Infrared study of the pyrolysis products of sporopollenin and lignite

The effect of pyrolysis at increasing temperature on sporopollenin, lignite and sporopollenin oxidized at 200°C has been investigated using measured infrared band absorption coefficients.Oxidation of sporopollenin in air at 200°C is marked by a decrease in the content of saturated hydrocarbon chains and a strong increase in the concentration of carboxylic acid groups.Pyrolysis of a thick bed of sporopollenin at increasing temperatures leads to the removal of a large proportion of oxygenated functions, before the removal of hydrocarbons. For lignite and oxidized sporopollenin, the loss of both types of functional groups extends over a broader temperature range. Reorganization of the carbonaceous residue at high temperature is hindered if a sufficiently low content of oxygenated functions, carbonyl and carboxyl as well as hydroxyl and ether groups, is not reached before the elimination of hydrocarbons.     

Fluvial incisions in the North‐Western Pyrenees (Aspe Valley): Dissection of a former planation surface and some tectonic implications

Dissected remnants of a high elevation low relief surface (HELRS) are encountered all along the Pyrenean range. All authors agree that the HELRS was shaped during the post‐shortening evolution of the belt, but doubt remains on its original elevation. Notably, whether a post‐shortening uplift event occurred after the generation of the Pyrenean planation surface is still debated. Based on a geomorphological study of the entrenchment of the Aspe River in the North‐Western Pyrenees, we describe a post‐Oligocene multi‐stage dissection of the HELRS linked to a regional post‐shortening uplift. Each incision stage is recorded by erosional triangular facets and associated stepped remnants of former smooth topographies. Compared analysis of patterns of incision in the Axial Zone and its northern border allows to evidence differential vertical motions. We discuss the forcing mechanism(s) that controlled this morphological evolution.     

Effet du vieillissement des céramiques poreuses sur leur capacité à évaluer la concentration de pesticide en solution

The soil solution sampling by ceramic cups allows pesticide transfer monitoring in the soil during long times. The ageing of material involves a bias in the sampling results. In laboratory, the comparison of two types of ceramic suction cups, new and installed in situ during four years, shows a modification of the hydrodynamic properties and a possible evolution of the adsorption capacity of the matrix. The passage rate, as well qualitative as quantitative, is better for the old material. Recommendations about site management are finally exposed. To cite this article: N. Domange et al., C. R. Geoscience 336 (2004).     

Superdense CO2 inclusions in Cretaceous quartz–stibnite veins hosted in low-grade Variscan basement of the Western Carpathians, Slovakia

CO₂ inclusions with density up to 1,197 kg m⁻³ occur in quartz–stibnite veins hosted in the low-grade Palaeozoic basement of the Gemericum tectonic unit in the Western Carpathians. Raman microanalysis corroborated CO₂ as dominant gas species accompanied by small amounts of nitrogen (<7.3 mol%) and methane (<2.5 mol%). The superdense CO₂ phase exsolved from an aqueous bulk fluid at temperatures of 183–237°C and pressures between 1.6 and 3.5 kbar, possibly up to 4.5 kbar. Low thermal gradients (∼12–13°C km⁻¹) and the CO₂–CH₄–N₂ fluid composition rule out a genetic link with the subjacent Permian granites and indicate an external, either metamorphogenic (oxidation of siderite, dedolomitization) or lower crustal/mantle, source of the ore-forming fluids.According to microprobe U–Pb–Th dating of monazite, the stibnite-bearing veins formed during early Cretaceous thrusting of the Gemeric basement over the adjacent Veporic unit. The 15- to 18-km depth of burial estimated from the fluid inclusion trapping PT parameters indicates a 8- to 11-km-thick Upper Palaeozoic–Jurassic accretionary complex overlying the Gemeric basement and its Permo-Triassic autochthonous cover.     

Finite volume approximation for an immiscible two-phase flow in porous media with discontinuous capillary pressure

We consider an immiscible incompressible two-phase flow in a porous medium composed of two different rocks so that the capillary pressure field is discontinuous at the interface between the rocks. This leads us to apply a concept of multivalued phase pressures and a notion of weak solution for the flow which have been introduced in Cancès and Pierre (SIAM J Math Anal 44(2):966–992, 2012). We discretize the problem by means of a numerical algorithm which reduces to a standard finite volume scheme in each rock and prove the convergence of the approximate solution to a weak solution of the two-phase flow problem. The numerical experiments show in particular that this scheme permits to reproduce the oil-trapping phenomenon.     

Petrogenesis of the amphibole-rich veins from the Lherz orogenic lherzolite massif (Eastern Pyrenees, France): a case study for the origin of orthopyroxene-bearing amphibole pyroxenites in the lithospheric mantle

