A Reflection on Mg, Cd, Ca, Li and Si Isotopic Measurements and Related Reference Materials

This contribution aims to report the reflections we had with the scientific community during two international workshops on reference materials for stable isotopes in Davos (2002) and Nice (2003). After evaluating the isotopic homogeneity of some existing reference materials, based on either certificates, literature data or specific inter-laboratory rounds, we confirm these as primary reference materials or propose new ones relative to which stable isotope compositions should be reported. We propose DSM-3 for Mg, NIST SRM 915a for Ca, L-SVEC for Li and NBS28 for Si. Cadmium does not yet have a well identified delta zero material, although three commercial mono-elemental Cd solutions have yielded the same isotopic composition relative to one another. In order to scale the linearity of any mass spectrometer, some secondary reference materials are also proposed: Cambridge-1 solution for Mg, the "Münster-Cd" and JEPPIM Cd solutions for Cd and the "Big Batch" silicate for Si. The team from Nancy propose to prepare a mixed spike solution for Li isotopes. Well-characterised natural samples such as ocean or continental waters, diatoms, sponges, rocks and minerals are needed to validate the entire analytical procedure, particularly to take into account the effect of sample mineralisation and of chemical manipulations for elemental separation prior to analysis.     

Precise/ Small Sample Size Determinations of Lithium Isotopic Compositions of Geological Reference Materials and Modern Seawater by MC-ICP-MS

The Li isotope ratios of four international rock reference materials, USGS BHVO-2, GSJ JB-2, JG-2, JA-1 and modern seawater (Mediterranean, Pacific and North Atlantic) were determined using multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). These reference materials of natural samples were chosen to span a considerable range in Li isotope ratios and cover several different matrices in order to provide a useful benchmark for future studies. Our new analytical technique achieves significantly higher precision and reproducibility (< ± O.3%o 2s) than previous methods, with the additional advantage of requiring very low sample masses of ca . 2 ng of Li.     

Nuclear Waste Disposal Simulations: Couplex Test Cases

We give some results obtained for the Couplex test cases proposed by the ANDRA. In this paper our aim is twofold. Firstly, to compute the release of nuclides out of the repository by concentrating on the 3D near field (Couplex 2). The simulation of the transport phenomena takes into account the dissolution of the glass containers and congruent emissions of the radio-nuclides including filiation chains and some simplified chemistry. Secondly, it is to use the near field computations in order to simulate the nuclide migrations in a 2D far field (Couplex 3). Coupling in between the two simulations takes into consideration the periodicity of the disposal modules and the geometry of the repository described in Couplex 1. The mixed finite element and discontinuous Galerkin methods are used to solve the convection–diffusion equations. In order to handle the nonlinear precipitation/dissolution term, we developed a new iterative technique that combines Picard and Newton–Raphson methods.     

Magnetic fabrics and rock magnetism of Proterozoic dike swarm from the southern São Francisco Craton, Minas Gerais State, Brazil

Magnetic fabric and rock magnetism studies were performed on 32 mafic dikes of a Proterozoic dike swarm from the southern São Francisco Craton (SFC; Minas Gerais State, SE Brazil). Magnetic anisotropies were determined by applying anisotropy of low-field magnetic susceptibility (AMS) and anisotropy of remanent magnetization (ARM). The latter was performed imposing both anhysteretic (total (AAR) and partial pAAR)) and isothermal remanence magnetizations (AIRM). Partial anhysteretic remanence anisotropy was performed based on remanent coercivity spectra from a pilot specimen of each site. In most sites, AMS is dominantly carried by ferromagnetic minerals, however, in some sites, the paramagnetic contribution exceeds 70% of bulk susceptibility. Rock magnetism and thin section analysis allow classifying the dikes as non-hydrothermalized and hydrothermalized. Magnetic measurement shows that the mean magnetic susceptibility is usually lower than 5×10⁻³ (SI). Ti-poor titanomagnetites up to pure magnetite pseudo-single-domain (PSD) grain sizes carry the majority of magnetic fabrics for non-hydrothermalized dikes whereas coarse to fine grained Ti-poor titanomagnetites carry the majority of magnetic fabrics for hydrothermalized dikes.Three primary AMS fabrics are recognized which are coaxial with ARM fabric, except for two dikes, from both non-hydrothermalized and hydrothermalized dikes. Normal AMS fabric surprisingly is not dominant (31%). The parallelism between AMS, pAAR_0–30, pAAR_30–60 and pAAR_60–90 fabrics in the hydrothermalized dikes indicates that magnetic grains formed due to late-stage crystallization or to remobilization of iron oxides due to hydrothermal alteration after dike emplacement have acquired a mimetic fabric coaxial with the primary fabric given by coarse-grained early crystallized Ti-poor titanomagnetites. This fabric is interpreted as magma flow in which the analysis of K_max inclination permitted the inference that the dikes were fed by horizontal or subhorizontal fluxes (K_max<30°). Intermediate AMS fabric is the most important (41%) in the investigated swarm. It is interpreted as due to vertical compaction of a static magma column with the minimum stress along the dike strike. ARM determinations for these sites also remained intermediate except for two dikes. In one of them, AIRM fabric resulted in normal AMS fabric while for the other AAR fabric resulted in inverse AMS fabric. A combination of AMS and ARM fabrics suggest that magmatic fabric for both dikes were overprinted by some late local event, probably related to Brasiliano orogenic processes after dike emplacement. InverseInverse AMS fabric is a minority (four dikes). ARM determinations also remained inverse suggesting a primary origin for inverse AMS fabric.     

