Sulfur isotope measurement of sulfate and sulfide by high-resolution MC-ICP-MS

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.     

Calcium isotope (δCa) fractionation along hydrothermal pathways, Logatchev field (Mid-Atlantic Ridge, 14°45′N)

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 δ^44/40Ca_HydEnd of −0.95 ± 0.07‰ relative to seawater (SW) and a ⁸⁷Sr/⁸⁶Sr isotope ratio of 0.7034(4). We demonstrate that δ^44/40Ca_HydEnd is higher than that of the bedrock at the Logatchev field. From mass balance calculations, we deduce a δ^44/40Ca 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 δ^44/40Ca 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 Δ^44/40Ca = −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 δ^44/40Ca 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.     

Adaptive fisheries management in Vietnam: The use of indicators and the introduction of a multi-disciplinary Marine Fisheries Specialist Team to support implementation

Vietnam is in the process of introducing adaptive management based on indicators and time-series to manage its marine fisheries. The development of indicator-based frameworks for fisheries management has accelerated in recent years. This article describes the suite of indicators being suggested or used in Vietnam including the data-collection system. The Vietnamese approach is supported by an institutional structure consisting of a multi-disciplinary advisory system to facilitate the process of using indicators and to introduce knowledge-based management. The article concludes by identifying current problems and weaknesses and by providing suggestions for future improvement of the system.     

Microfabrics of calcite ultramylonites as records of coaxial and non-coaxial deformation kinematics: Examples from the Rocher de l'Yret shear zone (Western Alps)

Microfabrics were analysed in calcite mylonites from the rim of the Pelvoux massif (Western Alps, France). WNW-directed emplacement of the internal Penninic units onto the Dauphinois domain produced intense deformation of an Eocene-age nummulitic limestone under lower anchizone metamorphic conditions (slightly below 300 °C). Two types of microfabrics developed primarily by dislocation creep accompanied by dynamic recrystallisation in the absence of twinning. Coaxial kinematics are inferred for samples exhibiting grain shape fabrics and textures with orthorhombic symmetry. Their texture (crystallographic preferred orientation, CPO) is characterised by two c-axis maxima, symmetrically oriented at 15° from the normal to the macroscopic foliation. Non-coaxial deformation is evident in samples with monoclinic shape fabrics and textures characterised by a single oblique c-axis maximum tilted with the sense of shear by about 15°. From the analysis of suitably oriented slip systems for the main texture components under given kinematics it is inferred that the orthorhombic textures, which developed in coaxial kinematics, favour activity of <10–11> and <02–21> slip along the f and r planes, respectively, with minor contributions of basal-<a> slip. In contrast, the monoclinic textures, which developed during simple shear, are most suited for duplex <a> slip along the basal plane. The transition between the dominating slip systems for the orthorhombic and monoclinic microfabrics is interpreted to be due to the effects of dynamic recrystallisation upon texture development. Since oblique c-axis maxima documented in the literature are most often rotated not with but against the shear sense, calcite textures alone should not be used as unequivocal shear sense indicators, but need to be complemented by microstructural criteria such as shape preferred orientations, grain size estimates and amount of twinning.     

Comparative Seismic Risk Studies for German Earthquake Regions on the Basis of the European Macroseismic Scale EMS-98

Within the framework of recent research projects, basic tools for GIS-based seismic risk assessment technologies were developed and applied to the building stock and regional particularities of German earthquake regions. Two study areas are investigated, being comparable by the level of seismic hazard and the hazard-consistent scenario events (related to mean return periods of 475, 2475 and 10000 years). Significant differences exist with respect to the number of inhabitants, the grade and extent of urbanisation, the quality and quantity of building inventory: the case study of Schmölln in Eastern Thuringia seems to be representative for the majority of smaller towns in Germany, the case study of Cologne (Köln) stands for larger cities. Due to the similarities of hazard and scenario intensities, the considerable differences do not only require proper decisions concerning the appropriate methods and acceptable efforts, they enable conclusions about future research strategies and needs for disaster reduction management. Not least important, results can sharpen the focus of public interest. Seismic risk maps are prepared for different scenario intensities recognising the scatter and uncertainties of site-dependent ground motion and also of the applied vulnerability functions. The paper illustrates the impact of model assumptions and the step-wise refinements of input variables like site conditions, building stock or vulnerability functions on the distribution of expected building damage within the study areas. Furthermore, and in contrast to common research strategies, results support the conclusion that in the case of stronger earthquakes the damage will be of higher concentration within smaller cities like Schmölln due to the site-amplification potential and/or the increased vulnerability of the building stock. The extent of damage will be pronounced by the large number of masonry buildings for which lower vulnerability classes have to be assigned. Due to the effect of deep sedimentary layers and the composition of building types, the urban centre of Cologne will be less affected by an earthquake of comparable intensity.     

