Establishing constraints on groundwater ages with Cl,C, H,and noble gases: A case study in the eastern Paris basin,France

Groundwaters from the Tithonian/Kimmeridgian, Oxfordian and Upper Dogger aquifers, within the eastern part of the Paris basin (France), were characterised using ³H, ¹⁴C and ³⁶Cl, and noble gases tracers, to evaluate their residence times and determine their recharge period. This information is an important prerequisite to evaluating the confinement properties of the Callovo-Oxfordian clay formation sandwiched between the Oxfordian aquifer and the Dogger aquifer, currently being investigated by the French nuclear waste management agency (Andra) for radioactive waste disposal. Data presented in this paper are used to test 4 hypotheses.     

Hydrous ferric oxide precipitation in the presence of nonmetabolizing bacteria: Constraints on the mechanism of a biotic effect

We have used room temperature and cryogenic ⁵⁷Fe Mössbauer spectroscopy, powder X-ray diffraction (pXRD), mineral magnetometry, and transmission electron microscopy (TEM), to study the synthetic precipitation of hydrous ferric oxides (HFOs) prepared either in the absence (abiotic, a-HFO) or presence (biotic, b-HFO) of nonmetabolizing bacterial cells (Bacillus subtilis or Bacillus licheniformis, ∼10⁸ cells/mL) and under otherwise identical chemical conditions, starting from Fe(II) (10⁻², 10⁻³, or 10⁻⁴ mol/L) under open oxic conditions and at different pH (6-9). We have also performed the first Mössbauer spectroscopy measurements of bacterial cell wall (Bacillus subtilis) surface complexed Fe, where Fe(III) (10^−3.5-10^−4.5 mol/L) was added to a fixed concentration of cells (∼10⁸ cells/mL) under open oxic conditions and at various pH (2.5-4.3). We find that non-metabolic bacterial cell wall surface complexation of Fe is not passive in that it affects Fe speciation in at least two ways: (1) it can reduce Fe(III) to sorbed-Fe²⁺ by a proposed steric and charge transfer effect and (2) it stabilizes Fe(II) as sorbed-Fe²⁺ against ambient oxidation. The cell wall sorption of Fe occurs in a manner that is not compatible with incorporation into the HFO structure (different coordination environment and stabilization of the ferrous state) and the cell wall-sorbed Fe is not chemically bonded to the HFO particle when they coexist (the sorbed Fe is not magnetically polarized by the HFO particle in its magnetically ordered state). This invalidates the concept that sorption is the first step in a heterogeneous nucleation of HFO onto bacterial cell walls. Both the a-HFOs and the b-HFOs are predominantly varieties of ferrihydrite (Fh), often containing admixtures of nanophase lepidocrocite (nLp), yet they show significant abiotic/biotic differences: Biotic Fh has less intraparticle (including surface region) atomic order (Mössbauer quadrupole splitting), smaller primary particle size (magnetometry blocking temperature), weaker Fe to particle bond strength (Mössbauer center shift), and no six-line Fh (6L-Fh) admixture (pXRD, magnetometry). Contrary to current belief, we find that 6L-Fh appears to be precipitated directly, under a-HFO conditions, from either Fe(II) or Fe(III), and depending on Fe concentration and pH, whereas the presence of bacteria disables all such 6L-Fh precipitation and produces two-line Fh (2L-Fh)-like biotic coprecipitates. Given the nature of the differences between a-HFO and b-HFO and their synthesis condition dependences, several biotic precipitation mechanisms (template effect, near-cell environment effect, catalyzed nucleation and/or growth effect, and substrate-based coprecipitation) are ruled out. The prevailing present view of a template or heterogeneous nucleation barrier reduction effect, in particular, is shown not to be the cause of the large observed biotic effects on the resulting HFOs. The only proposed mechanism (relevant to Fh) that is consistent with all our observations is coprecipitation with and possible surface poisoning by ancillary bacteriagenic compounds. That bacterial cell wall functional groups are redox active and the characteristics of biotic (i.e., natural) HFOs compared to those of abiotic (i.e., synthetic) HFOs have several possible biogeochemical implications regarding Fe cycling, in the photic zones of water columns in particular.     

