Surface chemistry and reactivity of plant phytoliths in aqueous solutions

In order to better understand the reactivity of plant phytoliths in soil solutions, we determined the solubility, surface properties (electrophoretic mobilities and surface charge) and dissolution kinetics of phytoliths extracted from fresh biomass of representative plant species (larch tree and elm, horsetail, fern, and four grasses) containing significant amount of biogenic silica. The solubility product of larch, horsetail, elm and fern phytoliths is close to that of amorphous silica and soil bamboo phytoliths. Electrophoretic measurements yield isoelectric point pH_IEP = 0.9, 1.1, 2.0 and 2.2 for four grasses, elm, larch and horsetail phytoliths respectively, which is very close to that of quartz or amorphous silica. Surface acid–base titrations allowed generation of a 2-pK surface complexation model (SCM) for larch, elm and horsetail phytoliths. Phytoliths dissolution rates, measured in mixed-flow reactors at far from equilibrium conditions at 1 ≤ pH ≤ 8, were found to be very similar among the species, and close to those of soil bamboo phytoliths. Mechanistic treatment of all plant phytoliths dissolution rates provided three-parameters equation sufficient to describe phytoliths reactivity in aqueous solutions:$R(\text{mol}/{\text{cm}}^2/\text{s})=6?{10}^{?16}?a_{\text{H+}}+5.0?{10}^{?18}+3.5?{10}^{?13}?a_{\text{OH}?}^{0.33}$Alternatively, the dissolution rate dependence on pH can be modeled within the concept of surface coordination theory assuming the rate proportional to concentration of > SiOH₂⁺, > SiOH⁰ and > SiO^? species. In the range of Al concentration from 20 to 5000 ppm in the phytoliths, we have not observed any correlation between their Al content and solubility, surface acid–base properties and dissolution kinetics.It follows from the results of this study that phytoliths dissolution rates exhibit a minimum at pH ～ 3. Mass-normalized dissolution rates are similar among all four types of plant species studied and these rates are an order of magnitude higher than those of typical soil clay minerals. The minimal half life time of larch and horsetail phytoliths in the interstitial soil solution ranges from 10–12 years at pH = 2–3 to < 1 year at pH above 6, comparable with mean residence time of phytoliths in soil from natural observations.     

Molecular and isotopic characterization of organic samples from the wreck of the Saint-Etienne merchant ship (XVIIIth century): Identification of pitch,fat, hair and sulfur

The wreck U Pezzo, excavated within the Saint Florent Gulf in northern Corsica was identified as the pink, Saint Etienne, a merchant ship which sank on January 31, 1769. In order to determine the composition of organic materials used to coat the hull or to waterproof different parts of the pink, a study of several samples, using molecular biomarker and carbon isotopic analysis, was initiated. The results revealed that the remarkable yellow coat, covering the outside planks of the ship’s bottom under the water line, is composed of sulfur, tallow (of ox and not of cetacean origin) and black pitch which corresponds to a mixture called “couroi” or “stuff”. Onboard ropes had been submitted to a tarring treatment with pitch. Hairs mixed with pitch were identified in samples collected between the two layers of the hull or under the sheathing planking. The study also provides a key model for weathering of pitch, as different degrees of degradation were found between the surface and the heart of several samples. Accordingly, molecular parameters for alteration were proposed. Furthermore novel mixed esters between terpenic and diterpenic alcohols and the free major fatty acids (C_14:0, C_16:0, C_18:0) were detected in the yellow coat.     

Two Cu–Co sulfide phases and contrasting fluid systems in the Katanga Copperbelt, Democratic Republic of Congo

The Katanga Copperbelt is the Congolese part of the well-known Central African Copperbelt, the largest sediment-hosted stratiform Cu–Co province on Earth. Petrographic examination of borehole samples from the Kamoto and Luiswishi mines in the Katanga Copperbelt recognized two generations of hypogene Cu–Co sulfides and associated gangue minerals (dolomite and quartz). The first generation is characterized by fine-grained Cu–Co sulfides and quartz replacing dolomite. The second generation is paragenetically later and characterized by coarse-grained Cu–Co sulfides and quartz overgrown and partly replaced by dolomite. Fluid inclusion microthermometric data were collected from two different types of fluid inclusions: type-I fluid inclusions (liquid + vapor) in the quartz of the first generation and type-II fluid inclusions (liquid + vapor + halite) in the quartz of the second generation. The microthermometric analyses indicate that the fluids represented by type-I and type-II fluid inclusions had very different temperatures and salinities and were not in thermal equilibrium with the host rock.Petrographic and microthermometric data indicate the presence of at least two main hypogene Cu–Co sulfide phases in the Katanga Copperbelt. The first is an early diagenetic typical stratiform phase, which produced fine-grained sulfides that are disseminated in the host rock and frequently concentrated in nodules and lenticular layers. This phase is related to a hydrothermal fluid with a moderate temperature (115 to 220 °C, or less if reequilibration of inclusions has occurred) and salinity (11.3 to 20.9 wt.% NaCl equiv.). The second hypogene Cu–Co phase produced syn-orogenic coarse-grained sulfides, which also occur disseminated in the host rock but mainly concentrated in a distinct type of stratiform nodules and layers and in stratabound veins and tectonic breccia cement. This second phase is related to a hydrothermal fluid with high temperature (270 to 385 °C) and salinity (35 to 45.5 wt.% NaCl equiv.).A review of available microthermometric and ore geochronological data of the Copperbelt in both the Democratic Republic of Congo and Zambia supports the regional presence of the two Cu–Co phases proposed in our study. Future geochemical analyses in the Copperbelt should take into account the presence of, at least, these two Cu–Co phases, their contrasting fluid systems and the possible overprint of the first phase by the second one.     

