Early Paleozoic Structural and Metamorphic Evolution of Western Sierra de San Luis (Argentina), in Relation to Cuyania Accretion

Structural, metamorphic and isotopic data obtained from the Nogoli Metamorphic Complex of western Sierra de San Luis indicate that the Early Paleozoic Famatinian Orogeny overprinted an already structured and metamorphosed older basement. The older geological features are relict NW trending fabric associated with high-grade (amphibolite facies) regional metamorphism preserved within thin strips of schists and paragneisses and in the core of mafic to ultramafic lenses. Arc magmatism, medium P (Barrovian type)/high T (amphibolite to granulite facies) regional metamorphism and penetrative NNE to NE trending foliation are related to the building of the Famatinian orogenic belt. The P-T conditions of the Famatinian prograde metamorphism reached a pressure peak of ca. 8 kb, with a thermal peak from -750°C up to -820°C. U-Pb conventional and chemical dating and Ar-Ar plateau ages constrain the peak of the main orogenic phase related to the Famatinian belt to 470–457 Ma (Early to Mid-Ordovician). Greenschist facies retrograde metamorphism closely associated with shear zones and secondary Ar-Ar plateau and Sm-Nd ages suggest that a late to post-orogenic phase of the Famatinian belt was active at least since -445 Ma. This phase continued during the Silurian to Late Devonian times through multiple reactivation of early shear zones. The Famatinian Orogeny reset a previous thermal history and therefore, the timing of the relict fabric could not be constrained conclusively with radiometric dates. Despite this difficulty, a range of 520 to 490 Ma suggests some inheritance from Pampean events registered by the older NW-SE fabric. The Early to Mid-Ordovician regional metamorphism and ductile deformation of the western Sierra de San Luis is interpreted as the orogenic effects of the collision of the allochthonous Cuyania terrane with the autochthonous proto-Pacific margin of Gondwana during the Famatinian Orogeny.     

Magma degassing and basaltic eruption styles: a case study of 2000 year BP Xitle volcano in central Mexico

To investigate the relationship between volatile abundances and eruption style, we have analyzed major element and volatile (H₂O, CO₂, S) concentrations in olivine-hosted melt inclusions in tephra from the 2000 yr BP eruption of Xitle volcano in the central Trans-Mexican Volcanic Belt. The Xitle eruption was dominantly effusive, with fluid lava flows accounting for 95% of the total dense rock erupted material (1.1 km³). However, in addition to the initial, Strombolian, cinder cone-building phase, there was a later explosive phase that interrupted effusive activity and deposited three widespread ash fall layers. Major element compositions of olivine-hosted melt inclusions from these ash layers range from 52 to 58 wt.% SiO₂, and olivine host compositions are Fo_84–86. Water concentrations in the melt inclusions are variable (0.2–1.3 wt.% H₂O), with an average of 0.45±0.3 (1σ) wt.% H₂O. Sulfur concentrations vary from below detection (50 ppm) to 1000 ppm but are mostly ≤200 ppm and show little correlation with H₂O. Only the two inclusions with the highest H₂O have detectable CO₂ (310–340 ppm), indicating inclusion entrapment at higher pressures (700–900 bars) than for the other inclusions (≤80 bars). The low and variable H₂O and S contents of melt inclusions combined with the absence of less soluble CO₂ indicates shallow-level degassing before olivine crystallization and melt inclusion formation. Olivine morphologies are consistent with the interpretation that most crystallization occurred rapidly during near-surface H₂O loss. During cinder cone eruptions, the switch from initial explosive activity to effusive eruption probably occurs when the ascent velocity of magma becomes slow enough to allow near-complete degassing of magma at shallow depths within the cone as a result of buoyantly rising gas bubbles. This allows degassed lavas to flow laterally and exit near the base of the cone while gas escapes through bubbly magma in the uppermost part of the conduit just below the crater. The major element compositions of melt inclusions at Xitle show that the short-lived phase of renewed explosive activity was triggered by a magma recharge event, which could have increased overpressure in the storage reservoir beneath Xitle, leading to increased ascent velocities and decreased time available for degassing during ascent.     

