Experimental Na-K distribution between amphiboles and aqueous chloride solutions, and a mixing model along the richterite – K-richterite join

The cation exchange equilibrium has been investigated by hydrothermal experiments at 700 and 800°C at 200 MPa. To avoid equilibration problems of conventional exchange experiments, we synthesized amphiboles with an excess fluid allowing exchange between solid and fluid during the experiment. The exchangeable cations Na and K were provided as excess 1 to 2n chloridic solution. These exchange syntheses can be described by the reaction equation with ^(aq) for hydroxides and chlorides in aqueous solutions and _{( s )} and _{( p )}?=?start and product fluid. The amphiboles grew in presence of the exchange fluid and adjusted their stoichiometry in equilibrium with the fluid phase. The solid products consist of more than 99% amphibole (Na,K-richterite_ss) with traces of diopside and quartz. The amphiboles are up to 1?mm long and often ≈ 40 μm thick. Detailed EMP- and HRTEM-observations show that they are chemically homogeneous and structurally wellordered. The experimental results give consistent phase relations in the reciprocal ternary system Na-richterite–K-richterite–NaCl–KCl. We analysed the product fluid with AAS- and ICP-methods. The Na-K distribution coefficients between fluid and amphiboles of the richterite–K-richterite join are close to unity at 700°C and 800°C at 200 MPa. Small systematic deviations are explained by a symmetric solution model for the A-position of the amphiboles. Using ideal mixing for H₂O-NaCl-KCl fluids, a mixing model for the system richterite–K-richterite is presented. We suggest that the composition of richterite solid solutions can be used as a sensor for NaCl/KCl-ratios in metamorphic fluids.     

The geochemical cycle of boron: Constraints from boron isotope partitioning experiments between mica and fluid

The fractionation of boron isotopes between synthetic boromuscovite and fluid was experimentally determined at 3.0 GPa/500 °C and 3.0 GPa/700 °C. For near-neutral fluids Δ¹¹B_(mica-fluid) = δ¹¹B_(mica) − δ¹¹B_(fluid) is − 10.9 ± 1.3‰ at 500 °C, and − 6.5 ± 0.4‰ at 700 °C. This supports earlier assumptions that the main fractionation effect is due to the change from trigonal coordination of boron in neutral fluids to tetrahedrally coordinated boron in micas, clays and melts. The T-dependence of this effect is approximated by the equation Δ¹¹B_{(mica,clay,melt–neutral fluid)} = − 10.69 · (1000/T [K]) + 3.88; R² = 0.992, valid from 25 °C for fluid–clay up to about 1000 °C for fluid–silicate melt. Experiments at 0.4 GPa that used strongly basic fluids produced significantly lower fractionations with Δ¹¹B_{(mica–fluid)} of − 7.4 ± 1.0‰ at 400 °C, and − 4.8 ± 1.0‰ at 500 °C, showing the reduced fractionation effect when large amounts of boron in basic fluids are tetrahedrally coordinated. Field studies have shown that boron concentrations and ¹¹B/¹⁰B-ratios in volcanic arcs systematically decrease across the arc with increasing distance from the trench, thus reflecting the thermal structure of the subducting slab. Our experiments show that the boron isotopic signature in volcanic arcs probably results from continuous dehydration of micas along a distinct P–T range. Continuous slab dehydration and boron transport via fluid into the mantle wedge is responsible for the boron isotopic signature in volcanic arcs.     

Chemical and isotopic effects of retrogression in metamorphic fluid inclusions

Fluid inclusions may provide compositional and isotopic information about fluids from which the host mineral precipitated as long as the host mineral does not react with the fluid. Our transmission electron microscope (TEM) investigation of grain boundaries and of fluid inclusions in zoisite and quartz of high-pressure metamorphic rocks from Dabie Shan (eastern China) demonstrates daughter minerals, such as margarite, muscovite, calcite, and anhydrite. Their precipitation changes (1) the composition of the fluid by selective and mineral-specific removal of CO₂ (carbonates), H₂O (sheet silicates, hydration of the walls), or S (gypsum, anhydrite, sulfides), (2) the concentrations and proportions of ions dissolved in the fluid, and (3) the isotopic composition of the fluid because of isotopic fractionation between mineral precipitate and fluid and between unmixed fluids. Fluid leakage from overpressurized fluid inclusions with daughter minerals changes the overall chemical and isotopic composition of the inclusion irreversibly, even when the daughter crystals later redissolve. Such fluid loss yields a wide range of compositionally and isotopically different fluids from a single starting fluid. Depending on the relation between mineral reactions in and fluid loss from the inclusion, the fluid remaining in the inclusion and the fluid lost from the inclusion may appear entirely unrelated.     

