Lithium speciation in aqueous fluids at high P and T studied by ab initio molecular dynamics and consequences for Li-isotope fractionation between minerals and fluids

Ab initio molecular dynamics simulations are performed to study the speciation changes in lithium bearing aqueous fluids at high temperature (T = 1000 K) and high pressures, P, between about 0.3 and 6.0 GPa. The simulations show a linear increase in Li coordination with fluid density, from 3.2 to about five in the considered pressure range. Towards low densities, associated LiF complexes are becoming increasingly stable, which is quantified by evaluating the dynamic behavior of the respective species. In the high-density region, HF complexes are observed. The differences in speciation may be related to structural changes of the solvent under compression. At a fluid density of 1.2 g/cm³, kinks in the pressure dependences of the oxygen–oxygen nearest neighbor distance and the oxygen–oxygen coordination are observed, which indicates a change in compaction mechanism. Assuming that the Li coordination difference between crystal and fluid is a major determinant for the isotopic fractionation between minerals and fluids, we expect only a small pressure dependence of the Li isotopic fractionation between Li bearing fluids and minerals. Our simulation results are consistent with experimental data that show reverse fractionation of ⁷Li between fluid and mineral, when Li is in tetrahedral instead of octahedral coordination in the crystal.     

Synthesis, structure, thermodynamic properties, and stability relations of K-cymrite, K[AlSi3O8]·H2O

Single-phase K-cymrite, K[AlSi₃O₈]·H₂O, has been synthesized in the P-T range 3≤P(GPa)≤4 and 350≤T(°C)≤650, and characterized by a variety of techniques like SEM, FTIR, and ²⁹Si MAS-NMR. Its thermal expansivity and compressibility have been measured up to 375?°C and 6.0?GPa, respectively. Within the uncertainty of the microchemical determination of H₂O by Karl-Fischer titration, it invariably contains 1?mol of H₂O per mol of KAlSi₃O₈. Under the SEM, it appears a small idiomorphic prisms. It is optically negative, with n _o=1.553(1) and n _e=1.521(1). FTIR spectrum identifies the water in its structure as molecular H₂O. Its lattice constants are a=5.3348(1)?Å, c=7.7057(1) Å, V= 189.924 ų, the space group being P6/mmm. The ²⁹Si MAS-NMR suggests a weak short-range order of Al and Si in the symmetrically equivalent tetrahedral sites. A Rietveld structure refinement demonstrates that it is isostructural with cymrite (BaAl₂Si₂O₈·H₂O), the structure comprising double tetrahedral sheets with H₂O molecules residing in their cavities, K serving as an interlayer cation. Whereas cymrite, with its ordered tetrahedral Al/Si distribution, shows a Pm symmetry, the weak short-range Al/Si order in K-cymrite (abbreviated below as KCym) makes it crystallize in the space group P6/mmm. Three reversal experiments on the reaction K[AlSi₃O₈]·H₂O (KCym)=K[AlSi₃O₈] (Kfs)+H₂O, executed in this study, confirm the earlier results of Thompson (1994) and supplement her data. A simultaneous treatment of those reversals, together with the thermodynamic data for Kfs and H₂O available in the literature, helps derive the standard enthalpy of formation (?4233±9.4?kJ/mol) and standard entropy (276.3±10.2 J/K·mol) for K-cymrite. The computed phase relations of KCym in the KAlSi₃O₈-H₂O binary are shown in Figure 4 for three different values of a_{H 2}O. Given a 5?°C/km isotherm in a subducting slab of metasediments in a ultra-high-pressure metamorphic environment, KCym will be expected to grow by hydration of Kfs, unless the a_{H 2}O had been substantially less than 0.5. Nevertheless, how far it can survive exhumation of the subducted terrain will depend critically on the rate of uplifting and on the a_{H 2}O prevailing during that process.     

