Lu–Hf garnet systematics of a polymetamorphic basement unit: new evidence for coherent exhumation of the Adula Nappe (Central Alps) from eclogite-facies conditions

The Adula Nappe in the Central Alps is a mixture of various pre-Mesozoic continental basement rocks, metabasics, ultrabasics, and Mesozoic cover rocks, which were pervasively deformed during Alpine orogeny. Metabasics, ultrabasics, and locally garnet–mica schists preserve eclogite-facies assemblages while the bulk of the nappe lacks such evidence. We provide garnet major-element data, Lu profiles, and Lu–Hf garnet geochronology from eclogites sampled along a north–south traverse. A southward increasing Alpine overprint over pre-Alpine garnets is observed throughout the nappe. Garnets in a sample from the northern Adula Nappe display a single growth cycle and yield a Variscan age of 323.8 ± 6.9 Ma. In contrast, a sample from Alpe Arami in the southernmost part contains unzoned garnets that fully equilibrated to Alpine high-pressure (HP) metamorphic conditions with temperatures exceeding 800 °C. We suggest that the respective Eocene Lu–Hf age of 34.1 ± 2.8 Ma is affected by partial re-equilibration after the Alpine pressure peak. A third sample from the central part of the nappe contains separable Alpine and Variscan garnet populations. The Alpine population yields a maximum age of 38.8 ± 4.3 Ma in line with a previously published garnet maximum age from the central nappe of 37.1 ± 0.9 Ma. The Adula Nappe represents a coherent basement unit, which preserves a continuous Alpine high-pressure metamorphic gradient. It was subducted as a whole in a single, short-lived event in the upper Eocene. Controversial HP ages and conditions in the Adula Nappe may result from partly preserved Variscan assemblages in Alpine metamorphic rocks.     

CO<Subscript>2</Subscript> fluid inclusions in Jack Hills zircons

The discovery of Hadean to Paleoarchean zircons in a metaconglomerate from Jack Hills, Western Australia, has catalyzed intensive study of these zircons and their mineral inclusions, as they represent unique geochemical archives that can be used to unravel the geological evolution of early Earth. Here, we report the occurrence and physical properties of previously undetected CO₂ inclusions that were identified in 3.36–3.47 Ga and 3.80–4.13 Ga zircon grains by confocal micro-Raman spectroscopy. Minimum P–T conditions of zircon formation were determined from the highest density of the inclusions, determined from the density-dependence of the Fermi diad splitting in the Raman spectrum and Ti-in-zircon thermometry. For both age periods, the CO₂ densities and Ti-in-zircon temperatures correspond to high-grade metamorphic conditions (≥5 to ≥7 kbar/~670 to 770 °C) that are typical of mid-crustal regional metamorphism throughout Earth’s history. In addition, fully enclosed, highly disordered graphitic carbon inclusions were identified in two zircon grains from the older population that also contained CO₂ inclusions. Transmission electron microscopy on one of these inclusions revealed that carbon forms a thin amorphous film on the inclusion wall, whereas the rest of the volume was probably occupied by CO₂ prior to analysis. This indicates a close relationship between CO₂ and the reduced carbon inclusions and, in particular that the carbon precipitated from a CO₂-rich fluid, which is inconsistent with the recently proposed biogenic origin of carbon inclusions found in Hadean zircons from Jack Hills.     

Experimental study of the aragonite to calcite transition in aqueous solution

The experimental replacement of aragonite by calcite was studied under hydrothermal conditions at temperatures between 160 and 200 °C using single inorganic aragonite crystals as a starting material. The initial saturation state and the total [Ca²⁺]:[CO₃²⁻] ratio of the experimental solutions was found to have a determining effect on the amount and abundance of calcite overgrowths as well as the extent of replacement observed within the crystals. The replacement process was accompanied by progressive formation of cracks and pores within the calcite, which led to extended fracturing of the initial aragonite. The overall shape and morphology of the parent aragonite crystal were preserved. The replaced regions were identified with scanning electron microscopy and Raman spectroscopy.Experiments using carbonate solutions prepared with water enriched in ¹⁸O (97%) were also performed in order to trace the course of this replacement process. The incorporation of the heavier oxygen isotope in the carbonate molecule within the calcite replacements was monitored with Raman spectroscopy. The heterogeneous distribution of ¹⁸O in the reaction products required a separate study of the kinetics of isotopic equilibration within the fluid to obtain a better understanding of the ¹⁸O distribution in the calcite replacement. An activation energy of 109 kJ/mol was calculated for the exchange of oxygen isotopes between [C¹⁶O₃²⁻]_aq and [H₂¹⁸O] and the time for oxygen isotope exchange in the fluid at 200 °C was estimated at ∼0.9 s. Given the exchange rate, analyses of the run products imply that the oxygen isotope composition in the calcite product is partly inherited from the oxygen isotope composition of the aragonite parent during the replacement process and is dependent on access of the fluid to the reaction interface rather than equilibration time. The aragonite to calcite fluid-mediated transformation is described by a coupled dissolution-reprecipitation mechanism, where aragonite dissolution is coupled to the precipitation of calcite at an inwardly moving reaction interface.