Speciation and thermodynamic properties for cobalt chloride complexes in hydrothermal fluids at 35-440 °C and 600 bar: An in-situ XAS study     

Weihua Liu  Stacey J. Borg  Denis Testemale  Barbara Etschmann  Jean-Louis Hazemann  Joël Brugger 《Geochimica et cosmochimica acta》2011,75(5):1227-1248

Aqueous Co(II) chloride complexes play a crucial role in cobalt transport and deposition in ore-forming hydrothermal systems, ore processing plants, and in the corrosion of special Co-bearing alloys. Reactive transport modelling of cobalt in hydrothermal fluids relies on the availability of thermodynamic properties for Co complexes over a wide range of temperature, pressure and salinity. Synchrotron X-ray absorption spectroscopy was used to determine the speciation of cobalt(II) in 0-6 m chloride solutions at temperatures between 35 and 440 °C at a constant pressure of 600 bar. Qualitative analysis of XANES spectra shows that octahedral species predominate in solution at 35 °C, while tetrahedral species become increasingly important with increasing temperature. Ab initio XANES calculations and EXAFS analyses suggest that in high temperature solutions the main species at high salinity (Cl:Co >> 2) is CoCl₄²⁻, while a lower order tetrahedral complex, most likely CoCl₂(H₂O)_2(aq), predominates at low salinity (Cl:Co ratios ∼2). EXAFS analyses further revealed the bonding distances for the octahedral Co(H₂O)₆²⁺ (^octCo-O = 2.075(19) Å), tetrahedral CoCl₄²⁻ (^tetCo-Cl = 2.252(19) Å) and tetrahedral CoCl₂(H₂O)_2(aq) (^tetCo-O = 2.038(54) Å and ^tetCo-Cl = 2.210(56) Å). An analysis of the Co(II) speciation in sodium bromide solutions shows a similar trend, with tetrahedral bromide complexes becoming predominant at higher temperature/salinity than in the chloride system. EXAFS analysis confirms that the limiting complex at high bromide concentration at high temperature is CoBr₄²⁻. Finally, XANES spectra were used to derive the thermodynamic properties for the CoCl₄²⁻ and CoCl₂(H₂O)_2(aq) complexes, enabling thermodynamic modelling of cobalt transport in hydrothermal fluids. Solubility calculations show that tetrahedral CoCl₄²⁻ is responsible for transport of cobalt in hydrothermal solutions with moderate chloride concentration (∼2 m NaCl) at temperatures of 250 °C and higher, and both cooling and dilution processes can cause deposition of cobalt from hydrothermal fluids.  相似文献   

Structural inversion and its controls : examples from the Alpine foreland and the French Alps     

Ralph Gillcrist  Mike Coward  Jean-Louis Mugnier 《Geodinamica Acta》2013,26(1):5-34

Abstract

Positive structural inversion involves the uplift of rocks on the hanging-walls of faults, by dip slip or oblique slip movements. Controlling factors include the strike and dip of the earlier normal faults, the type of normal faults — whether they were listric or rotated blocks, the time lapsed since extension and the amount of contraction relative to extension. Steeply dipping faults are difficult to invert by dip slip movements; they form buttresses to displacement on both cover detachments and on deeper level but gently inclined basement faults. The decrease in displacement on the hanging-walls of such steep buttresses leads to the generation of layer parallel shortening, gentle to tight folds — depending on the amount of contractional displacement, back-folds and back-thrust systems, and short-cut thrust geometries — where the contractional fault slices across the footwall of the earlier normal fault to enclose a “floating horse”. However, early steeply dipping normal faults readily form oblique to strike slip inversion structures and often tramline the subsequent shortening into particular directions.

Examples are given from the strongly inverted structures of the western Alps and the weakly inverted structures of the Alpine foreland. Extensional faulting developed during the Triassic to Jurassic, during the initial opening of the central Atlantic, while the main phases of inversion date from the end Cretaceous when spreading began in the north Atlantic and there was a change of relative motion between Europe and Africa. During the mid-Tertiary well over 100 km of Alpine shortening took place; Alpine thrusts, often detached along, or close to, the basement-cover interface, stacking the late Jurassic to Cretaceous sediments of the post-extensional subsidence phase. These high level detachments were joined and breached by lower level faults in the basement which, in the external zones of the western Alps, generally reactivated and rotated the earlier east dipping half-graben bounding faults. The external massifs are essentially uplifted half-graben blocks. There was more reactivation and stacking of basement sheets in the eastern part of this external zone, where the faults had been rotated into more gentle dips above a shallower extensional detachment than on the steeper faults to the west.

