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1.
We have developed a technique for the accurate and precise determination of 34S/32S isotope ratios (δ34S) in sulfur-bearing minerals using solution and laser ablation multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). We have examined and determined rigorous corrections for analytical difficulties such as instrumental mass bias, unresolved isobaric interferences, blanks, and laser ablation- and matrix-induced isotopic fractionation. Use of high resolution sector-field mass spectrometry removes major isobaric interferences from O2+. Standard-sample bracketing is used to correct for the instrumental mass bias of unknown samples. Background on sulfur masses arising from memory effects and residual oxygen-tailing are typically minor (< 0.2‰, within analytical error), and are mathematically removed by on-peak zero subtraction and by bracketing of samples with standards determined at the same signal intensity (within 20%). Matrix effects are significant (up to 0.7‰) for matrix compositions relevant to many natural sulfur-bearing minerals. For solution analysis, sulfur isotope compositions are best determined using purified (matrix-clean) sulfur standards and sample solutions using the chemical purification protocol we present. For in situ analysis, where the complex matrix cannot be removed prior to analysis, appropriately matrix-matching standards and samples removes matrix artifacts and yields sulfur isotope ratios consistent with conventional techniques using matrix-clean analytes. Our method enables solid samples to be calibrated against aqueous standards; a consideration that is important when certified, isotopically-homogeneous and appropriately matrix-matched solid standards do not exist. Further, bulk and in situ analyses can be performed interchangeably in a single analytical session because the instrumental setup is identical for both. We validated the robustness of our analytical method through multiple isotope analyses of a range of reference materials and have compared these with isotope ratios determined using independent techniques. Long-term reproducibility of S isotope compositions is typically 0.20‰ and 0.45‰ (2σ) for solution and laser analysis, respectively. Our method affords the opportunity to make accurate and relatively precise S isotope measurement for a wide range of sulfur-bearing materials, and is particularly appropriate for geologic samples with complex matrix and for which high-resolution in situ analysis is critical.  相似文献   
2.
We investigate the Logatchev Hydrothermal Field at the Mid-Atlantic Ridge, 14°45′N to constrain the calcium isotope hydrothermal flux into the ocean. During the transformation of seawater to a hydrothermal solution, the Ca concentration of pristine seawater ([Ca]SW) increases from about 10 mM to about 32 mM in the hydrothermal fluid endmember ([Ca]HydEnd) and thereby adopts a δ44/40CaHydEnd of −0.95 ± 0.07‰ relative to seawater (SW) and a 87Sr/86Sr isotope ratio of 0.7034(4). We demonstrate that δ44/40CaHydEnd is higher than that of the bedrock at the Logatchev field. From mass balance calculations, we deduce a δ44/40Ca of −1.17 ± 0.04‰ (SW) for the host-rocks in the reaction zone and −1.45 ± 0.05‰ (SW) for the isotopic composition of the entire hydrothermal cell of the Logatchev field. The values are isotopically lighter than the currently assumed δ44/40Ca for Bulk Earth of −0.92 ± 0.18‰ (SW) [Skulan J., DePaolo D. J. and Owens T. L. (1997) Biological control of calcium isotopic abundances in the global calcium cycle. Geochim. Cosmochim. Acta61,(12) 2505-2510] and challenge previous assumptions of no Ca isotope fractionation between hydrothermal fluid and the oceanic crust [Zhu P. and Macdougall J. D. (1998) Calcium isotopes in the marine environment and the oceanic calcium cycle. Geochim. Cosmochim. Acta62,(10) 1691-1698; Schmitt A. -D., Chabeaux F. and Stille P. (2003) The calcium riverine and hydrothermal isotopic fluxes and the oceanic calcium mass balance. Earth Planet. Sci. Lett. 6731, 1-16]. Here we propose that Ca isotope fractionation along the fluid flow pathway of the Logatchev field occurs during the precipitation of anhydrite. Two anhydrite samples from the Logatchev Hydrothermal Field show an average fractionation of about Δ44/40Ca = −0.5‰ relative to their assumed parental solutions. Ca isotope ratios in aragonites from carbonate veins from ODP drill cores indicate aragonite precipitation directly from seawater at low temperatures with an average δ44/40Ca of −1.54 ± 0.08‰ (SW). The relatively large fractionation between the aragonite precipitates and seawater in combination with their frequent abundance in weathered mafic and ultramafic rocks suggest a reconsideration of the marine Ca isotope budget, in particular with regard to ocean crust alteration.  相似文献   
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Radon has been used to determine groundwater velocity and groundwater discharge into wetlands at the southern downstream boundary of the Crau aquifer, southeastern France. This aquifer constitutes an important high-quality freshwater resource exploited for agriculture, industry and human consumption. An increase in salinity occurs close to the sea, highlighting the need to investigate the water balance and groundwater behavior. Darcy velocity was estimated using radon activities in well waters according to the Hamada “single-well method” (involving comparison with radon in groundwater in the aquifer itself). Measurements done at three depths (7, 15 and 21 m) provided velocity ranging from a few mm/day to more than 20 cm/day, with highest velocities observed at the 15-m depth. Resulting hydraulic conductivities agree with the known geology. Waters showing high radon activity and high salinity were found near the presumed shoreline at 3,000 years BP, highlighting the presence of ancient saltwater. Radon activity has also been measured in canals, rivers and ponds, to trace groundwater discharges and evaluate water balance. A model of the radon spatial evolution explains the observed radon activities. Groundwater discharge to surface water is low in pond waters (4 % of total inputs) but significant in canals (55 l/m2/day).  相似文献   
6.