The Lherz orogenic lherzolite massif (Eastern French Pyrenees) displays one of the best exposures of subcontinental lithospheric mantle containing veins of amphibole pyroxenites and hornblendites. A reappraisal of the petrogenesis of these rocks has been attempted from a comprehensive study of their mutual structural relationships, their petrography and their mineral compositions. Amphibole pyroxenites comprise clinopyroxene, orthopyroxene and spinel as early cumulus phases, with garnet and late-magmatic K₂O-poor pargasite replacing clinopyroxene, and subsolidus exsolution products (olivine, spinel II, garnet II, plagioclase). The original magmatic mineralogy and rock compositions were partly obscured by late-intrusive hornblendites and over a few centimetres by vein–wallrock exchange reactions which continued down to subsolidus temperatures for Mg–Fe. Thermobarometric data and liquidus parageneses indicate that amphibole pyroxenites started to crystallize at P ≥ 13 kbar and recrystallized at P < 12 kbar. The high Al^VI/Al^IV ratio (>1) of clinopyroxenes, the early precipitation of orthopyroxene and the late-magmatic amphibole are arguments for parental melts richer in silica but poorer in water than alkali basalts. Their modelled major element compositions are similar to transitional alkali basalt with about 1–3 wt% H₂O. In contrast to amphibole pyroxenites, hornblendites only show kaersutite as liquidus phase, and phlogopite as intercumulus phase. They are interpreted as crystalline segregates from primary basanitic magmas (mg=0.6; 4–6 wt% H₂O). These latter cannot be related to the parental liquids of amphibole pyroxenites by a fractional crystallization process. Rather, basanitic liquids mostly reused pre-existing pyroxenite vein conduits at a higher structural level (P ≤ 10 kbar). A continuous process of redox melting and/or alkali melt/peridotite interaction in a veined lithospheric mantle is proposed to account for the origin of the Lherz hydrous veins. The transitional basalt composition is interpreted in terms of extensive dissolution of olivine and orthopyroxene from wallrock peridotite by alkaline melts produced at the mechanical boundary layer/thermal boundary layer transition (about 45–50 km deep). Continuous fluid ingress allowed remelting of the deeper veined mantle to produce the basanitic, strongly volatiles enriched, melts that precipitated hornblendites. A similar model could be valid for the few orthopyroxene-rich hydrous pyroxenites described in basalt-hosted mantle xenoliths. Received: 15 September 1999 / Accepted: 31 January 2000     

Enregistrement de la variabilité hydroclimatique au cours des 6500 dernières années sur le littoral de Cabo Frio (Rio de Janeiro,Brésil)

This study concerns a core collected in Brejo do Espinho's lagoon from Cabo Frio littoral (Brazil) submitted to dry influence of local upwelling controlled by north-east trade winds from the South Atlantic and particularly strengthened during El Niño events. Diatoms study supported by sedimentological and isotopic analyses shows dry phases infrequent before 4000 yr, a highly variable climatic phase between 3600 and 2900 yr and from 2400 yr onward a dryness enhancement. To cite this article: B. Laslandes et al., C. R. Geoscience 338 (2006).     

Hydrothermal mixing,carbonate dissolution and sulfide precipitation in Mississippi Valley-type deposits

A large number of Mississippi Valley-Type (MVT) deposits are located within dissolution zones in carbonate host rocks. Some genetic models propose the existence of cavities generated by an earlier event such as a shallow karstification, that were subsequently filled with hydrothermal minerals. Alternative models propose carbonate dissolution caused by the simultaneous precipitation of sulfides. These models fail to explain either the deep geological setting of the cavities, or the observational features which suggest that the dissolution of carbonates and the precipitation of minerals filling the cavities are not strictly coeval. We present a genetic model inspired by the textural characteristics of MVT deposits that accounts for both the dissolution of carbonate and precipitation of sulfides and later carbonates in variable volumes. The model is based on the mixing of two hydrothermal fluids with a different chemistry. Depending on the proportion of the end members, the mixture dissolves and precipitates carbonates even though the two mixing solutions are both independently saturated in carbonates. We perform reactive transport simulations of mixing of a regional groundwater and brine ascending through a fracture, both saturated in calcite, but with different overall chemistries (Ca and carbonate concentrations, pH, etc). As a result of the intrinsic effects of chemical mixing, a carbonate dissolution zone, which is enhanced by acid brines, appears above the fracture, and another zone of calcite precipitation builds up between the cavity and the surrounding rock. Sulfide forms near the fracture and occupies a volume smaller than the cavity. A decline of the fluid flux in the fracture would cause the precipitation of calcite within the previously formed cavities. Therefore, dissolution of carbonate host rock, sulfide precipitation within the forming cavity, and later filling by carbonates may be part of the same overall process of mixing of fluids in the carbonate host rock.Editorial handling: C. Everett     

Dissolution of calcitic marble and dolomitic rock in high iron concentrated acid mine drainage: application to anoxic limestone drains

Oxidation of sulphide mining waste can generate acid mine drainage (AMD) that has the potential to seriously affect the ecosystems. Acid mine drainage is characterised by a high acidity, high concentrations of sulphates and metals. To reduce the environmental impacts due to AMD, neutralisation using limestone drains is an option proposed in the literature and used around the world. The present study focuses on the influence of the carbonate rock mineralogy and their particle size on the neutralising capacity. The tests were performed in two different anoxic conditions: in batch reactors, and in columns having a hydraulic retention time of 15?h. The results showed that the neutralisation capacity of calcite was more important than for dolomitic rock, and smaller particle size gave higher alkalinity production (fine calcite dissolved faster in contact with AMD). A characterization of metal precipitate in sludge and in limestone coating was performed and demonstrated that gypsum, lepidocrocite and goethite were the predominant secondary minerals to be formed. Finally, this study underlines that anoxic limestone drain cannot be used alone to treat high iron concentrated AMD.