Manganiferous minerals of the epidote group from the Archaean basement of West Greenland

The chemical compositions and crystal structures of Mn3+-containing minerals from the epidote group in Greenland rocks are investigated and described in detail. They occur in hydrothermally altered Archaean mafic sequences within the gneissic complex of the North Atlantic craton of West Greenland. The Mn-containing minerals have a characteristic red to pink colour. A detailed microchemical study shows a significant inter- and intra-sample variation in Mn content. The samples from different parageneses can be classified as Mn-bearing epidote and Mn-bearing clinozoisite. The intra-sample variation in the content of Al, Fe and Mn is on a very fine scale, but still allows for identification of a negative correlation between Mn and Fe. Textures indicate different stages of growth. Crystal chemical data are compared with literature data and illustrate the basic systematic differences between the influence of Fe and Mn on the crystal structure of the epidote group minerals.

Ce(III) and Ce(IV) (re)distribution and fractionation in a laterite profile from Madagascar: Insights from in situ XANES spectroscopy at the Ce LIII-edge

The distribution of trivalent and tetravalent cerium, Ce(III) and Ce(IV) respectively, in a lateritic profile from Madagascar, has been characterized by X-ray-absorption near-edge structure (XANES) spectroscopy at the Ce LIII-edge on the LUCIA beamline (SOLEIL synchrotron, France). XANES spectra were acquired on bulk-rock samples as well as on specific lateritic minerals or polymineral zones (in-situ measurements) of the tonalite bedrock and the three overlying weathered horizons (C-, B- and A-horizons). Geochemically, the bedrock, and the A- and C-horizons show similar rare earth element content (REE = 363–405 mg/kg). They also display the same positive Ce-anomaly (CeCN/Ce∗ = 1.12–1.45), which is therefore likely to be inherited from the bedrock. In the B-horizon, the higher REE content (REE = 2194 mg/kg) and the larger Ce-anomaly (CeCN/Ce∗ = 4.26) are consistent with an accumulation zone caused by the evaporation of groundwater during the dry season. There is a good agreement between the Ce(III)/Cetotal ratio (XCe(III)) deduced from the positive Ce-anomaly (bulk-rock geochemical data) and that derived from XANES spectroscopy on the same bulk-rock samples (BR-XCe(III)-XANES) in the bedrock, and the C- and B-horizons. In the A-horizon, XANES measurements on bulk rock and minerals revealed a higher BR-XCe(III)-XANES (up to 100%) compared to the XCe(III) deduced from geochemical data (XCe(III) = 79%). The preservation of a positive Ce-anomaly in the A-horizon suggests that the Ce mobilization and redistribution during weathering occurred with no significant Ce fractionation from other trivalent REE. Remarkably, the only investigated sample where cerianite is observed belongs to the B-horizon. Within this horizon, Ce oxidation state varies depending on the microstructural position (porosity, cracks, clay-rich groundmass). The highest Ce(IV) concentrations are measured in cerianite (and aluminophosphates) localized in pores at the vicinity of Mn-rich domains (XCe(III)-XANES = 30–51%). Therefore, Ce fractionation from other REE is attributed to a Ce oxidation and precipitation potentially assisted by oxyhydroxide scavenging. In the C-horizon, Ce(III) and Ce(IV) are mainly distributed in REE-minerals of the rhabdophane group found in pores and cracks. The similarity between the Ce(III) proportion of rhabdophane grains (XCe(III)-XANES = 74–89%) with that of the bedrock (BR-XCe(III)-XANES = 79%) suggests no significant fractionation of Ce(III) and Ce(IV) between solution and mineral during the successive stages of primary REE-mineral alteration, transport in solution and secondary precipitation in the incipient stages of weathering. Overall, our novel spectroscopic approach shows that Ce is not necessarily oxidized nor fractionated from other REE during weathering in lateritic conditions. This implies that like Ce(III), Ce(IV) can be mobilized in aqueous fluids during weathering, possibly thanks to complexation with organic molecules, and can precipitate together with Ce(III) in secondary REE-bearing minerals. The corollary is that (paleo)redox reconstructions in soils and/or sediments based on Ce-anomaly in weathered rocks or minerals must be interpreted with caution.

Linking megathrust earthquakes to brittle deformation in a fossil accretionary complex

Seismological data from recent subduction earthquakes suggest that megathrust earthquakes induce transient stress changes in the upper plate that shift accretionary wedges into an unstable state. These stress changes have, however, never been linked to geological structures preserved in fossil accretionary complexes. The importance of coseismically induced wedge failure has therefore remained largely elusive. Here we show that brittle faulting and vein formation in the palaeo-accretionary complex of the European Alps record stress changes generated by subduction-related earthquakes. Early veins formed at shallow levels by bedding-parallel shear during coseismic compression of the outer wedge. In contrast, subsequent vein formation occurred by normal faulting and extensional fracturing at deeper levels in response to coseismic extension of the inner wedge. Our study demonstrates how mineral veins can be used to reveal the dynamics of outer and inner wedges, which respond in opposite ways to megathrust earthquakes by compressional and extensional faulting, respectively.

