Natural attenuation of TCE, As, Hg linked to the heterogeneous oxidation of Fe(II): an AFM study

Hydrous ferric oxide (HFO) colloids formed, in strictly anoxic conditions upon oxidation of Fe²⁺ ions adsorbed on mineral surface, were investigated under in situ conditions by contact mode atomic force microscopy (AFM). Freshly cleaved and acid-etched large single crystals of near endmember phlogopite were pre-equilibrated with dissolved Fe(II) and then reacted with Hg(II), As(V) and trichlorethene (TCE)-bearing solutions at 25 °C and 1 atm. HFO structures are found to be of nanometer scale. The As(V)–Fe(II) and Hg(II)–Fe(II) reaction products are round (25 nm) microcrystallites located predominantly on the layer edges and are indicative of an accelerated Fe(II) oxidation rate upon formation of Fe(II) inner sphere surface complexes with the phyllosilicate edge surface sites. On the other hand, TCE–Fe(II)–phlogopite reaction products are needle-shaped (45 nm long) particles located on the basal plane along the Periodic Bond Chains (PCBs) directions. Experiments with additions of sodium chloride confirm the importance of the Fe(II) adsorption step in the control of the overall heterogeneous Fe(II)–TCE electron transfer reaction.

Kinetic measurements at the nanomolar level of Hg° formed upon reduction of Hg(II) by Fe(II) in presence of phlogopite particles provide further convincing evidence for reduction of Hg(II)_aq coupled to the oxidation of Fe(II) adsorbed at the phlogopite–fluid interface, and indicate that sorption of Fe(II) to mineral surfaces enhances the reduction rate of Hg(II) species. The Hg(II) reduction reaction follows a first-order kinetic law. Under our experimental conditions, which were representative of many natural systems, 80% of the mercury is transferred to the atmosphere as Hg° in less than 2 h.

The reduction of a heavy metal (Hg), a toxic oxyanion (arsenate ion) and a chlorinated solvent (TCE) thus appear to be driven by the high reactivity of adsorbed Fe(II). This is of environmental relevance since these three priority pollutants are that way reductively transformed to a volatile, an immobilizable and a biodegradable species, respectively. Such kinetic data and reaction pathways are important in the evaluation of natural evaluation scenarios, in the optimization of Fe(II)/mineral mixtures as reductants in technical systems, and in general, in predicting the fate and transport of pollutants in natural systems.     

Integration of local participatory and regional planning: A GIS data aggregation procedure

This paper presents an approach for GIS integrating local participatory land management information used for regional planning, and contributing to a bottom-up approach to land use planning. In participatory planning, the integration between local and regional levels should facilitate the communication and co-operation among the parties at both levels, for an efficient use of available resources. For coherently linking these two levels it is necessary to transform the data produced at one level, in order to be usable by the other. This transformation consists of a spatial procedure, which allows scaling-up the local participatory rural appraisal (PRA) information for regional purposes and scaling down the regional information for local use, using a GIS. Such an integration procedure is presented and discussed using data from a case study in south-western Burkina Faso.     

Strain analysis of a shear zone in a granodiorite

A ductile shear zone in a late Precambrian granodiorite, from the Rouergue (southwest part of the French Massif Central) has been studied.A single episode of deformation is responsible for the formation of a foliation and a well-defined lineation which are localized into an elongated zone, a few decimeters wide.The strain features can be attributed to a simple-shear mechanism (Ramsay and Graham, 1970), so that the main parameters of the deformation are defined.At stages of increasing deformation, the quartz isotropic sub-fabric of the undeformed host rock is progressively transformed into an anisotropic fabric composed of a single oblique girdle while the subgrain size progressively decrease and the dislocation density remains constant. It is suggested that the gliding planes of quartz are the basal plane (0001) and a predominant prismatic plane 101̄0 the slip directions may be a for both glide-planes.The results obtained in this investigation provide a basis for a high voltage electron microscope (H.V.E.M.) study which shows that the fabrics development may be related to dislocation processes. The difference of strain rates in the host rock and in the shear zone is calculated from the dislocation microstructures.     

