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.     

Stable Isotope Ratios and the Evolution of Acidulous Ground Water

Ground waters in North Hesse (Germany) are conspicuous by high amounts of dissolved inorganic carbon (DIC) at low pH. The DIC is received from the uptake of soil CO₂ and CO₂ of volcanic origin and the subsequent dissolution ofTriassic and Permian limestone and dolomites. The volcanic CO₂ is related to Miocene basaltic magma which has liberated gaseous CO₂ during thebreakthrough to Triassic and Permian sediments. The volcanic CO₂ (-6 < ¹³CCO₂ < -3, PDB) was trapped within pore spacesand intra- and intergranulares of Permian evaporites and Triassic sandstones and was stored within such reservoirs until recent times. The uptake of volcanic CO₂ occurs as ground water migrates through such reservoirs. The ¹³ C/¹² C-signatures of the DIC indicate mixture of soil-CO₂and CO₂ of volcanic origin for the dissolution of marine limestone and dolomites. The obtained two types for CO₂ of volcanic origin with ¹³C_{CO 2}-values of -10 ± 3 and +2 ± 2 can be explained by diffusion of CO₂ through micropores, faults, and interfacesof solids. This mobilisation of CO₂ is accompanied with a kinetic fractionation of -9. ¹³ C-depleted CO₂ is liberated from the reservoir,whereas ¹³ CO₂ is accumulated in the residue     

Isotopic constraints on genetic relationships among group IIIF iron meteorites,Fitzwater Pass,and the Zinder pallasite

Complex interelement trends among magmatic IIIF iron meteorites are difficult to explain by fractional crystallization and have raised uncertainty about their genetic relationships. Nucleosynthetic Mo isotope anomalies provide a powerful tool to assess if individual IIIF irons are related to each other. However, while trace element data are available for all nine IIIF irons, Mo isotopic data are limited to three samples. We present Mo isotopic data for all but one IIIF irons that help assess the genetic relationships among these irons, together with new Mo and W isotopic data for Fitzwater Pass (classified IIIF), and the Zinder pallasite (for which a cogenetic link with IIIF irons has been proposed). After correction for cosmic-ray exposure, the Mo isotopic compositions of the IIIF irons are identical within uncertainty and confirm their belonging to carbonaceous chondrite (CC)-type meteorites. The mean Mo isotopic composition of group IIIF overlaps those groups IIF and IID, but a common parent body for these groups is ruled out based on distinct trace element systematics. The new Mo isotopic data do not argue against a single parent body for the IIIF irons, and suggest a close genetic link among these samples. In contrast, Fitzwater Pass has distinct Mo and W isotopic compositions, identical to those of some non-magmatic IAB irons. The Mo and W isotope data for Zinder indicate that this meteorite is not related to IIIF irons, but belongs to the non-carbonaceous (NC) type and has the same Mo and W isotopic composition as main-group pallasites.     

Thermal history of Northwest Africa 5073––A coarse‐grained Stannern‐trend eucrite containing cm‐sized pyroxenes and large zircon grains

Abstract– We report on the bulk chemical composition, petrology, oxygen isotopic composition, trace element composition of silicates, and degree of self‐irradiation damage on zircon grains of the eucrite Northwest Africa (NWA) 5073 to constrain its formation and postcrystallization thermal history, and to discuss their implications for the geologic history of its parent body. This unequilibrated and unbrecciated meteorite is a new member of the rare Stannern‐trend eucrites. It is mainly composed of elongated, zoned pyroxene phenocrysts up to 1.2 cm, plagioclase laths up to 0.3 cm in length, and is rich in mesostasis. The latter contains zircon grains up to 30 μm in diameter, metal, sulfide, tridymite, and Ca‐phosphates. Textural observations and silicate compositions, coupled with the occurrence of extraordinary Fe‐rich olivine veins that are restricted to large pyroxene laths, indicate that NWA 5073 underwent a complex thermal history. This is also supported by the annealed state of zircon grains inferred from μ‐Raman spectroscopic measurements along with U and Th data obtained by electron probe microanalyses.     

Voigt profile fitting to quasar absorption lines: an analytic approximation to the Voigt–Hjerting function

The Voigt–Hjerting function is fundamental in order to correctly model the profiles of absorption lines imprinted on the spectra of bright background sources by intervening absorbing systems. In this work, we present a simple analytic approximation to this function in the context of absorption-line profiles of intergalactic H  i absorbers. Using basic calculus tools, we derive an analytic expression for the Voigt–Hjerting function that contains only fourth-order polynomial and Gaussian functions. In connection with the absorption coefficient of intergalactic neutral hydrogen, this approximation is suitable for modelling Voigt profiles with an accuracy of 10⁻⁴ or better for an arbitrary wavelength baseline, for column densities up to   N _H I= 10 ²² cm⁻²  , and for damping parameters   a ≲ 10⁻⁴  , that is, the entire range of parameters characteristic to all Lyman transitions arising in a variety of H  i absorbing systems such as Lyman α (Lyα) forest clouds, Lyman limit systems and damped Lyα systems. We hence present an approximation to the Voigt–Hjerting function that is both accurate and flexible to implement in various types of programming languages and machines, and with which Voigt profiles can be calculated in a reliable and very simple manner.     

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.     

Regionalization of constraints on expected watershed response behavior for improved predictions in ungauged basins

Approaches to modeling the continuous hydrologic response of ungauged basins use observable physical characteristics of watersheds to either directly infer values for the parameters of hydrologic models, or to establish regression relationships between watershed structure and model parameters. Both these approaches still have widely discussed limitations, including impacts of model structural uncertainty. In this paper we introduce an alternative, model independent, approach to streamflow prediction in ungauged basins based on empirical evidence of relationships between watershed structure, climate and watershed response behavior. Instead of directly estimating values for model parameters, different hydrologic response behaviors of the watershed, quantified through model independent streamflow indices, are estimated and subsequently regionalized in an uncertainty framework. This results in expected ranges of streamflow indices in ungauged watersheds. A pilot study using 30 UK watersheds shows how this regionalized information can be used to constrain ensemble predictions of any model at ungauged sites. Dominant controlling characteristics were found to be climate (wetness index), watershed topography (slope), and hydrogeology. Main streamflow indices were high pulse count, runoff ratio, and the slope of the flow duration curve. This new approach provided sharp and reliable predictions of continuous streamflow at the ungauged sites tested.