Relating orogen width to shortening, erosion, and exhumation during Alpine collision

We investigate along-strike width changes of the thickened, accreted lower plate (TALP) in the Central and in the Eastern Alps. We set the width of the TALP in relation to the inferred amount of collisional shortening and exhumation along six orogen-scale cross sections. Taking the present-day, along-strike gradients in the amount of collisional shortening to represent the temporal evolution of the collisional wedge, it may be concluded that the cross-sectional area of the TALP diminishes during ongoing shortening, indicating that the erosional flux outpaced the accretionary flux. Higher amounts of collisional shortening systematically coincide with smaller widths of the TALP and dramatic increases of the reconstructed eroded rock column. Higher amounts of shortening also coincide with larger amplitudes of orogen-scale, upright folds, with higher exhumation and with higher exhumation rates. Hence, erosion did play a major role in reducing by >30 km the vertical crustal thickness in order to accommodate and allow shortening by folding. Long-term climate differences cannot explain alternating changes of width by a factor of almost 2 along straight segments of the orogen on length scales less than 200 km, as observed from the western Central Alps to the easternmost Eastern Alps. Sedimentary or paleontological evidences supporting such paleo-climatic differences are lacking, suggesting that erosional processes did not directly control the width of the orogen.

Exhumation rates in the Archean from pressure-ime paths: Examplefrom the Skjoldungen Orogen (SE Greenland)

The discussions on the orogenic evolution during Earth's history converge to the question of a different thermal structure in the Archean compared to the Phanerozoic and the applicability of the plate tectonic paradigm. However, geothermal structures are transient in orogens and are difficult to translate into large-scale tectonics and exhumation rates. Therefore, we propose depth–time data in the Archean Skjoldungen Orogen (SE Greenland, North Atlantic Craton) that allow for reconstruction of an exhumation rate independent of geothermal gradients. The resulting exhumation rate of ca. 0.4 km/Ma is similar to exhumation rates during erosion-controlled processes in modern orogens. These exhumation rates can only be established by erosion time constants similar to modern orogens. The occurrence of erosion-controlled exhumation is best explained by a stiff foreland promoting localized deformation in the orogen. Therefore, a switch from magmatic-dominated processes to localized deformation is proposed in the Skjoldungen Orogen area. This is supported by a change in magma composition and volume, from widespread granodiorite to localized alkaline intrusions. In addition, the involved metasedimentary rocks include detrital zircons of the only 50 Ma older foreland, which also correspond to erosion and tectonics as in modern orogens, i.e. flysh-type sediments. Relatively fast exhumation rates and the structural-magmatic evolution of the Neoarchean Skjoldungen Orogen thus indicate modern-style tectonic processes where stiff Mesoarchean continental crust forms a foreland to a collisional orogen instead of typical accretionary tectonics of weak island arc-like terranes in granite-greenstone terranes.

Inherited structural controls on fault geometry, architecture and hydrothermal activity: an example from Grimsel Pass, Switzerland

Exhumed faults hosting hydrothermal systems provide direct insight into relationships between faulting and fluid flow, which in turn are valuable for making hydrogeological predictions in blind settings. The Grimsel Breccia Fault (Aar massif, Central Swiss Alps) is a late Neogene, exhumed dextral strike-slip fault with a maximum displacement of 25–45 m, and is associated with both fossil and active hydrothermal circulation. We mapped the fault system and modelled it in three dimensions, using the distinctive hydrothermal mineralisation as well as active thermal fluid discharge (the highest elevation documented in the Alps) to reveal the structural controls on fluid pathway extent and morphology. With progressive uplift and cooling, brittle deformation inherited the mylonitic shear zone network at Grimsel Pass; preconditioning fault geometry into segmented brittle reactivations of ductile shear zones and brittle inter-shear zone linkages. We describe ‘pipe’-like, vertically oriented fluid pathways: (1) within brittle fault linkage zones and (2) through alongstrike- restricted segments of formerly ductile shear zones reactivated by brittle deformation. In both cases, low-permeability mylonitic shear zones that escaped brittle reactivation provide important hydraulic seals. These observations show that fluid flow along brittle fault planes is not planar, but rather highly channelised into sub-vertical flow domains, with important implications for the exploration and exploitation of geothermal energy.