There is no direct relationship between the weaker inversion of the Alpine foreland and the major orogenic contraction of the western Alps; the inversion structures of southern Britain and the Channel were separated from the Alps by a zone of rifting from late Eocene to Miocene which affected the Rhone, Bresse and Rhine regions. Though they relate to the same plate movements which formed the Alps, the weaker inversion structures must have been generated by within plate stresses, or from those emanating from the Atlantic rather than the Tethyan margin.  相似文献   

Book reviews     

Djordje Grujic  Helmut Weissert  Jean-Louis Bodinier 《Geodinamica Acta》2013,26(5):249-252

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Miocene to Recent exhumation of the central Himalaya determined from combined detrital zircon fission-track and U/Pb analysis of Siwalik sediments, western Nepal     

Matthias Bernet  Peter van der Beek  Raphaël Pik†  Pascale Huyghe‡  Jean-Louis Mugnier‡  Erika Labrin‡  Adam Szulc§ 《Basin Research》2006,18(4):393-412

Fission‐track (FT) analysis of detrital zircon from synorogenic sediment is a well‐established tool to examine the cooling and exhumation history of convergent mountain belts, but has so far not been used to determine the long‐term evolution of the central Himalaya. This study presents FT analysis of detrital zircon from 22 sandstone and modern sediment samples that were collected along three stratigraphic sections within the Miocene to Pliocene Siwalik Group, and from modern rivers, in western and central Nepal. The results provide evidence for widespread cooling in the Nepalese Himalaya at about 16.0±1.4 Ma, and continuous exhumation at a rate of about 1.4±0.2 km Myr^?1 thereafter. The ～16 Ma cooling is likely related to a combination of tectonic and erosional activity, including movement on the Main Central thrust and Southern Tibetan Detachment system, as well as emplacement of the Ramgarh thrust on Lesser Himalayan sedimentary and meta‐sedimentary units. The continuous exhumation signal following the ～16 Ma cooling event is seen in connection with ongoing tectonic uplift, river incision and erosion of lower Lesser Himalayan rocks exposed below the MCT and Higher Himalayan rocks in the hanging wall of the MCT, controlled by orographic precipitation and crustal extrusion. Provenance analysis, to distinguish between Higher Himalayan and Lesser Himalayan zircon sources, is based on double dating of individual zircons with the FT and U/Pb methods. Zircons with pre‐Himalayan FT cooling ages may be derived from either nonmetamorphic parts of the Tethyan sedimentary succession or Higher Himalayan protolith that formerly covered the Dadeldhura and Ramgarh thrust sheets, but that have been removed by erosion. Both the Higher and Lesser Himalaya appear to be sources for the zircons that record either ～16 Ma cooling or the continuous exhumation afterwards.  相似文献   

Flow and nutrient transport in intermittent rivers: a modelling case-study on the Vène River using SWAT 2005     

Nanée Chahinian  Marie-George Tournoud  Jean-Louis Perrin  Bernadette Picot 《水文科学杂志》2013,58(2):268-287

Abstract

Intermittent rivers have a specific hydrological behaviour which also influences water quality dynamics. The objective of this work was to model the flow and water quality dynamics of a coastal Mediterranean intermittent river using the Soil and Water Assessment Tool (SWAT 2005). Flow, sediment, nitrogen and phosphorus transport were simulated on the Vène experimental catchment, France. The model was sequentially calibrated at sub-catchment scale and validated both at sub-catchment and catchment scales. A procedure for building the data records for the point sources is presented. The results indicate that, while the model produces good results for flow simulation, its performance for sediment transport is less satisfactory. This in turn impacts on the nutrient transport module. The reasons behind these shortcomings are analysed, taking into account the length of the data records, their distribution and the equations used in the SWAT model. The need for a thorough multi-objective model validation is illustrated.