Quantifying the role of sandy–silty sediments in generating slope failures during earthquakes: example from the Algerian margin

The Algerian margin is a seismically active region, where during the last century, several large magnitude earthquakes took place. This study combines geotechnical and sedimentological data with numerical modelling to quantitatively assess the present-day slope stability of the Algerian margin. Geotechnical laboratory tests, such as cyclic triaxial tests, oedometric tests and vane shear tests were carried out on sediment cores collected on the study area. The liquefaction potential of a sediment column located about 30 km from the Boumerdès earthquake epicentre of 21st May 2003 was evaluated theoretically for an earthquake of M _w  = 6.8. We show that thin sand and silt beds such as those described on recovered sediment cores are the main cause of sediment deformation and liquefaction during earthquakes. Numerical calculations showed that the slope failure may occur during an earthquake characterised by a PGA in excess of 0.1g, and also that, under a PGA of 0.2g liquefaction could be triggered in shallow silty–sandy deposits. Moreover, comparison of the predicted slope failure with failure geometries inferred from seafloor morphology showed that earthquakes and subsequent mass movements could explain the present-day morphology of the study area.     

Thermal Infrared Spectra of Comet Hale-Bopp at Heliocentric Distances of 4 and 2.9 AU

We present 10 and 20 μm spectra of comet Hale-Bopp taken at UKIRT on 1996 June 20 and 1996 September 29.The 10 μm spectra clearly show a strong silicate feature with peaks at 10.0 and 11.2 μm. The 20 μm spectrum on September 29 has strong excess flux relative to a blackbody and a peak near 19μm, in good agreement with the ISO SWS spectra obtained a week later. However, the 20 μm spectrum on June 20 has significantly lower flux than would be expected based on a blackbody extrapolation from the flux at 12.5 μm. This revised version was published online in July 2006 with corrections to the Cover Date.     

Imaging of the Moho depth in Madagascar through the inversion of gravity data: geodynamic implications

Several E-W profiles of Bouguer anomalies across the Precambrian basement were inverted by applying a linearized inversion procedure in the spectral domain and using a simplified two-layer model with a crust-upper mantle interface of constant density contrast. From these inverted profiles, a contour map of Moho topography has been constructed which covers the area of exposed Precambrian basement in the eastern and central parts of the island. Such imaging of the Moho depth in particular exhibits a N20°E-trending zone of substantially thinned crust along the axis of the island. This parallels the east coast margin which resulted from the northward motion of India relative to Madagascar in the Upper Cretaceous. From combined analysis of geological, tectonic and metamorphic observations, this prominent crustal feature in the Precambrian basement of Madagascar is interpreted as the relic of continental lithospheric extension and thinning possibly related to Panafrican collapse tectonics on the eastern edge of the Mozambique belt. This extensional feature would have been reactivated only in part during the rifting and dislocation stages of the Madagascar and India continental blocks as evidenced by an axis of Cretaceous volcanism emphasized by the Ankaratra and Itasy massifs. Final separation nevertheless occurred further east, at the site of the east coast margin.     

Spiral Structures and Chaotic Scattering of Coorbital Satellites

The fractal nature of the transitions between two sets of orbits separated by heteroclinic or homoclinic orbits is well known. We analyze in detail this phenomenon in Hill's problem where one set of orbits corresponds to coorbital satellites exchanging semi-major axis after close encounter (horse-shoe orbits) and the other corresponds to orbits which do not exchange semi-major axis (passing-by orbits). With the help of a normalized approximation of the vicinity of unstable periodic orbits, we show that the fractal structure is intimately tied to a special spiral structure of the Poincaré maps. We show that each basin is composed of a few well behaved areas and of an infinity of intertwined tongues and subtongues winding around them. This behaviour is generic and is likely to be present in large classes of chaotic scattering problems.This revised version was published online in October 2005 with corrections to the Cover Date.     

Impact of imperfect rainfall knowledge on the efficiency and the parameters of watershed models

It is crucial to analyze the sensitivity of watershed (rainfall-runoff) models to imperfect knowledge of rainfall input, in order to judge whether or not they are reliable and robust, especially if they are to be used for operational purposes. In this paper, a new approach to sensitivity analysis is proposed, based on a comparison between the efficiency ratings and parameter values of the models and the quality of rainfall input estimate (GORE and BALANCE indexes, assessing the quality of rainfall time distribution and the total depth respectively). Data from three watersheds of increasing size (71, 1120, and 10700 km²), are used to test three watershed models of varying complexity (three-parameter GR3J model and six-parameter modified versions of TOPMODEL and IHACRES).

These models are able to cope with imperfect rainfall input estimates, and react to improvements in rainfall input accuracy by better performance and reduced variability of efficiency. Two different types of model behavior were identified: the models either benefit from improved rainfall data by producing more consistent parameter values, or they are unable to take advantage of the improvements. Although the watershed size seems to be immaterial, the smaller watersheds appear to need more precise areal rainfall estimates (a higher concentration of raingages) to ensure good modeling results.