Seismic image of the deep crust at the eastern margin of the Alps (Austria): indications for crustal extension in a convergent orogen

A 39-km-long deep seismic reflection profile recorded during two field campaigns in 1996 and 2002 provides a first detailed image of the deep crust at the eastern margin of the Eastern Alps (Austria). The ESE–WNW-trending, low-fold seismic line crosses Austroalpine basement units and extends approximately from 20 km west of the Penninic window group of Rechnitz to 60 km SSE of the Alpine thrust front.The explosive-source seismic data reveals a transparent shallow crust down to 5 km depth, a complexly reflective upper crust and a highly reflective lowermost crust. The upper crust is dominated by three prominent west-dipping packages of high-amplitude subparallel reflections. The upper two of these prominent packages commence at the eastern end of the profile at about 5 and 10 km depth and are interpreted as low-angle normal shear zones related to the Miocene exhumation of the Rechnitz metamorphic core complex. In the western portion of the upper crust, east-dipping and less significant reflections prevail. The lowermost package of these reflections is suggested to represent the overall top of the European crystalline basement.Along the western portion of the line, the lower crust is characterised by a 6–8-km-thick band of high-amplitude reflection lamellae, typically observed in extensional provinces. The Moho can be clearly defined at the base of this band, at approximately 32.5 km depth. Due to insufficient signal penetration, outstanding reflections are missing in the central and eastern portion of the lower crust. We speculate that the result of accompanying gravity measurements and lower crustal sporadic reflections can be interpreted as an indication for a shallower Moho in the east, preferable at about 30.5 km depth.The high reflectivity of the lowermost part of the lower crust and prominent reflection packages in the upper crust, the latter interpreted to represent broad extensional mylonite zones, emphasises the latest extensional processes in accordance with eastward extrusion.     

The 1.80–1.74-Ga gabbro–anorthosite–rapakivi Korosten Pluton in the Ukrainian Shield: a 3-D geophysical reconstruction of deep structure

The deep structure of the gabbro–anorthosite–rapakivi granite (“AMCG-type”) Korosten Pluton (KP) in the northwestern Ukrainian Shield was studied by 3-D modelling of the gravity and magnetic fields together with previous seismic data. The KP occupies an area of ca. 12,500 km² and comprises several layered gabbro-anorthositic intrusions enveloped by large volumes of rapakivi-type granitoids. Between 1.80 and 1.74 Ga, the emplacement of mafic and associated granitoid melts took place in several pulses. The 3-D geophysical reconstruction included: (a) modelling of the density distribution in the crust using the observed Bouguer anomaly field constrained by seismic data on Moho depth, and (b) modelling of the magnetic anomaly field in order to outline rock domains of various magnetisation, size and shape in the upper and lower crust. The density modelling was referred to three depth levels of 0 to 5, 5 to 18, and 18 km to Moho, respectively. The 3-D reconstruction demonstrates close links between the subsurface geology of the KP and the structure of the lower crust. The existence of a non-magnetic body with anomalously high seismic velocity and density is documented. Most plausibly, it represents a gabbroic stock (a parent magma chamber) with a vertical extent of ca. 20 km, penetrating the entire lower crust. This stock has a half-cylindrical shape and a diameter of ca. 90 km. It appears to be connected with a crust–mantle transitional lens previously discovered by EUROBRIDGE seismic profiling. The position of the stock relative to the subsurface outlines of the KP is somewhat asymmetric. This may be due to a connection between the magmatism and sets of opposite-dipping faults initially developed during late Palaeoproterozoic collisional deformation in the Sarmatian crustal segment. Continuing movements and disturbances of the upper mantle and the lower crust during post-collisional tectonic events between 1.80 and 1.74 Ga may account for the long-lived, recurrent AMCG magmatism.     

