Interpreting tracer breakthrough tailing in a conduit-dominated karstic aquifer

Breakthrough tailing has been observed during dye-tracing recovery tests in the Norville aquifer system (chalk), France. Karst-conduit flow and transport parameters were assessed using two different interpretative methods: the linear graphical method and the Chatwin method (implemented in the Qtracer2 program). The linear graphical method was used to model the observed tailing effects, which was explained by a second smaller delayed breakthrough curve. By comparing the results of tracer-test interpretation for the two methods, it was possible to relate the area of this second curve to the importance of turbulent flow in spring discharge. The more turbulent the flow, the less important the contribution of the second breakthrough curve and the tailing effect. The observed tailing could possibly be controlled by hydrodynamics to a greater extent than usually expected, the tailing effects being mostly attributed to diffusion phenomena. Tailing effects were expected to increase with discharge and the piezometric level, which would have resulted in overpressure in conduits, fissure flooding, etc. Instead, breakthrough tailing tended to disappear with increasing aquifer discharge, which would support the hypothesis of there being mostly hydrodynamic-controlled tailing effects instead of matrix- or fissure-diffusion.An erratum to this article can be found at     

Late Mesozoic compressional to extensional tectonics in the Yiwulüshan massif,NE China and its bearing on the evolution of the Yinshan–Yanshan orogenic belt: Part I: Structural analyses and geochronological constraints

With a cratonic nucleus, the North China Craton (NCC) experienced a complex tectonic evolution with multiphase compressional and extensional events during Mesozoic times. Along the northern part of the NCC, the Yinshan–Yanshan fold and thrust belt was a typical intraplate orogen. Jurassic and Cretaceous continental sedimentation, magmatism, widespread intraplate characterize the Yinshan–Yanshan orogenic belt. The geodynamic significance of these tectonic events is still in dispute. In the western part of the Liaoning province, the Yiwulüshan massif crops out at the eastern end of the Yinshan–Yanshan orogenic belt. The Yiwulüshan massif presents an elliptical domal shape with a NE–SW striking long axis. The structural evolution of this massif brings new insights for the understanding of the Mesozoic plutonic–tectonic history of the NCC. A multidisciplinary study involving structural geology, geochronology, Anisotropy of Magnetic Susceptibility (AMS) and gravity modeling have been carried out. The presentation of the new results splits into two parts. Part I (this paper) deals with field and laboratory structural observations, and presents the main geochronological results. The AMS, gravity modeling data will be provided in a companion paper (Part II). The early compressional deformation (D₁) corresponds to a Late Jurassic to Early Cretaceous southward thrusting. The subsequent deformation is related to the Early Cretaceous exhumation of the Yiwulüshan massif. A detailed structural analysis allows us to distinguish several deformation events (D₂, D₃, and D₄). The Cretaceous extensional structures, such as syntectonic plutons bounded by ductile normal faults, metamorphic core complexes, and half-graben basins are recognized in many places in East Asia. These new data from the Yiwulüshan massif constitute a link between Transbaikalia, Mongolia, North China and South China, indicating that NW–SE extensional Mesozoic tectonics occurred throughout the entire region.     

A New Reference Material for Tritium Organic Molecules in Sediment: Results of an International Intercomparison Exercise

Solid matrix ³H reference materials are challenging to prepare given the volatile nature of ³H and are often unrepresentative of the range of ³H forms that may be encountered during routine analysis. As a result, few ³H reference materials are currently available, undermining verification of analytical techniques for environmental ³H measurement. To address this, an International Working Group on Organically‐Bound Tritium Analysis determined to produce a tritium natural matrix reference material (NMRM). The reference material comprises marine sediment blended with sewage sludge contaminated with ³H‐organic species arising from authorised discharges from a radiopharmaceutical manufacturing site. Previous studies have demonstrated that the ³H species have persisted in the environment over three decades providing valuable supporting data to underpin the characterisation of the NMRM. The preparation and characterisation of the NMRM are described along with the subsequent application of the reference material in an international intercomparison exercise involving nineteen laboratories from nine countries. A reference value of 168 ± 22 Bq kg^?1 was derived from the data arising from the proficiency test.     