The eastern Tonale fault zone: a ‘natural laboratory’ for crystal plastic deformation of quartz over a temperature range from 250 to 700 °C

Near the eastern end of the Tonale fault zone, a segment of the Periadriatic fault system in the Italian Alps, the Adamello intrusion produced a syn-kinematic contact aureole. A temperature gradient from 250 to 700 °C was determined across the Tonale fault zone using critical syn-kinematic mineral assemblages from the metasedimentary host rocks surrounding deformed quartz veins. Deformed quartz veins sampled along this temperature gradient display a transition from cataclasites to mylonites (frictional–viscous transition) at 280±30 °C. Within the mylonites, zones characterized by different dynamic recrystallization mechanisms were defined: Bulging recrystallization (BLG) was dominant between 280 and 400 °C, subgrain rotation recrystallization (SGR) in the 400–500 °C interval, and the transition to dominant grain boundary migration recrystallization (GBM) occurred at 500 °C. The microstructures associated with the three recrystallization mechanisms and the transitions between them can be correlated with experimentally derived dislocation creep regimes. Bulk texture X-ray goniometry and computer-automated analysis of preferred [c]-axis orientations of porphyroclasts and recrystallized grains are used to quantify textural differences that correspond to the observed microstructural changes. Within the BLG- and SGR zones, porphyroclasts show predominantly single [c]-axis maxima. At the transition from the SGR- to the GBM zone, the texture of recrystallized grains indicates a change from [c]-axis girdles, diagnostic of multiple slip systems, to a single maximum in Y. Within the GBM zone, above 630±30 °C, the textures also include submaxima, which are indicative of combined basal a- and prism [c] slip.     

Post-mid-Cretaceous eastern North Sea evolution inferred from 3D thermo-mechanical modelling

The Late Cretaceous–Cenozoic evolution of the eastern North Sea region is investigated by 3D thermo-mechanical modelling. The model quantifies the integrated effects on basin evolution of large-scale lithospheric processes, rheology, strength heterogeneities, tectonics, eustasy, sedimentation and erosion.

The evolution of the area is influenced by a number of factors: (1) thermal subsidence centred in the central North Sea providing accommodation space for thick sediment deposits; (2) 250-m eustatic fall from the Late Cretaceous to present, which causes exhumation of the North Sea Basin margins; (3) varying sediment supply; (4) isostatic adjustments following erosion and sedimentation; (5) Late Cretaceous–early Cenozoic Alpine compressional phases causing tectonic inversion of the Sorgenfrei–Tornquist Zone (STZ) and other weak zones.

The stress field and the lateral variations in lithospheric strength control lithospheric deformation under compression. The lithosphere is relatively weak in areas where Moho is deep and the upper mantle warm and weak. In these areas the lithosphere is thickened during compression producing surface uplift and erosion (e.g., at the Ringkøbing–Fyn High and in the southern part of Sweden). Observed late Cretaceous–early Cenozoic shallow water depths at the Ringkøbing–Fyn High as well as Cenozoic surface uplift in southern Sweden (the South Swedish Dome (SSD)) are explained by this mechanism.

The STZ is a prominent crustal structural weakness zone. Under compression, this zone is inverted and its surface uplifted and eroded. Contemporaneously, marginal depositional troughs develop. Post-compressional relaxation causes a regional uplift of this zone.

The model predicts sediment distributions and paleo-water depths in accordance with observations. Sediment truncation and exhumation at the North Sea Basin margins are explained by fall in global sea level, isostatic adjustments to exhumation, and uplift of the inverted STZ. This underlines the importance of the mechanisms dealt with in this paper for the evolution of intra-cratonic sedimentary basins.