Japan Sea: a pull-apart basin?

Recent field work in the Hokkaido Central Belt and marine geology studies along the eastern margin of Japan Sea in addition to previously published data lead us to propose a new model of opening of the Japan Sea. The synthesis of both on-land and offshore structural data gives new constraints about the structural evolution of the system. The rhombohedral shape of the Japan Basin and the particular tectonic behaviour of the margins on both east and west sides can be explained by an early Eo-Oligocene rifting of a pull-apart basin accommodated along two large right-lateral shear zones, east of Korea and west of northeast Japan and Sakhalin. It is followed, during Upper Oligocene/Lower Miocene, by the main opening of the Japan Basin as a mega pull-apart. Then a back-arc spreading probably related to the subduction process, induced the creation of the Yamato and Tsushima Basins at the end of Lower Miocene and in Middle Miocene. Clockwise rotation of southwest Japan larger than 20° or major bending of Honshu mainland deduced from paleomagnetic studies is unlikely at this time. Since 1 or 2 My B.P. to Present, compression prevails along the eastern margin of the Japan Sea. The generation of marginal basins as pull-apart basins along intracontinental strike-slip faults is a mechanism which has been proposed by other authors concerning the South China Sea, the question then is whether the fragmentation of the Asiatic continent is an intracontinental deformation related process as proposed here or a subduction related one.     

Evolution qualitative à long terme des rotifères du Lac Léman

Seventy-five species and lower taxonomic units of rotifers have been identified in Lake Geneva (= lac Léman); seven species and one form are new for the lake. When using indicators of trophic conditions, the qualitative composition of the biocenosis is still dominated by oligo-mesotrophic lake indicators, mixed with eutrophic and oligotrophic ones. However the rotifer biocenosis has not yet reached a steady state.

     

Optimization framework for calibration of constitutive models enhanced by neural networks

A two‐level procedure designed for the estimation of constitutive model parameters is presented in this paper. The neural network (NN) approach at the first level is applied to achieve the first approximation of parameters. This technique is used to avoid potential pitfalls related to the conventional gradient‐based optimization techniques, considered here as a corrector that improves predicted parameters. The feed‐forward NN (FFNN) and the modified Gauss–Newton algorithms are briefly presented. The proposed framework is verified for the elasto‐plastic modified Cam Clay model that can be calibrated based on standard triaxial laboratory tests, i.e. the isotropic consolidation test and the drained compression test. Two different formulations of the input data to the NN, enhanced by a dimensional reduction of experimental data using principal component analysis, are presented. The determination of model characteristics is demonstrated, first on numerical pseudo‐experiments and then on the experimental data. The efficiency of the proposed approach by means of accuracy and computational effort is also discussed. Copyright © 2008 John Wiley & Sons, Ltd.     

Seismically induced shale diapirism: the Mine d’Or section,Vilaine estuary,Southern Brittany

The Pénestin section (southern Brittany) presents large regular undulations, commonly interpreted as evidence of periglacial pingos. It is an upper Neogene palaeoestuary of the Vilaine River reactivated during the middle Quaternary (middle terrace). It is incised into a thick kaolinitic saprolite and deformed by saprolite diapirs. This paper presents the arguments leading to a mechanistic interpretation of the deformations at Pénestin. Neither recent transpressive tectonics nor diagnostic evidence of periglacial pingo have been found despite evidence for a late paleo-permafrost. The major deformational process is shale diapirism, initially triggered by co-seismic water supply, with further loading and lateral spreading on an already deformed and deeply weathered basement, which allowed the shale diapirism to develop. Deformations are favoured by the liquefaction of the saprolite and a seaward mass movement and recorded, rather distant, effects of an earthquake (c. 280 ka B.P.) resulting from the progressive subsidence of the southern Armorican margin. These deformations triggered by an earthquake are similar to those induced by classical shale diapirism. They are probably common in tectonically active continental environments with shallow water table.