Presumed magnetic biosignatures observed in magnetite derived from abiotic reductive alteration of nanogoethite

The oriented chains of nanoscale Fe-oxide particles produced by magnetotactic bacteria are a striking example of biomineralization. Several distinguishing features of magnetite particles that comprise bacterial magnetosomes have been proposed to collectively constitute a biosignature of magnetotactic bacteria (Thomas-Keprta et al., 2001). These features include high crystallinity, chemical purity, a single-domain magnetic structure, well-defined crystal morphology, and arrangement of particles in chain structures. Here, we show that magnetite derived from the inorganic breakdown of nanocrystalline goethite exhibits magnetic properties and morphologies remarkably similar to those of biogenic magnetite from magnetosomes. During heating in reducing conditions, oriented nanogoethite aggregates undergo dehydroxylation and transform into stoichiometric magnetite. We demonstrate that highly crystalline single-domain magnetite with euhedral grain morphologies produced abiogenically from goethite meets several of the biogenicity criteria commonly used for the identi?cation of magnetofossils. Furthermore, the suboxic conditions necessary for magnetofossil preservation in sediments are conducive to the reductive alteration of nanogoethite, as well as the preservation of detrital magnetite originally formed from goethite. The findings of this study have potential implications for the identification of biogenic magnetite, particularly in older sediments where diagenesis commonly disrupts the chain structure of magnetosomes. Our results indicate that isolated magnetofossils cannot be positively distinguished from inorganic magnetite on the basis of their magnetic properties and morphology, and that intact chain structures remain the only reliable distinguishing feature of fossil magnetosomes.     

Chemical and textural equilibration of garnet during amphibolite facies metamorphism: The influence of coupled dissolution–reprecipitation

Metamorphic equilibration requires chemical communication between minerals and may be inhibited through sluggish volume diffusion and or slow rates of dissolution in a fluid phase. Relatively slow diffusion and the perceived robust nature of chemical growth zoning may preclude garnet porphyroblasts from readily participating in low‐temperature amphibolite facies metamorphic reactions. Garnet is widely assumed to be a reactant in staurolite‐isograd reactions, and the evidence for this has been assessed in the Late Proterozoic Dalradian pelitic schists of the Scottish Highlands. The 3D imaging of garnet porphyroblasts in staurolite‐bearing schists reveals a good crystal shape and little evidence of marginal dissolution; however, there is also lack of evidence for the involvement of either chlorite or chloritoid in the reaction. Staurolite forms directly adjacent to the garnet, and its nucleation is strongly associated with deformation of the muscovite‐rich fabrics around the porphyroblasts. “Cloudy” fluid inclusion‐rich garnet forms in both marginal and internal parts of the garnet porphyroblast and is linked both to the production of staurolite and to the introduction of abundant quartz inclusions within the garnet. Such cloudy garnet typically has a Mg‐rich, Mn‐poor composition and is interpreted to have formed during a coupled dissolution–reprecipitation process, triggered by a local influx of fluid. All garnet in the muscovite‐bearing schists present in this area is potentially reactive, irrespective of the garnet composition, but very few of the schists contain staurolite. The staurolite‐producing reaction appears to be substantially overstepped during the relatively high‐pressure Barrovian regional metamorphism reflecting the limited permeability of the schists in peak metamorphic conditions. Fluid influx and hence reaction progress appear to be strongly controlled by subtle differences in deformation history. The remaining garnet fails to achieve chemical equilibrium during the reaction creating distinctive patchy compositional zoning. Such zoning in metamorphic garnet created during coupled dissolution–reprecipitation reactions may be difficult to recognize in higher grade pelites due to subsequent diffusive re‐equilibration. Fundamental assumptions about metamorphic processes are questioned by the lack of chemical equilibrium during this reaction and the restricted permeability of the regional metamorphic pelitic schists. In addition, the partial loss of prograde chemical and textural information from the garnet porphyroblasts cautions against their routine use as a reliable monitor of metamorphic history. However, the partial re‐equilibration of the porphyroblasts during coupled dissolution–reprecipitation opens possibilities of mapping reaction progress in garnet as a means of assessing fluid access during peak metamorphic conditions.     

Leaching of lead metallurgical slags and pollutant mobility far from equilibrium conditions

Lead metallurgical slags are partially vitrified materials containing residual amounts of Zn, Pb, Cr, Cd and As. These hazardous materials are generally buried on heaps exposed to weathering. In this study, leaching behavior of lead blast furnace slags has been tested using pure water and open flow experiments. It appears that in such far from equilibrium and slightly acidic conditions, the main phase to be altered is the vitreous phase. As for lunar, basaltic and nuclear glasses, alkalis/proton exchanges prevail and lead to the formation of a non-protective altered layer enriched in Si, Fe and Al. The composition of the altered layer is quite constant except for Si whose concentration decreases towards the leachate interface. Owing to their sizes, micrometric Pb droplets are not always totally dissolved at the slag surface. Nevertheless, nanometric Pb droplets are instantaneously dissolved while a surrounding altered layer is formed. This leads to high Pb releases in open flow systems. Leachate chemistry and dissolution rates of the vitreous phase are closely comparable to previous leaching tests with basaltic and nuclear glasses in conditions far from equilibrium. Moreover, this study confirms that Fe is a stable element in such conditions.     