Whether or not fishers comply with regulation depends on the economic and social context in which they operate their vessels. This is how conventional theory explains the phenomenon of non-compliance. It treats state–community interaction processes not as direct causes for non-compliance but rather as background conditions shaping individual fishers’ perception and decisions for action. This paper argues that conventional theory fails to include the dynamics of tempo-relational processes between state and communities, which explains collective patterns of non-compliance in fisheries. The paper addresses this hiatus in the literature, using a process-sociological approach to analyse non-compliance in Vietnamese marine fisheries. The analysis highlights that Vietnamese marine fisheries are mainly regulated through informal networks of trust and mistrust, which function through their interplay with the highly centralised and formalised Vietnamese state. Based on this assessment, the paper concludes that outcomes of processes of the dynamic social interplay between state and communities are semi-dependent on individual perception and action, and as such have a causal effect of their own on patterns of non-compliance in fisheries.  相似文献   
7.
Based upon a re-interpretation of previous data and a new field campaign, a structural evolution is proposed for the early history of Piton de la Fournaise volcano from 500,000 to 50,000 years. Conceptually, it is shown that the formation of a caldera in which lava flows are contained inside the caldera depression, gives time for erosion to excavate deep canyons on the external slopes of the volcano, for example, the Rivière des Remparts, the Rivière Langevin and the Rivière de l'Est canyons on Piton de la Fournaise volcano. These canyons are infilled when lavas, filling the caldera and overflowing its rim, are able again to flow on the external slopes of the volcano. In the past, this excavating/infilling process has occurred twice following the formation of the Rivière des Remparts and Morne Langevin calderas. The formation of the third caldera, the Plaine des Sables caldera, was followed by the excavation of the current canyons. In addition to this process, two large landslides have been documented in the field. The first, which happened about 300,000 years ago, is apparently the first episode of the break up of Piton de la Fournaise volcano, predating the formation of the four large calderas. The second landslide, which occurred 150,000 years ago and is considered to be less extensive, has carried away the entire southern flank of the Rivière des Remparts caldera.  相似文献   
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A clear model of structures and associated stress fields of a volcano can provide a framework in which to study and monitor activity. We propose a volcano-tectonic model for the dynamics of the summit of Piton de la Fournaise (La Reunion Island, Indian Ocean). The summit contains two main pit crater structures (Dolomieu and Bory), two active rift zones, and a slumping eastern sector, all of which contribute to the actual fracture system. Dolomieu has developed over 100 years by sudden large collapse events and subsequent smaller drops that include terrace formation. Small intra-pit collapse scars and eruptive fissures are located along the southern floor of Dolomieu. The western pit wall of Dolomieu has a superficial inward dipping normal fault boundary connected to a deeper ring fault system. Outside Dolomieu, an oval extension zone containing sub-parallel pit-related fractures extends to a maximum distance of 225 m from the pit. At the summit the main trend for eruptive fissures is N80°, normal to the north–south rift zone. The terraced structure of Dolomieu has been reproduced by analogue models with a roof to width ratio of approximately 1, suggesting an original magma chamber depth of about 1 km. Such a chamber may continue to act as a storage location today. The east flank has a convex–concave profile and is bounded by strike-slip fractures that define a gravity slump. This zone is bound to the north by strike-slip fractures that may delineate a shear zone. The southern reciprocal shear zone is probably marked by an alignment of large scoria cones and is hidden by recent aa lavas. The slump head intersects Dolomieu pit and may slide on a hydrothermally altered layer known to be located at a depth of around 300 m. Our model has the summit activity controlled by the pit crater collapse structure, not the rifts. The rifts become important on the mid-flanks of the cone, away from pit-related fractures. On the east flank the superficial structures are controlled by the slump. We suggest that during pit subsidence intra-pit eruptions may occur. During tumescence, however, the pit system may become blocked and a flank eruption is more likely. Intrusions along the rift may cause deformation that subsequently increases the slump’s potential to deform. Conversely, slumping may influence the east flank stress distribution and locally control intrusion direction. These predictions can be tested with monitoring data to validate the model and, eventually, improve monitoring.  相似文献   
10.
Noble gas concentrations and isotopic compositions have been determined for four submarine volcanic glasses from the Valu Fa Ridge (VFR) in the southern Lau Basin. The samples are the least differentiated ones from this area, and they display enrichments in fluid-mobile elements similar to the nearby island arc. 3He/4He ratios are slightly below average MORB (6.8–7.8 times atmospheric), whereas Ne, Ar, Kr, and Xe have isotopic compositions very similar to air. Together with previously published data from the Valu Fa Ridge and other spreading segments in the Lau Basin, our data show a systematic latitudinal variation of increasing Ne, Ar, Kr, and Xe abundances from north to south as well as Ne and Ar isotopic compositions changing from MORB-like to atmosphere-like in the same direction. Moreover, isotopic compositions and noble gas abundances of the lavas correlate strongly with Ba/Nb ratios and H2O concentrations. Based on these observations and mass balance arguments, we propose that the atmospheric noble gases come from the subducting oceanic crust and are not due to shallow contamination with air dissolved in seawater or assimilation of old crust. Our data suggest that the noble gases released from the subducting slab are atmospheric and thus contain little or no solar He and Ne. In addition to the fact that ratios of He to heavy noble gases are small in aged ocean crust, He has possibly fractionated from the other noble gases due to its higher diffusivity, and thus He transport from the subducting slab into the mantle wedge is probably insignificant. We propose that the 3He/4He ratios lower than MORB observed in the VFR lavas result from radiogenic ingrowth of He in a highly depleted, and hence degassed, mantle wedge after the enrichment of U and Th released from the downgoing slab.  相似文献   
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