Citation Chahinian, N., Tournoud, M.-G., Perrin, J.-L. & Picot, B. (2011) Flow and nutrient transport in intermittent rivers: a modelling case-study on the Vène River using SWAT 2005. Hydrol. Sci. J. 56(2), 268–287.  相似文献   

Long Wave Resonance in Tropical Oceans and Implications on Climate: the Atlantic Ocean     

Jean-Louis Pinault 《Pure and Applied Geophysics》2013,170(11):1913-1930

Based on the well established importance of long, non-dispersive baroclinic Kelvin and Rossby waves, a resonance of tropical planetary waves is demonstrated. Three main basin modes are highlighted through joint wavelet analyses of sea surface height (SSH) and surface current velocity (SCV), scale-averaged over relevant bands to address the co-variability of variables: (1) a 1-year period quasi-stationary wave (QSW) formed from gravest mode baroclinic planetary waves which consists of a northern, an equatorial and a southern antinode, and a major node off the South American coast that straddles the north equatorial current (NEC) and the north equatorial counter current (NECC), (2) a half-a-year period harmonic, (3) an 8-year sub-harmonic. Contrary to what is commonly accepted, the 1-year period QSW is not composed of wind-generated Kelvin and Rossby beams but results from the excitation of a tuned basin mode. Trade winds sustain a free tropical basin mode, the natural frequency of which is tuned to synchronize the excitation and the ridge of the QSWs. The functioning of the 1-year period basin mode is confirmed by solving the momentum equations, expanding in terms of Fourier series both the coefficients and the forcing terms. The terms of Fourier series have singularities, highlighting resonances and the relation between the resonance frequency and the wavenumbers. This ill-posed problem is regularized by considering Rayleigh friction. The waves are supposed to be semi-infinite, i.e. they do not reflect at the western and eastern boundaries of the basin, which would assume the waves vanish at these boundaries. At the western boundary the equatorial Rossby wave is deflected towards the northern antinode while forming the NECC that induces a positive Doppler-shifted wavenumber. At the eastern boundary, the Kelvin wave splits into coastal Kelvin waves that flow mainly southward to leave the Gulf of Guinea. In turn, off-tropical waves extend as an equatorially trapped Kelvin wave, being deflected off the western boundary. The succession of warm and cold waters transferred by baroclinic waves during a cycle leaves the tropical ocean by radiation and contributes to western boundary currents. The main manifestation of the basin modes concerns the variability of the NECC, of the branch of the South Equatorial Current (SEC) along the equator, of the western boundary currents as well as the formation of remote resonances, as will be presented in a future work. Remote resonances occur at midlatitudes, the role of which is suspected of being crucial in the functioning of subtropical gyres and in climate variability.  相似文献   

Influence of sample location and livestock numbers on Sporormiella concentrations and accumulation rates in surface sediments of Lake Allos, French Alps     

David Etienne  Bruno Wilhelm  Pierre Sabatier  Jean-Louis Reyss  Fabien Arnaud 《Journal of Paleolimnology》2013,49(2):117-127

Spores of coprophilous fungi, especially Sporormiella, are often well preserved in lake sediment cores. It has been hypothesized that such spores can be used to quantify past livestock abundance. The quantitative relationship between fungal spore abundance and livestock populations, however, is not well established, nor are the mechanisms of spore transport and deposition in lacustrine systems. Multiple cores from Lake Allos, a large high-elevation lake in the French Alps, were used to map the modern abundance of Sordaria and Sporormiella spores throughout the lake. We observed high spatial heterogeneity with respect to spore numbers. No correlation with the distance from shoreline was found. There was, however, a relation with distance from the two main lake inlets. These results were used to select two fungi-rich sediment cores to investigate grazing pressure over the last two centuries. Comparisons were made between spore influx and historic data on livestock densities in the catchment. A sharp decrease in Sporormiella influx ca. 1894–1895 was associated with a reported reduction in sheep in the Allos catchment at that time. Mean influx of Sporormiella decreased by a factor of three between the nineteenth and twentieth centuries, reflecting a reduction in the reported number of animals in the Lake Allos catchment, from 6,000 to 2,000. This study confirmed that Sporormiella spore abundance in lake sediments can be used as a proxy for catchment herbivore numbers in paleoecological reconstructions. Nevertheless, our data indicate that before spore accumulation can be used to infer past domestic herbivore density, one must understand the processes of coprophilous spore transfer from the catchment to the lake and the influence of core location on spore numbers in the sediment.  相似文献   