TEM evidence for intracellular accumulation of lead by bacteria in subsurface environments

We monitored near-surface atmospheric fallout (15-cm above ground) and soil solution (at 15, 35 and 55 cm below ground) derived nanoparticles over an 8-month period by collecting the particles directly onto TEM grids in anthropogenically-influenced (vineyard) and pristine (native forest) sites in France. Particle clusters trapped on the grid were selected randomly and individual particles were binned into eight different groups (euhedral clays, weathered clays, salts, oxi-hydroxides, bacteria, non-living organic matter, aggregates and undetermined). Bacteria represent 9–23% of the collected nanoparticle area (ave. 9.4% and 18% for two atmospheric collection sites and ave. 23% for soil infiltration samples). Bacteria were most often associated with non-living organic matter and comprised a variety of morpho-types. Interestingly, 45% of all the bacteria analyzed by transmission electron microscopy and electron dispersive spectroscopy (TEM-EDX) showed the presence of intracellular grains significantly enriched in lead and phosphorus. Intracellular sequestration of Pb into polyphosphate bodies has been observed in the laboratory, but this is the first observation of this phenomenon in a natural environment. Furthermore, this suggests that microbial-bound Pb may be an important transport mechanism in subsurface environments.     

HP–UHP metamorphism as an indicator of slab dip variations in the Alpine arc

HP/UHP and LT metamorphic units that commonly occur in the inner parts of mountain belts result from the subduction of continental and oceanic material, most often exhumed prior to continental collision. The prograde pressure–temperature history of HP–UHP rocks strongly depends on the convergence rate and on the subduction zone geometry. The maximum pressure recorded provides a proxy for the depth of shearing off and stacking of HP metamorphic nappes. A 2-D thermal model of continental subduction at lithospheric scale is used to compute the length and pressure peak of detached HP metamorphic units as a function of the slab dip angle and the convergence rate. Model results are applied to the metamorphic nappe pile of the inner Alps. A mean convergence rate of 1 cm/year during the subduction of the Briançonnais terrane is indicated by the paleogeographic reconstructions between 46 and 38 Ma. On this basis, the available petrological data and lengths of metamorphic units are used to compute the variations of the slab dip angle. The slab dip angle is shown to increase, from the northeast to the southwest, along the Alpine arc with estimated values of 20° for Suretta, 30–45° for Monte Rosa and Gran Paradiso, and 60° for Dora Maira. From Eocene to Oligocene times, the increase in slab dip angle is controlled by changes of buoyancy, due to the spatial configuration of the Valaisan trough and the incoming of crustal material within the subduction zone.     

Earthquakes in Switzerland and surrounding regions during 2006

This report of the Swiss Seismological Service summarizes the seismic activity in Switzerland and surrounding regions during 2006. During this period, 572 earthquakes and 91 quarry blasts were detected and located in the region under consideration. Of these earthquakes, two occurred in conjunction with the construction of the new Gotthard railway tunnel and 165 were induced artificially by the stimulation of a proposed geothermal reservoir beneath the city of Basel. With 20 events with M _L ≥ 2.5, five of which were artificially induced, the seismic activity in the year 2006 was far below the average over the previous 31 years. Nevertheless, six events were felt by the public, most prominently the strongest of the induced Basel events (M _L 3.4), which caused some non-structural building damage. Noteworthy are also the two earthquakes near Cortaillod (M _L 3.2), on the shore of Lake Neuchatel, and in Val Mora (M _L 3.5), between the Engadin and Val Müstair, as well as the 42 aftershocks of the M _L 4.9 Vallorcine earthquake, between Martigny and Chamonix, of September 2005. Editorial handling: Stefan Bucher     

A computer simulation study of natural silicate melts. Part I: Low pressure properties

In implementing into a molecular dynamics simulation code a simple interionic potential developed to describe the nine component system K₂O-Na₂O-CaO-MgO-FeO-Fe₂O₃-Al₂O₃-TiO₂-SiO₂ (KNCMFATS), it has been possible to reproduce satisfactorily a number of thermodynamic, structural and transport properties of a representative set of natural silicate melts. An important conclusion reached in this study is the good transferability of the potential from felsic to ultramafic compositions although this transferability becomes less accurate with high silica contents (rhyolitic composition and beyond) and with very iron-rich silicates (e.g. fayalite). A key feature of the simulation is to make the link between macroscopic properties of the melt and its microscopic structure and dynamics. We thus obtain a relationship between the molar volume of the melt, the number of network modifiers and the oxygen coordination number. The simulation also allows one to quantify the coordination environment around the cations as function of the melt composition. Furthermore, the electrical conductivity of the high temperature liquid is investigated.