Uptake of dissolved Cd by biogenic and abiogenic aragonite: a comparison with sorption onto calcite

The uptake of Cd²⁺ by aragonite and calcite is investigated by combining macroscopic measurements with some qualitative sorption experiments performed in a hydrogel medium. Both biogenic and abiogenic aragonites were studied in order to evaluate the process on materials with different textures. Assuming that sorption occurs by surface precipitation of metal-bearing solids, the gel produces a drastic decrease in the nucleation density, which allows for the precipitation of crystallites that are large enough to be analysed by scanning electron microscopy and characterized by glancing-incidence X-ray techniques. The macroscopic study reveals that aragonite is a powerful sorbent for cadmium in aqueous environments. Microscopic observations indicate that cadmium is sorbed onto aragonite by surface precipitation of (Cd, Ca)CO₃ solid solutions with a calcite-type structure. The precipitating individuals grow randomly oriented on the surface to reach sizes in the micrometre range. As a consequence, the concentration of cadmium in the aqueous solution decreases dramatically to values controlled by the low solubility of the cadmium-rich end member. This mechanism involves simultaneous dissolution-crystallization and is the same for both abiogenic and biogenic aragonites, the only difference being a result of the higher specific surface area of the biogenic starting material. Long-term uptake of cadmium by calcite occurs through a similar dissolution-crystallization mechanism, the final outcome being virtually the same, that is, surface precipitation of (Cd,Ca)CO₃ solid solutions. In this case, however, substrate and precipitate are isostructural and the process occurs by oriented overgrowth of thin lamellar crystallites, which spread to quickly cover the surface by a layer a few nanometers thick. This epitaxial layer armors the substrate from further dissolution, so that the process stops when only a small amount of cadmium has been removed from the fluid. As a result, the “sorption capacity” of calcite is considerably lower than that of aragonite. The study illustrates reaction pathways and “partial” equilibrium endpoints in surface-precipitation processes involving solid solutions.     

Oxidative dissolution of pyritic sludge from the Aznalcóllar mine (SW Spain)

As a result of the collapse of a mine tailing dam, a large extension of the Guadiamar valley was covered with a layer of pyritic sludge. Despite the removal of most of the sludge, a small amount remained in the soil, constituting a potential risk of water contamination. The kinetics of the sludge oxidation was studied by means of laboratory flow-through experiments at different pH and oxygen pressures. The sludge is composed mainly of pyrite (76%), together with quartz, gypsum, clays, and sulphides of zinc, copper, and lead. Trace elements, such as arsenic and cadmium, also constitute a potential source of pollution. The sludge is fine grained (median of 12 μm) and exhibits a large surface (BET area of 1.4±0.2 m² g⁻¹).

The dissolution rate law of sludge obtained is r=10^{−6.1(±0.3)} [O₂(aq)]^0.41(±0.04) a_H+^0.09(±0.06) g_sludge m⁻² s⁻¹ (22 °C, pH=2.5–4.7). The dissolution rate law of pyrite obtained is r=10^{−7.8(±0.3)} [O₂(aq)]^0.50(±0.04) a_H+^0.10(±0.08) mol m⁻² s⁻¹ (22 °C, pH=2.5–4.7). Under the same experimental conditions, sphalerite dissolved faster than pyrite but chalcopyrite dissolves at a rate similar to that of pyrite. No clear dependence on pH or oxygen pressure was observed. Only galena dissolution seemed to be promoted by proton activity. Arsenic and antimony were released consistently with sulphate, except at low pH conditions under which they were released faster, suggesting that additional sources other than pyrite such as arsenopyrite could be present in the sludge. Cobalt dissolved congruently with pyrite, but Tl and Cd seemed to be related to galena and sphalerite, respectively.

A mechanism for pyrite dissolution where the rate-limiting step is the surface oxidation of sulphide to sulphate after the adsorption of O₂ onto pyrite surface is proposed.     