Evidence for Neotethys rooted within the Vardar suture zone from the Voras Massif, northernmost Greece

Three conflicting models are currently proposed for the location and tectonic setting of the Eurasian continental margin and adjacent Tethys ocean in the Balkan region during Mesozoic–Early Tertiary time. Model 1 places the Eurasian margin within the Rhodope zone relatively close to the Moesian platform. A Tethyan oceanic basin was located to the south bordering a large “Serbo-Pelagonian” microcontinent. Model 2 correlates an integral “Serbo-Pelagonian” continental unit with the Eurasian margin and locates the Tethys further southwest. Model 3 envisages the Pelagonian zone and the Serbo-Macedonian zone as conjugate continental units separated by a Tethyan ocean that was sutured in Early Tertiary time to create the Vardar zone of northern Greece and former Yugoslavia. These published alternatives are tested in this paper based on a study of the tectono-stratigraphy of a completely exposed transect located in the Voras Mountains of northernmost Greece. The outcrop extends across the Vardar zone, from the Pelagonian zone in the west to the Serbo-Macedonian zone in the east.Within the Voras Massif, six east-dipping imbricate thrust sheets are recognised. Of these, Units 1–4 correlate with the regional Pelagonian zone in the west (and related Almopias sub-zone). By contrast, Units 5–6 show a contrasting tectono-stratigraphy and correlate with the Paikon Massif and the Serbo-Macedonian zone to the east. These units form a stack of thrust sheets, with Unit 1 at the base and Unit 6 at the top. Unstacking these thrust sheets places ophiolitic units between the Pelagonian zone and the Serbo-Macedonian zone, as in Model 3. Additional implications are, first, that the Paikon Massif cannot be seen as a window of Pelagonian basement, as in Model 1, and, secondly, Jurassic andesitic volcanics of the Paikon Massif locally preserve a gneissose continental basement, ruling out a recently suggested origin as an intra-oceanic arc.We envisage that the Almopias (Vardar) ocean rifted in Triassic time, followed by seafloor spreading. The Almopias ocean was consumed beneath the Serbo-Macedonian margin in Jurassic time, generating subduction-related arc volcanism in the Paikon Massif and related units. Ophiolites were emplaced onto the Pelagonian margin in the west and covered by Late Jurassic (pre-Kimmeridgian) conglomerates. Other ophiolitic rocks formed within the Vardar zone (Ano Garefi ophiolite, Unit 4) in latest Jurassic–Early Cretaceous time and were not deformed until Early Tertiary time. The Vardar zone finally sutured in the Early Tertiary creating the present imbricate thrust structure of the Voras Mountains.     

Tectonic evolution of the Intra-Pontide suture zone in the Armutlu Peninsula, NW Turkey

The Armutlu Peninsula and adjacent areas in NW Turkey play a critical role in tectonic reconstructions of the southern margin of Eurasia in NW Turkey. This region includes an inferred Intra-Pontide oceanic basin that rifted from Eurasia in Early Mesozoic time and closed by Late Cretaceous time. The Armutlu Peninsula is divisible into two metamorphic units. The first, the Armutlu Metamorphics, comprises a ?Precambrian high-grade metamorphic basement, unconformably overlain by a ?Palaeozoic low-grade, mixed siliciclastic/carbonate/volcanogenic succession, including bimodal volcanics of inferred extensional origin, with a possibly inherited subduction signature. The second unit, the low-grade znik Metamorphics, is interpreted as a Triassic rift infilled with terrigenous, calcareous and volcanogenic lithologies, including basalts of within-plate type. The Triassic rift was unconformably overlain by a subsiding Jurassic–Late Cretaceous (Cenomanian) passive margin including siliciclastic/carbonate turbidites, radiolarian cherts and manganese deposits. The margin later collapsed to form a flexural foredeep associated with the emplacement of ophiolitic rocks in Turonian time. Geochemical evidence from meta-basalt blocks within ophiolite-derived melange suggests a supra-subduction zone origin for the ophiolite. The above major tectonic units of the Armutlu Peninsula were sealed by a Maastrichtian unconformity. Comparative evidence comes from the separate Almacık Flake further east.Considering alternatives, it is concluded that a Mesozoic Intra-Pontide oceanic basin separated Eurasia from a Sakarya microcontinent, with a wider Northern Neotethys to the south. Lateral displacement of exotic terranes along the south-Eurasian continental margin probably also played a role, e.g. during Late Cretaceous suturing, in addition to overthrusting.     