The 1905 Chamonix earthquakes: active tectonics in the Mont Blanc and Aiguilles Rouges massifs

Linking earthquakes of moderate size to known tectonic sources is a challenge for seismic hazard studies in northwestern Europe because of overall low strain rates. Here we present a combined study of macroseismic information, tectonic observations, and seismic waveform modelling to document the largest instrumentally known event in the French northern Alps, the April 29, 1905, Chamonix earthquake. The moment magnitude of this event is estimated at M_w 5.3 ± 0.3 from records in Göttingen (Germany) and Uppsala (Sweden). The event of April 29 was followed by several afterschocks and in particular a second broadly felt earthquake on August 13, 1905. Macroseismic investigations allow us to favour a location of the epicentres 5–10 km N–NE of Chamonix. Tectonic analysis shows that potentially one amongst several faults might have been activated in 1905. Among them the right lateral strike-slip fault responsible for the recent 2005 M_w = 4.4 Vallorcine earthquake and a quasi-normal fault northeast of the Aiguilles Rouges massif are the most likely candidates. Discussion of tectonic, macroseismic, and instrumental data favour the normal fault hypothesis for the 1905 Chamonix earthquake sequence.     

Active faulting in the western Pyrénées (France): Paleoseismic evidence for late Holocene ruptures

We have identified a 50-km-long active fault scarp, called herewith the Lourdes Fault, between the city of Lourdes and Arette village in the French Pyrénées. This region was affected by large and moderate earthquakes in 1660 (Io = VIII–IX, MSK 64,), in 1750 (Io = VIII, MSK 64) and in 1967 (M_d = 5.3, Io = VIII, MSK 64). Most earthquakes in this area are shallow and the few available focal mechanism solutions do not indicate a consistent pattern of active deformation. Field investigations in active tectonics indicate an East–West trending and up to 50-m-high fault scarp, in average, made of 3 contiguous linear fault sub-segments. To the north, the fault controls Quaternary basins and shows uplifted and tilted alluvial terraces. Deviated and abandoned stream channels of the southern block are likely due to the successive uplift of the northern block of the fault. Paleoseismic investigations coupled with geomorphic studies, georadar prospecting and trenching along the fault scarp illustrate the cumulative fault movements during the late Holocene. Trenches exhibit shear contacts with flexural slip faulting and thrust ruptures showing deformed alluvial units in buried channels. ¹⁴C dating of alluvial and colluvial units indicates a consistent age bracket from two different trenches and shows that the most recent fault movements occurred between 4221 BC and 2918 BC. Fault parameters and paleoseismic results imply that the Lourdes Fault and related sub-segments may produce a M_W 6.5 to 7.1 earthquake. Fault parameters imply that the Lourdes Fault segment corresponds to a major seismic source in the western Pyrénées that may generate earthquakes possibly larger than the 1660 historical event.     

Mineralogical confirmation of a near-P:Fe = 1:2 limiting stoichiometric ratio in colloidal P-bearing ferrihydrite-like hydrous ferric oxide

We present a chemical and mineralogical explanation, derived from powder X-ray diffraction and Mössbauer spectroscopy measurements of synthetic samples, of the P:Fe = 1:2 limiting ratio of P incorporation (as PO₄) that was previously observed in natural aquatic oxic iron precipitates. The ⁵⁷Fe Mössbauer hyperfine parameters are interpreted with the help of state-of-the-art ab initio electronic structure calculations. We find that there is a strong tendency for solid solution P-Fe mixing in the P-bearing hydrous ferric oxide (P-HFO) aqueous coprecipitate system, interpreted as occurring between the P-free (ferrihydrite) end-member and an inferred P:Fe = 1:2 end-member beyond which P is not incorporated in the structure of the P-HFO solid. Up to and somewhat beyond the limiting end-member P:Fe ratio, all available P is scavenged by the coprecipitation reaction, suggesting strong P-Fe complexation in the precipitation-precursor dissolved species. The P-HFO solids are more stable (i.e., have stronger chemical bonds) than the P-free ferrihydrite end-member. We show that in coprecipitation the P specifically incorporates within the nanoparticle structure rather than complexing to the nanoparticle surface. Our results are relevant to the question of the mechanisms of coupling between the Fe and P cycles in natural aqueous environments and highlight a strong affinity between Fe and P in aqueous environments.     

Le front de la « Zone des marbres » (Pyrénées basco-cantabriques,Espagne), un chevauchement fini-crétacé fossilisé par les brèches marines paléocènes ?

The post-metamorphic breccias which underline the frontal overthrust of the ‘Marble Zone’ (Basque–Cantabrian Pyrenees, Province of Navarre, Spain), interpreted by P. Lamare as ‘mylonites’, correspond to sedimentary breccias of submarine canyon, filling former incised valleys dug within the metamorphic Jurassic/Early Cretaceous carbonates already folded and cleaved (Pyrenean Cretaceous tectorogen). Associated to microrhythmic hemipelagites containing Danian–Selandian planktonic foraminifera from the P1c–P3 interval, these breccias are now assigned to Palaeocene. Stratified and horizontal, they seal Late-Cretaceous structures, of which the overthrusting front of the ‘Marble Zone’ could be the principal regional element.