The L3–6 chondritic regolith breccia Northwest Africa (NWA) 869: (I) Petrology,chemistry, oxygen isotopes,and Ar‐Ar age determinations

Abstract– Northwest Africa (NWA) 869 consists of thousands of individual stones with an estimated total weight of about 7 metric tons. It is an L3–6 chondrite and probably represents the largest sample of the rare regolith breccias from the L–chondrite asteroid. It contains unequilibrated and equilibrated chondrite clasts, some of which display shock‐darkening. Impact melt rocks (IMRs), both clast‐free and clast‐poor, are strongly depleted in Fe,Ni metal, and sulfides. An unequilibrated microbreccia, two different light inclusions and two different SiO₂‐bearing objects were found. Although the matrix of this breccia appears partly clastic, it is not a simple mixture of fine‐grained debris formed from the above lithologies, but mainly represents an additional specific lithology of low petrologic type. We speculate that this material stems from a region of the parent body that was only weakly consolidated. One IMR clast and one SiO₂‐bearing object show Δ¹⁷O values similar to bulk NWA 869, suggesting that both are related to the host rock. In contrast, one light inclusion and one IMR clast appear to be unrelated to NWA 869, suggesting that the IMR clast is contaminated with impactor material. ⁴⁰Ar‐³⁹Ar analyses of a type 4 chondrite clast yield a plateau age of 4402 ± 7 Ma, which is interpreted to be the result of impact heating. Other impact events are recorded by an IMR clast at 1790 ± 36 Ma and a shock‐darkened clast at 2216 ± 40 Ma, demonstrating that NWA 869 escaped major reset in the course of the event at approximately 470 Ma that affected many L–chondrites.     

Excess heat capacity and entropy of mixing in the high-structural state (K,Ca)-feldspar binary

Low- and high-temperature heat capacities were measured for a series of synthetic high-structural state (K,Ca)-feldspars (Or–An) using both a relaxation and a differential scanning calorimeter. The data were collected at temperatures between 5 and 800 K on polycrystalline samples that had been synthesised and characterised in a previous study. Below T = 300 K, Or₉₀An₁₀, and Or₈₀An₂₀ showed excess heat capacities of mixing with maximum values of ~3 J mol⁻¹ K⁻¹. The other members of this binary (An > 20 mol%) had lower excess heat capacity values of up to ~1 J mol⁻¹ K⁻¹. Above T = 300 K, some compositions exhibited negative excess heat capacities of mixing (with maximum values of −2 J mol⁻¹ K⁻¹). The vibrational entropy at 298.15 K for Or₉₀An₁₀ and Or₈₀An₂₀ deviated strongly from the behaviour of a mechanical mixture, with excess entropy values of ~3.5 J mol⁻¹ K⁻¹. More An-rich members had only small excess vibrational entropies at T = 298.15 K. The difference in behaviour between members with An > 20 mol% and those with An ≤ 20 mol% is probably a consequence of the structural state of the (K,Ca)-feldspars, i.e., (K,Ca)-feldspars with An ≤ 20 mol% have monoclinic symmetry, whereas those with An > 20 mol% are triclinic. At T = 800 K, the vibrational entropy values were found to scatter around the values expected for a mechanical mixture and, thus, correspond to a quasi-ideal behaviour. The solvus for the (K,Ca)-feldspar binary was calculated based on the entropy data from this study in combination with enthalpy and volume of mixing data from a previous study.     

A ternary feldspar-mixing model based on calorimetric data: development and application

A mixing model for high structural state ternary feldspars in the NaAlSi₃O₈–KAlSi₃O₈–CaAl₂Si₂O₈ system is presented based exclusively on calorimetric and volumetric measurements. Comparisons with existing mixing models, which are based on phase-equilibrium experiments, reveal distinct differences. The incorporation of K into Ca-rich plagioclase and of Ca into K-rich alkali feldspar is more strongly limited by our calorimetry-based model, whereas the stability field of Na-rich feldspars is broadened. Natural feldspar assemblages from well-studied magmatic and high-grade metamorphic rocks (i.e. a teschenite sill in Scotland, the Klokken syenogabbro in Greenland, and a granulite-facies metapelite in Sri Lanka) were used to test the mixing models. It was found that the new model largely eliminates discrepancies between observed and predicted feldspar compositions that were present in earlier attempts. The reasons for the problems associated with phase-equilibrium based mixing models are discussed.     

Wechselwirkungsreaktionen Untertagedeponie-relevanter chemisch-toxischer Abfälle mit hochsalinaren Lösungen

The complex reactions between high saline solutions and toxic chemical wastes were investigated by means of laboratory experiments and geochemical modelling. The specific boundary conditions of an underground repository in salt formations were taken into account. In order to determine the chemical equilibrium compositions of the resulting solutions a new leaching procedure was developed and successfully employed with several toxic wastes. The results for a fly ash waste stemming from a glass smelting furnace are given in detail. Zinc and cadmium are the two most prominent heavy metals, that accumulate significantly in the leachates. In order to gain an insight into the complex dissolution and precipitation processes in such multi-component systems, geochemical modelling was performed using the program code EQ3/6 and the Pitzer formalism for calculating the activity coefficients. The thermodynamic database used was extended and Pitzer coefficients for Zn and Cd in high saline solutions were derived from literature data and added to the database. The results of the geochemical modelling of the investigated reactions were in good agreement with the experimental data. On this basis the maximum concentrations that can be leached from the investigated fly ash into a Mg-rich saline solution, that is typical for a salt repository in Northern Germany, are predicted to be 0,181 mol/kg H₂O zinc and 0,00317 mol/kg H₂O cadmium, respectively.     

Theoretical Studies of the Parameterization of the Non-Neutral Surface Boundary Layer

The parameterization of the non-neutral atmospheric surface layer has been reexamined using the basic principles of small-scale energetics and thermodynamics. On the basis of this more complete treatment, the K- parameterization has been reformulated. It is found that the linear regression laws between fluxes and driving gradient forces of the turbulent heat and humidity exchanges in the surface layer can be derived in a much more comprehensive manner than by using the commonly used K-theory. With respect to stationary conditions and in the context of similarity concepts, a system of algebraic equations has been formulated which provides reasonable estimates of the distributions of the dimension-less rates of viscous energy dissipation as well as turbulent kinetic and thermal-diffusive energy transport as functions of the variable z/L. Quantitative calculations have been performed using the scaling height formulations of Takeuchi and Yokoyama, Prandtl, and von Kármán as closure conditions of the equations.