Proposal for applying a component-based mixture approach for ecotoxicological assessment of fracturing fluids

Hydraulic fracturing is increasingly being used to produce gas from unconventional resource sites for energy supply. Therefore, concerns about risks of this technology related to human health and the environment have to be addressed. Among the major issues is the potential contamination of surrounding water systems by chemical additives used in fracturing fluids. In this study, the ecotoxicological hazards of fracturing fluids, both, their individual components (chemicals) as well as their mixtures (product) were assessed using a component-based mixture approach. For five exemplary fracturing fluids, 40–90 wt% of the contained substances could unambiguously be defined in their chemical identity. The concentrations used in the applied fluid mixture were considered as (maximum) exposure concentrations. For components with mass fractions between 10 and 74 wt%, the effect concentrations for acute and chronic toxicity of fish, daphnia and algae were retrieved from experimental databases and through predictive modeling. The hazard indices calculated from the ratio of exposure to effect concentration were >1 for all fracturing fluids, using different scenarios. This indicated a hazard from the undiluted fracturing fluids. The assessment framework presented in this study allows for dealing with data gaps and uncertainties in a tiered fashion and in particular accommodates for combined effects resulting from chemical mixtures. It might be employed for ecotoxicological risk assessment of products containing chemical mixtures and optimization of their environmental performance.     

Generation and emplacement of shear-related highly mobile crustal melts: the synkinematic leucogranites from the Variscan Tormes Dome, Western Spain

The Tormes dome consists of S-type granites that intruded into Ordovician augen gneisses and Neoproterozoic–Lower Cambrian metapelites/metagreywackes at different extents of migmatization. S-type granites are mainly equigranular two-mica granites, occurring as: (1) enclave-laden subvertical feeder dykes, (2) small external sill-like bodies with size and shape relations indicative for self-similar pluton growth, and (3) as large pluton bodies, emplaced at higher levels than the external ones. These magmas were highly mobile as it is inferred from the high contents of fluxing components, the disintegration and alignment of pelitic xenoliths in feeder dykes and at the bottom of some sill-like bodies. Field relations relate this 311?Ma magmatism (U–Pb monazite) to the regional shearing of the D₃ Variscan event. Partial melting modeling and the relatively high estimated liquidus temperatures indicate biotite-dehydration partial melting (800–840°C and 400–650?MPa) rather than water-fluxed melting, implying that there was no partial melting triggered by externally derived fluids in the shear zones. Instead, the subvertical shear zones favored extraction of melts that formed during the regional migmatization event around 320?Ma. Nd isotope variation among the granites might reflect disequilibrium partial melting or different protoliths. Mass-balance and trace element partial melting modeling strongly suggest two kinds of fertile crustal protoliths: augen gneisses and metapelites. Slight compositional variation among the leucogranites does not reflect different extent of protolith melting but is related to a small amount of fractional crystallization (<13% for the equigranular granites), which is generally more pronounced in shallower batholitic leucogranites than in the small and homogeneous sill-like bodies. The lower extent of fractional crystallization and the higher-pressure emplacement conditions of the sill-like bodies support a more restricted movement through the crust than for batholitic leucogranites.     

Interwedging and inversion structures around the trans-European suture zone in the Baltic Sea, a manifestation of compressive tectonic phases

During the evolution of continents, compressive tectonic phases can leave certain tectonic patterns in the lithosphere to be observed by reflection seismology. Also, in the area of the trans-European suture zone (TESZ) in the Baltic Sea, several relatively short, but occasionally strong, compressive phases have left their marks in the lithosphere in form of characteristic fault and thrust zones in the rigid parts of crust and mantle, especially clear and well investigated in some sediment troughs. At depth, interwedging processes seem to be generated by colliding tectonic units with different rheology, creating bi-vergent fault structures, possibly—but not necessarily—initiated by a previous subduction of intervening oceanic lithosphere. Near the surface, reactivation and inversion of previous faults are very selective. Transpressional processes and the reduced friction inside the faults are suggested to play a major role. It is assumed that the transfer of plate boundary stressed over long distances is performed mainly through the thick and rigid mantle lid, not through the thin, rigid, and heterogeneous upper crust. This assumption involves mechanisms of a vertical transfer of stresses from the mantle into the inversion area, and some signs of such a process are seen around the Tornquist Zone (TZ). Several examples of compressive transfer of stresses are shown.