Zircon coronas around Fe–Ti oxides: a physical reference frame for metamorphic and metasomatic reactions

Ilmenite in coronitic gabbros from the Bamble and Kongsberg sectors, southern Norway, is surrounded by zircons ranging in diameters from a fraction of a micrometer to 10 μm across. The zircons are inert during subsequent metamorphism (amphibolite- to pumpellyite–prehnite facies) and metasomatism (scapolitization and albitization) and can be found as trails in silicates (phlogopite, talc, chlorite, amphibole, albite, and tourmaline) in the altered rocks. The trails link up to form polygons outlining the former oxide grain boundary. This 3-dimensional framework of zircons is used to (a) recognize metasomatic origin of rocks, (b) quantify the mobility of elements during mineral replacement, (c) establish the growth direction of reaction fronts and to identify the reaction mechanism as dissolution–reprecipitation. Zircon coronas on Fe–Ti oxides have been described from a number of terrains and appear to be common in mafic rocks (gabbros and granulites) providing a tool for a better understanding of metasomatic and metamorphic reactions.     

Complex replacement patterns in garnets from Bergen Arcs eclogites: A combined EBSD and analytical TEM study

Eclogite-facies rocks within the Bergen Arcs, western Norway, have formed from granulites along shear zones and fluid pathways. Garnets that were inherited from granulite facies protoliths show different types of replacement patterns due to an incomplete eclogitisation process including concentric rim zoning, zoning along vein fillings and inclusion trails, and zoning bands without inclusions. The interfacial part between the granulitic core and the eclogitic rim of garnet as well as the microstructure of other relevant minerals (omphacite, plagioclase) has been analysed using analytical transmission electron microscopy (ATEM). In garnet, the interface is characterised by gradual changes in composition from X_alm=0.31, X_pyr=0.50 to X_alm=0.54, and X_pyr=0.25 within ≈20 μm and exhibits no distinct change in microstructure. Granulitic plagioclase shows exsolution lamellae of the Bøggild intergrowth. In omphacite, anti-phase domains (APDs) which potentially record the temperature of cation ordering after mineral growth have been observed and their size suggest eclogitisation at 600–700 °C. The electron backscatter diffraction (EBSD) analysis revealed that the lattice orientation of the granulitic feldspar is basically unrelated to tectonic axes whereas newly formed eclogitic minerals omphacite and kyanite show a crystallographic relation to the foliation. In garnet, no change in the basic crystallographic orientation between the eclogitic and granulitic garnet composition was confirmed. However, misorientation analysis suggests a cellular microstructure not more than 1° misorientation in the core of the garnets, which is missing in the eclogitic rim indicating textural equilibration of the latter. The heterogeneous replacement patterns are characteristic for dissolution and re-precipitation reactions in an open system limited to fluid availability. The appearance of the compositional profile in garnet is interpreted as a diffusional re-equilibration step after the time-limited, fluid-mediated eclogitisation event that apparently obscured the initially sharp interface within the further retrograde metamorphic history.     

The influence of island generated eddies on the carbon dioxide system, south of the Canary Islands

Measurements of surface partial pressure of CO₂ and water column alkalinity, pH_T, nutrients, oxygen, fluorescence and hydrography were carried out, south of the Canary Islands during September 1998. Cyclonic and anticyclonic eddies were alternatively observed from the northwestern area to the central area of the Canary Islands. Nutrient pumping and vertical uplifting of the deep chlorophyll maximum by cyclonic eddies were also ascertained by upward displacement of dissolved inorganic carbon. A model was applied to determine the net inorganic carbon balance in the cyclonic eddy. The fluxes were determined considering both the diffusive and convective contributions from the upward pumping and the corresponding horizontal transport of water outside the area. An increase in the total inorganic carbon concentration in the upper layers inside the eddy field of 133 mmol C m^− 2 d^− 1 was determined. The upward flux of inorganic carbon decreased the effect of the increased primary production on the carbon dioxide chemistry. The reduced fCO₂ inside the cyclonic eddy, 15 μatm lower than that observed in non-affected surface water, was explained by thermodynamic aspects, biological activity, eddy upward pumping and diffusion and air–sea water exchange effects.     

The Glueckstadt Graben of the North-German Basin: new insights into the structure from 3D and 2D gravity analyses

The structure of the Glueckstadt Graben has been investigated by use of 3D gravity backstripping technique and by 2D gravity and magnetic modelling. Subtracting the gravity effects of the Meso-Cenozoic sediments together with Permian salt reveals a positive residual anomaly within the Glueckstadt Graben. This anomaly includes two local maxima over the Westholstein and Eastholstein Troughs. The 2D gravity models point to the presence of a high-density body within the lower crust of the Glueckstadt Graben. In addition, the results of 2D magnetic modelling indicate that the central part of the high-density body is overlain by an area with high susceptibility. Most probable, the formation of this high-density body is a result of complex poly-phase tectonic history of the study area. Finally, the results of gravity modelling indicate that Permian salt is not homogeneous. 3D gravity analysis and, especially, 2D gravity modelling have distinguished the differences in degree of salt saturation in salt-rich bodies, and elucidate the proportion of Rotliegend salt.     