Slab behaviour and its surface expression: new insights from gravity modelling in the SE-Carpathians

We use lithosphere-scale gravity models to calculate gravity anomalies resulting from oceanic subduction, continental collision, slab steepening, delamination, and break-off. Local isostasy was assumed for determining vertical movements caused by mass changes related to these tectonic processes. Our results show that subduction is accompanied by basin subsidence on the upper plate caused by the heavy lithospheric root of the subducting slab. The basin evolution goes parallel with the slab evolution and shows considerable modifications when the processes at depth change (slab steepening, delamination, break-off). Characteristic gravity anomaly curves were acquired for the different tectonic scenarios. These curves together with other data (e.g. basin evolution on the upper and the lower plate) were used for the reconstruction of the tectonic evolution of the SE-Carpathians which includes Tertiary subduction and collision followed by slab steepening and delamination.     

U–Pb geochronology of the southern Brasília belt (SE-Brazil): sedimentary provenance, Neoproterozoic orogeny and assembly of West Gondwana

The Brasília belt borders the western margin of the São Francisco Craton and records the history of ocean opening and closing related to the formation of West Gondwana. This study reports new U–Pb data from the southern sector of the belt in order to provide temporal limits for the deposition and ages of provenance of sediments accumulated in passive margin successions around the south and southwestern margins of the São Francisco Craton, and date the orogenic events leading to the amalgamation of West Gondwana.Ages of detrital zircons (by ID–TIMS and LA-MC-ICPMS) were obtained from metasedimentary units of the passive margin of the São Francisco Craton from the main tectonic domains of the belt: the internal allochthons (Araxá Group in the Áraxá and Passos Nappes), the external allochthons (Canastra Group, Serra da Boa Esperança Metasedimentary Sequence and Andrelândia Group) and the autochthonous or Cratonic Domain (Andrelândia Group). The patterns of provenance ages for these units are uniform and are characterised as follows: Archean–Paleoproterozoic ages (3.4–3.3, 3.1–2.7, and 2.5–2.4 Ga); Paleoproterozoic ages attributed to the Transamazonian event (2.3–1.9 Ga, with a peak at ca. 2.15 Ga) and to the ca. 1.75 Ga Espinhaço rifting of the São Francisco Craton; ages between 1.6 and 1.2 Ga, with a peak at 1.3 Ga, revealing an unexpected variety of Mesoproterozoic sources, still undetected in the São Francisco Craton; and ages between 0.9 and 1.0 Ga related to the rifting event that led to the individualisation of the São Francisco paleo-continent and formation of its passive margins. An amphibolite intercalation in the Araxá Group yields a rutile age of ca. 0.9 Ga and documents the occurrence of mafic magmatism coeval with sedimentation in the marginal basin.Detrital zircons from the autochthonous and parautochthonous Andrelândia Group, deposited on the southern margin of the São Francisco Craton, yielded a provenance pattern similar to that of the allochthonous units. This result implies that 1.6–1.2 Ga source rocks must be present in the São Francisco Craton. They could be located either in the cratonic area, which is mostly covered by the Neoproterozoic epicontinental deposits of the Bambuí Group, or in the outer paleo-continental margin, buried under the allochthonous units of the Brasília belt.Crustal melting and generation of syntectonic crustal granites and migmatisation at ca. 630 Ma mark the orogenic event that started with westward subduction of the São Francisco plate and ended with continental collision against the Paraná block (and Goiás terrane). Continuing collision led to the exhumation and cooling of the Araxá and Passos metamorphic nappes, as indicated by monazite ages of ca. 605 Ma and mark the final stages of tectonometamorphic activity in the southern Brasília belt.Whilst continent–continent collision was proceeding on the western margin of the São Francisco Craton along the southern Brasília belt, eastward subduction in the East was generating the 634–599 Ma Rio Negro magmatic arc which collided with the eastern São Francisco margin at 595–560 Ma, much later than in the Brasília belt. Thus, the tectonic effects of the Ribeira belt reached the southernmost sector of the Brasília belt creating a zone of superposition. The thermal front of this event affected the proximal Andrelândia Group at ca. 588 Ma, as indicated by monazite age.The participation of the Amazonian craton in the assembly of western Gondwana occurred at 545–500 Ma in the Paraguay belt and ca. 500 Ma in the Araguaia belt. This, together with the results presented in this work lead to the conclusion that the collision between the Paraná block and Goiás terrane with the São Francisco Craton along the Brasília belt preceded the accretion of the Amazonian craton by 50–100 million years.