Strontium,SO42−/Cl− and Mg2+/Ca2+ ratios as tracers for the evolution of seawater into coastal aquifers: the example of Castell de Ferro aquifer (SE Spain)

The strontium content and the SO₄^2?/Cl^? and Mg²⁺/Ca²⁺ ratios were used as natural tracers of the residence time of seawater intrusion into the Castell de Ferro aquifer. Analysis of these parameters indicated the existence of two principal flowpaths in the aquifer. The first flows through the eastern part of the aquifer, through the karstified Castell de Ferro massif; it accommodates a larger and more rapid flow, so that the residence time is shorter, leading to lower SO₄²⁺/Cl^? ratios, lower Sr²⁺ content and higher Mg²⁺/Ca²⁺ ratios. The second flowpath is in the western sector, and flows exclusively through alluvial deposits; the flow here is slower, particularly that flowing towards the sea. Thus the residence time of the water here will be longer and there is scant flushing of the intruded seawater; this is manifested in the high Sr²⁺ content, high SO₄²⁺/Cl^? and low Mg²⁺/Ca²⁺ ratios. To cite this article: P. Pulido-Leboeuf et al., C. R. Geoscience 335 (2003).     

Estimation of chlorophyll fluorescence under natural illumination from hyperspectral data

This paper reports a series of laboratory and field measurements of spectral reflectance under artificial and natural light conditions which demonstrate that effects of natural chlorophyll fluorescence are observable in the reflectance red edge spectral region. These are results from the progress made to link physiologically-based indicators to optical indices from hyperspectral remote sensing in the Bioindicators of Forest Sustainability Project. This study is carried out on twelve sites of Acer saccharum M. in the Algoma Region, Ontario (Canada), where field measurements, laboratory-simulation experiments, and hyperspectral CASI imagery have been carried out in 1997, 1998, 1999 and 2000 campaigns. Leaf samples from the study sites have been used for reflectance and transmittance measurements with the Li-Cor Model 1800 integrating sphere apparatus coupled to an Ocean Optics Model ST1000 fibre spectrometer in which the same leaves are illuminated alternatively with and without fluorescence-exciting radiation. A study of the diurnal change in leaf reflectance spectra, combined with fluorescence measurements with the PAM-2000 Fluorometer show that the difference spectra are consistent with observed diurnal changes in steady-state fluorescence. Small canopies of Acer saccharum M. have been used for laboratory measurements with the CASI hyperspectral sensor, and under natural light conditions with a fibre spectrometer in diurnal trials, in which the variation of measured reflectance is shown experimentally to be consistent with a fluorescence signature imposed on the inherent leaf reflectance signature. Such reflectance changes due to CF are measurable under natural illumination conditions, although airborne experiments with the CASI hyperspectral sensor produced promising but less convincing results in two diurnal experiments carried out in 1999 and 2000, where small variations of reflectance due to the effect of CF were observed.     

Mechanical aspects of thrust faulting driven by far-field compression and their implications for fold geometry

In this paper we present a mechanical model that intends to captures the kinematical aspects of thrust fault related folds induced by regional-scale far-field contraction. Fold shapes may be the only surface evidence of the geometry of underlying faults, so complex fault interactions are assessed in terms of how they influence fold geometry. We use the finite element method to model the fold and finite deformation frictional contact to model the activation and evolution of slip throughout preexisting faults. From several simulated 2D fault patterns we infer how one may form an anticline similar to that observed at Sheep Mountain Anticline, Wyoming.     

Persistence of lutetium disilicate

RE₂Si₂O₇ is one of the final products of the chemical interaction of radioactive cation simulators and the silicates used in the engineered barrier of deep geological repositories. The aim of this paper is to study the chemical and structural behaviour of Lu₂Si₂O₇ (Lu as actinide tripositive state simulator) in several different chemical systems. The conditions expected at the repositories are simulated in the laboratory with solutions of different compositions and pH. Both the solid products and remnant solutions were analyzed using techniques that give information on the short- and long-range structural order. The results show good stability of Lu₂Si₂O₇, under the studied conditions, and, therefore, encapsulation of the radioactive actinide cations as a disilicate phase could be considered a viable method to ensure the long-term safety of the repositories.