spain to unravel the far field effects of the Alpine plate tectonic history of Iberia. The modelled thermal histories reveal complex cooling in the Cenozoic, indicative of intermittent denudation. Accelerated cooling events occurred across the Spanish Central System (SCS) from the Middle Eocene to Recent. These accelerated cooling events resulted in up to 2.8±0.9 km of denudation in the western Sierra de Gredos and 3.6±1.0 km in the central and eastern Gredos (assuming a paleogeothermal gradient of 28±5 °C and a surface temperature of 10 °C). The greatest amount of denudation (5.0±1.6 km) occurred in the Sierra de Guadarrama. Accompanying rock uplift was 4.7±1.0 and 5.9±1.6 km in the eastern Gredos and Guadarrama, respectively. Most denudation in the Gredos occurred from the Middle Eocene to the Early Miocene and can be related to the N–S stress field, induced by the Pyrenean compression. In the Guadarrama, the greatest denudation was Pliocene to Recent of age and seems related to the ongoing NW–SE Betic compression. The fact that the formation of the E–W trending Gredos coincides with the N–S Pyrenean compression and the creation of the present day morphology of the NE–SW trending Guadarrama with the younger NW–SE Betic compression, indicates that they record the far field effects of Alpine plate tectonics on Iberia. The trend of pre-existing lineaments was of major importance in influencing the style and magnitude of these of far field effects. 相似文献
The discovery of crude oils and condensates at ever higher temperatures casts doubt on the validity of the usual geochemical modelling approach, that uses empirical reactions and rate constants. The solution used to account for such a high thermal stability is presently to adjust the rate parameters, but the physical meaning and scientific value of such a strategy can be questioned. We have developed a mechanistic model consisting of 5200 lumped free radical reactions to describe the thermal evolution of a mixture of 52 organic species meant to represent light petroleum. Rate constants used are those available in the literature or estimated using well established thermochemistry-reactivity correlations. Chemical structures included in the model are linear, branched and cyclic hydrocarbons, hydro- and alkyl-aromatics, PAHs, and three heteroatomic compounds. Reactions include cracking and alkylation chains and inhibiting and accelerating reactions from the various reactants. This model has been applied to several mixtures with various proportions of reaction inhibitors and accelerators, and to a composition representing a light mature oil. From the results obtained, we conclude that mature oils will be stable up to 240–260 °C, depending on their composition, and that the thermal cracking of oil to gas is not possible under reasonable basin conditions. The kinetics of petroleum cracking are thus much slower than generally recognized. 相似文献
As a result of the collapse of the Aznalcollar mine tailings dam, a large extension of the Guadiamar valley in SW Spain was covered with a layer of pyrite sludge. Although most of the sludge was removed, a small amount remains in the soil, constituting a potential source of water pollution. A column experiment was carried out in order to determine the rate of sludge oxidation in the soil, and the existence of metal retention processes. The column was filled with a mixture of sludge and a sandy soil common in the region. At different time intervals, the column was leached with water and the resulting solution analysed.
The pH of the water dropped to values around 2 after 260 days and then remained constant due to the buffering role of silicate dissolution. The concentration of Zn, Cd and Co in the leachates matched the expected values from flow-through experiments at atmospheric oxygen pressure. This indicates that oxygen diffusion in the pores was complete. Moreover, no efficient processes existed for retaining Zn, Cd and Co, which formed soluble salts and were entirely incorporated into the infiltrating water. During the first 2 months of the experiment, when pH was higher than 4.5, the concentrations of Fe and Al were very low. Saturation indices showed that the solution was in equilibrium with amorphous Fe(OH)3 and Al(OH)3. Subsequently, at lower pH values, jarosite [(Na,K)Fe3(SO4)2(OH)6] formed. This solid phase was identified by X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM). Jarosite was also responsible for the depletion of As, Pb, Sb and probably Tl in the water resulting from infiltration. 相似文献
Lithium is an important geochemical tracer for fluids or solids. However, because the electron microprobe cannot detect Li, variations of Li abundance at the micrometric scale are most often estimated from bulk analyses. In this study, the Li intense emission line at 670.706 nm in optical emission spectroscopy was used to perfect the analysis of Li at the micrometric scale by means of laser-induced breakdown spectroscopy (LIBS). To estimate lithium content for different geological materials, LIBS calibration of the emission line at 670.706 nm was achieved by use of synthetic glasses and natural minerals. The detection limit for this method is ∼5 ppm Li. Three applications to geological materials show the potential of LIBS for lithium determination, namely for Li-bearing minerals, melt inclusions, quartz, and associated fluid inclusions.For spodumene and petalite from granite pegmatite dikes (Portugal), the Li2O concentrations are 7.6 ± 1.6 wt% and 6.3 ± 1.3 wt%, respectively, by use of LIBS. These values agree with ion microprobe analyses, bulk analyses, or both. For eucryptite crystals, the Li concentrations are scattered because grain size is smaller than the LIBS spatial resolution (6 to 8 μm). Lithium concentrations of melt inclusions from the Streltsovka U deposit (Siberia) are in the range of 2 to 6.2 wt% (Li2O) for Li-rich daughter minerals. Lithium estimations on silicate glasses display values between 90 and 400 ppm.Lithium was also analyzed as a trace element in quartz. Transverse profiles were performed in hydrothermal barren quartz veins from the Spanish Central System (Sierra de Guadarrama). The highest Li concentrations (250 to 370 ppm) were found in specific growth bands in conjunction with the observed variation in optical cathodoluminescence intensity. Considering the fluid inclusion analysis, the source of fluid responsible to the Li enrichment in quartz is probably high-salinity fluids derived from sedimentary basins. 相似文献
Most seismic time-lapse studies so far have been of a qualitative nature. Identification of areas with minor or no seismic changes has been used to plan new infill drilling targets. Increased accuracy in seismic acquisition methods, in both conventional streamer surveys and newer methods such as multicomponent sea-bed seismic and permanent sensors, opens possibilities for the next step: quantitative time-lapse analysis. Quantitative methods here mean the estimation of, for instance, a change in fluid saturation from 20% water to 90% water or the estimation of a pore pressure change of 5 MPa. Explicit expressions for the uncertainties associated with estimated changes in, for instance, reservoir pressure and fluid saturation are derived. These formulae can be used to compare relative uncertainties between estimated parameters as well as to identify the critical factors in various estimation techniques. The importance of accurate rock physics input, as well as that of highly repeatable time-lapse seismic data, is emphasized. Furthermore, uncertainty analysis can be used to find optimal weight factors when the same parameter (e.g. saturation change) is estimated by two or three different techniques. 相似文献