Anticipation of ENSO: what teach us the resonantly forced baroclinic waves     

Jean-Louis Pinault 《地球物理与天体物理流体动力学》2016,110(6):518-528

The El Niño-Southern Oscillation (ENSO) is characterized based on the date the events are mature. Their time lag defined relative to the central value of successive intervals of 4 years length, e.g. 01/1868–01/1872, 01/1872–01/1876 …, 01/1996–01/2000 … affects their evolution and, for a given amplitude, their variability. It specifies the dynamics of the quadrennial Quasi-Stationary Wave (QSW) in the tropical Pacific since ENSO always occurs at the end of the eastward phase propagation of that QSW. A third of events are unlagged with very low variability, SST anomalies being nearly concomitant between the extreme eastern and the central-eastern Pacific. A third of events are weakly lagged, in phase with the annual QSW, whose variability is much greater. Several months may elapse between the maximum SST anomalies east of the basin and along its equatorial central part. The last third of the events exhibits considerable variability, whether they are out of phase with the annual QSW or strongly lagged. The SST anomaly between 5°N and 20°N plays a key role in the maturation of the events out of phase. The events in phase (10% of the total population) are characterized by a negative SST anomaly in the central-eastern Pacific that reverses just before the maturation stage of ENSO. Sea water temperature 125 m deep in the central-eastern Pacific carries the earliest relevant information with a lead time of one year for forecasting the amplitude of unlagged ENSO while reporting how SST anomalies will develop until ENSO is fully developed. Besides, long-term forecast of the resumption of La Niña can be achieved accurately when weakly lagged events in phase with the annual QSW occur. The well differentiated typology of events vs. their time lag is the best clue to prove the leading role of the quadrennial QSW in the genesis of ENSO, while the related dynamic of the atmosphere ensues.  相似文献   

Long Wave Resonance in Tropical Oceans and Implications on Climate: The Pacific Ocean     

Jean-Louis Pinault 《Pure and Applied Geophysics》2016,173(6):2119-2145

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Causes and impacts of changes in the Arctic freshwater budget during the twentieth and twenty-first centuries in an AOGCM   总被引：2，自引：1，他引：1  

Olivier Arzel  Thierry Fichefet  Hugues Goosse  Jean-Louis Dufresne 《Climate Dynamics》2008,30(1):37-58

The fourth version of the atmosphere-ocean general circulation (AOGCM) model developed at the Institut Pierre-Simon Laplace (IPSL-CM4) is used to investigate the mechanisms influencing the Arctic freshwater balance in response to anthropogenic greenhouse gas forcing. The freshwater influence on the interannual variability of deep winter oceanic convection in the Nordic Seas is also studied on the basis of correlation and regression analyses of detrended variables. The model shows that the Fram Strait outflow, which is an important source of freshwater for the northern North Atlantic, experiences a rapid and strong transition from a weak state toward a relatively strong state during 1990–2010. The authors propose that this climate shift is triggered by the retreat of sea ice in the Barents Sea during the late twentieth century. This sea ice reduction initiates a positive feedback in the atmosphere-sea ice-ocean system that alters both the atmospheric and oceanic circulations in the Greenland-Iceland-Norwegian (GIN)-Barents Seas sector. Around year 2080, the model predicts a second transition threshold beyond which the Fram Strait outflow is restored toward its original weak value. The long-term freshening of the GIN Seas is invoked to explain this rapid transition. It is further found that the mechanism of interannual changes in deep mixing differ fundamentally between the twentieth and twenty-first centuries. This difference is caused by the dominant influence of freshwater over the twenty-first century. In the GIN Seas, the interannual changes in the liquid freshwater export out of the Arctic Ocean through Fram Strait combined with the interannual changes in the liquid freshwater import from the North Atlantic are shown to have a major influence in driving the interannual variability of the deep convection during the twenty-first century. South of Iceland, the other region of deep water renewal in the model, changes in freshwater import from the North Atlantic constitute the dominant forcing of deep convection on interannual time scales over the twenty-first century.  相似文献