On the initiation of boudinage and folding instabilities in layered elasto-visco-plastic solids - Insights from natural microstructures and numerical simulations

The present understanding of the initiation of boudinage and folding structures is based on viscosity contrasts and stress exponents, considering an intrinsically unstable state of the layer. The criterion of localization is believed to be prescribed by geometry-material interactions, which are often encountered in natural structures. An alternative localization phenomenon has been established for ductile materials, in which instability emerges for critical material parameters and loading rates from homogeneous conditions. In this thesis, conditions are sought under which this type of instability prevails and whether localization in geological materials necessarily requires a trigger by geometric imperfections. The relevance of critical deformation conditions, material parameters and the spatial configuration of instabilities are discussed in a geological context. In order to analyze boudinage geometries, a numerical eigenmode analysis is introduced. This method allows determining natural frequencies and wavelengths of a structure and inducing perturbations on these frequencies. In the subsequent coupled thermo-mechanical simulations, using a grain size evolution and end-member flow laws, localization emerges when material softening through grain size sensitive viscous creep sets in. Pinch-and-swell structures evolve along slip lines through a positive feedback between the matrix response and material bifurcations inside the layer, independent from the mesh-discretization length scale. Since boudinage and folding are considered to express the same general instability, both structures should arise independently of the sign of the loading conditions and for identical material parameters. To this end, the link between material to energy instabilities is approached by means of bifurcation analyses of the field equations and finite element simulations of the coupled system of equations. Boudinage and folding structures develop at the same critical energy threshold, where dissipative work by temperature-sensitive creep overcomes the diffusive capacity of the layer. This finding provides basis for a unified theory for strain localization in layered ductile materials. The numerical simulations are compared to natural pinch-and-swell microstructures, tracing the adaption of grain sizes, textures and creep mechanisms in calcite veins. The switch from dislocation to diffusion creep relates to strain-rate weakening, which is induced by dissipated heat from grain size reduction, and marks the onset of continuous necking. The time-dependent sequence uncovers multiple steady states at different time intervals. Microstructurally and mechanically stable conditions are finally expressed in the pinch-and-swell end members. The major outcome of this study is that boudinage and folding can be described as the same coupled energy-mechanical bifurcation, or as one critical energy attractor. This finding allows the derivation of critical deformation conditions and fundamental material parameters directly from localized structures in the field.

Grain coarsening maps: A new tool to predict microfabric evolution of polymineralic rocks

Polymineralic rocks undergo grain coarsening with increasing temperature in both static and deformational environments, as long as no mineral reactions occur. The grain coarsening in such rocks is complex because the different phases influence each other, and it is this interaction that controls the rate of grain coarsening of the entire aggregate. We present a mathematical approach to investigate coupled grain coarsening using a set of microstructural parameters, including grain size and volume fraction of both second phases and matrix mineral in combination with temperature information. Based on samples from polymineralic carbonate mylonites that were deformed at different temperatures, we demonstrate how the mathematical relation can be calibrated for this natural system. Using such data sets for other lithologies, grain coarsening maps can be generated, which allow the prediction of microstructural evolution in polymineralic rocks. Such predictions are crucial for all subdisciplines in the earth sciences that require fundamental knowledge about microstructural changes and rheology of an orogen at different depths, such as structural geology, geophysics, geodynamics, and metamorphic petrology.

Grain coarsening in contact metamorphic carbonates: effects of second-phase particles, fluid flow and thermal perturbations

Under contact metamorphic conditions, carbonate rocks in the direct vicinity of the Adamello pluton reflect a temperature-induced grain coarsening. Despite this large-scale trend, a considerable grain size scatter occurs on the outcrop-scale indicating local influence of second-order effects such as thermal perturbations, fluid flow and second-phase particles. Second-phase particles, whose sizes range from nano- to the micron-scale, induce the most pronounced data scatter resulting in grain sizes too small by up to a factor of 10, compared with theoretical grain growth in a pure system. Such values are restricted to relatively impure samples consisting of up to 10 vol.% micron-scale second-phase particles, or to samples containing a large number of nano-scale particles. The obtained data set suggests that the second phases induce a temperature-controlled reduction on calcite grain growth. The mean calcite grain size can therefore be expressed in the form D 1⁄4 C2 eQ*/RT(dp/fp)m*, where C2 is a constant, Q* is an activation energy, T the temperature and m* the exponent of the ratio dp/fp, i.e. of the average size of the second phases divided by their volume fraction. However, more data are needed to obtain reliable values for C2 and Q*. Besides variations in the average grain size, the presence of second-phase particles generates crystal size distribution (CSD) shapes characterized by lognormal distributions, which differ from the Gaussian-type distributions of the pure samples. In contrast, fluid-enhanced grain growth does not change the shape of the CSDs, but due to enhanced transport properties, the average grain sizes increase by a factor of 2 and the variance of the distribution increases. Stable d18O and d13C isotope ratios in fluid-affected zones only deviate slightly from the host rock values, suggesting low fluid/rock ratios. Grain growth modelling indicates that the fluid-induced grain size variations can develop within several ka. As inferred from a combination of thermal and grain growth modelling, dykes with widths of up to 1 m have only a restricted influence on grain size deviations smaller than a factor of 1.1.To summarize, considerable grain size variations of up to one order of magnitude can locally result from second-order effects. Such effects require special attention when comparing experimentally derived grain growth kinetics with field studies.