Monte Carlo simulation of mixing in Ca3Fe2Ge3O12–Ca4Ge4O12 garnets and implications for the thermodynamic stability of pyrope–majorite solid solution

Static lattice energy calculations, based on empirical pair potentials, were performed for a large set of structures differing in the arrangement of octahedral cations within the garnet 2 × 2 × 2 supercell. The compositions of these structures varied between Ca₃Fe₂Ge₃O₁₂ and Ca₄Ge₄O₁₂. The energies were cluster expanded using pair and quaternary terms. The derived ordering constants were used to constrain Monte Carlo simulations of temperature-dependent mixing properties in the ranges of 1,073–3,673 K and 0–10 GPa. The free energies of mixing were calculated using the method of thermodynamic integration. The calculations predict a wide miscibility gap between Fe-rich (cubic) and Fe-pure (tetragonal) garnets consistent with recent experimental observations of Iezzi et al. (Phys Chem Miner 32:197–207, 2005). It is shown that the miscibility gap arises due to a very strong cation ordering at the Fe-pure composition, driven by the charge difference between Ca²⁺ and Ge⁴⁺ cations. The structural and thermodynamic analogies between Ca–Ge and Mg–Si systems suggest that a similar miscibility gap should exist between pyrope and Mg–Si-majorite.     

The kinetics of nucleation of solid solutions from aqueous solutions: a new model for calculating non-equilibrium distribution coefficients

The nucleation kinetics of binary solid solutions, with general formula B_xC_1−xA, crystallising from aqueous solution can be described using a generalised expression for the nucleation rate: the function, J(x), in which supersaturation, interfacial free energy and other parameters of the classical nucleation rate equation are considered as functions of the solid composition. As an example, we studied the behaviour of such J(x) functions for the case of the (Ba,Sr)SO₄ and (Ba,Sr)CO₃ solid solutions. J(x) functions are very sensitive to slight changes in the composition of the aqueous solution, which result in strong modifications of the nucleation kinetics. The implications of the relationship between supersaturation and nucleation rate functions for the general nucleation behaviour in solid solution-aqueous solution (SS-AS) systems are discussed. Finally, we present a method for constructing non-equilibrium Roozeboom diagrams based on the nucleation kinetics in SS-AS systems. Our Roozeboom diagrams calculated for different departures from equilibrium conditions are consistent with previous experimental work and they can be used to predict actual distribution coefficients.     

Geomechanical model for the post-Variscan evolution of the Permocarboniferous–Mesozoic basins in Northeast Germany

The Permocarboniferous basins in Northeast Germany formed on the heterogeneous and eroded parts of the Variscan orogene and its deformed northern foreland. Transtensional tectonic movements and thermal re-equilibration lead to medium-scale crustal fragmentation, fast subsidence rates and regional emplacement of large amounts of mostly acidic volcanics. The later basin formation and differentiation was triggered by reversals of the large-scale stress field and reactivation of prominent zones of weakness like the Elbe Fault System and the Rhenohercynian/Saxothuringian boundary that separate different Variscan basement domains in the area. The geomechanical behaviour of the latter plays an important role for the geodynamic evolution of the medium to large-scale structural units, which we can observe today in three dimensions on structural maps, geophysical recordings and digital models. This study concentrates on an area that comprises the southern Northeast German Basin, the Saale Basin, the Flechtingen High, the Harz Mountains High and the Subhercynian Basin. The presented data include re-evaluations of special geological and structural maps, the most recent interpretation of the DEKORP BASIN 9601 seismic profile and observations of exposed rock sections in Northeast Germany. On the basis of different structural inventories and different basement properties, we distinguish two structural units to the south and one structural unit to the north of the Elbe Fault System. For each unit, we propose a geomechanical model of basin formation and basin inversion, and show that the Rhenohercynian Fold and Thrust Belt domain is deformed in a thin-skinned manner, while the Mid-German Crystalline Rise Domain, which is the western part of the Saxothuringian Zone, rather shows a thick-skinned deformation pattern. The geomechanical model for the unit north to the Elbe Fault System takes account to the fact that the base of the Zechstein beneath the present Northeast German basin shows hardly any evidence for brittle deformation, which indicates a relative stable basement. Our geomechanical model suggests that the Permocarboniferous deposits may have contributed to the structural stiffness by covering small to medium scale structures of the upper parts of the brittle basement. It is further suggested that the pre-Zechstein successions underneath the present Northeast German basin were possibly strengthening during the Cretaceous basin inversion, which resulted in stress transfer to the long-lived master faults, as indicated for example by the shape of the salt domes in the vicinity of the latter faults. Contrary to this, post-Zechstein successions deformed in a different and rather complex way that was strongly biased by intensive salt tectonic movements.     

Supersaturation functions in binary solid solution-aqueous solution systems

In this paper, we present a brief review of the thermodynamic equilibrium of binary solid solution-aqueous solution (SS-AS) systems and derive an expression that allows us to evaluate the supersaturation or undersaturation of a given aqueous solution with respect to the whole range of solid compositions: the δ(x) function. Such an expression is based on the two conditions that define the SS-AS thermodynamic equilibrium. The derivation of the new supersaturation function, δ(x), was made by considering in detail the compositional relationships between solid and aqueous phases. To represent the new formulation on Lippmann diagrams, we have defined a new thermodynamic concept: the “actual activity.” In addition, we show how our supersaturation function behaves for both ideal and subregular solid solutions. The behaviour and applicability of both the δ(x) function and a previous supersaturation function, β(x), defined by Prieto et al. (1993), is discussed.