A stochastic model for 3-dimensional flow patterns in infiltration experiments

Modelling the 3-dimensional water flux at field scale is important for the design and the analysis of dye tracer experiments. Furthermore, it enables the estimation of the risk to groundwater by pollutants, and the visualisation and classification of flux patterns. A stochastic model is presented that allows for the modelling of a wide range of flow patterns in soils as they appear in dye tracer experiments. The leading idea is that infiltrating water runs along paths, not necessarily preferential ones, and water spreads into the soil uniformly from the paths into the matrix. The model is essentially based on a Poisson point process and three independent random fields. The point process defines the starting points of the paths at the surface. The values of two random fields determine the course of the paths. The third random field governs the depth of the infiltration front. As an extension of the model, we present two simulated examples for stratified soils.     

Episodic mineralization of hydrothermal illite in the Soultz-sous-Forêts granite (Upper Rhine Graben, France)

Episodic and localized illite mineralization is documented in the hydrothermally altered Soultz-sous-Forêts granite (Upper Rhine Graben, France). Separated grain-size fractions of altered granite and argillite vein samples contain mixtures of 2M₁ and 1M trans-vacant illite varieties. The platy pseudohexagonal 2M₁ illite phases dominate the vein fillings, whereas the 1M illite occurs largely as a fibrous pore-filling variety, which is particularly abundant in the granite matrix. Multiple phases of fluid injections into the granite body have resulted in different illite assemblages, each sample containing a mixture of polytype generations formed during different crystal growth events. On the basis of mineralogical and K–Ar isotopic constraints, the ages of these vein-mineralizing events are determined by plotting the K–Ar values of the various grain-size fractions against polytype abundance and the fitted volume-weighted crystallite thickness distributions. The results suggest a Permian age for the formation of the studied argillite veins, characterized by successive injections of hydrothermal fluids. Secondary episodes of illite crystallization occurred during Jurassic and Cretaceous (or even younger times) in both the veins and the granite matrix. There are indications that the polytype structure and composition of illite were strongly influenced by variations in fluid chemistry and the degree of fluid–rock interaction as the granite was progressively sealed during post-Variscan, episodic hydrothermal activity.     

Palaeoenvironmental Reconstructions Based on Geochemical Parameters from Annually Laminated Sediments of Sacrower See (northeastern Germany) Since the 17th Century

The history of hardwater lake Sacrower See (Brandenburg, northeastern Germany) was reconstructed back to the 17th century based on a multi-proxy study of five short sediment cores dated by varve chronology, ²¹⁰Pb and ¹³⁷Cs isotopes. We were able to distinguish three main phases: The lake was mesotrophic prior to the 1830s with an oxic hypolimnion. From the early 19th century on, δ¹³C of organic matter indicates that primary productivity starts to increase slowly. Between the 1830s and 1872, the lake went through a transition towards eutrophy. Low calcite contents in the homogeneous sediment are caused by dissolution connected to increasing primary productivity and growing importance of decomposition processes. After 1873, and accelerated since 1963, Sacrower See is characterised by growing nutrient input, and thus further increasing primary productivity. The lake is eutrophic, and decomposition of organic matter causes high oxygen consumption in the hypolimnion, which becomes regularly anoxic during thermal summer stratification. Biogenic varves are preserved in the sediment, characterised by layers of autochthonous, biochemically precipitated calcite crystals. In this study, we were able to demonstrate that Sacrower See is an example of exceptional slow increase of anthropogenically enhanced nutrient input, and of the imprint which these processes have on sediments of a hardwater lake.     

Improvement of surface run‐off in the hydrological model ParFlow by a scale‐consistent river parameterization

We propose an improvement of the overland‐flow parameterization in a distributed hydrological model, which uses a constant horizontal grid resolution and employs the kinematic wave approximation for both hillslope and river channel flow. The standard parameterization lacks any channel flow characteristics for rivers, which results in reduced river flow velocities for streams narrower than the horizontal grid resolution. Moreover, the surface areas, through which these wider model rivers may exchange water with the subsurface, are larger than the real river channels potentially leading to unrealistic vertical flows. We propose an approximation of the subscale channel flow by scaling Manning's roughness in the kinematic wave formulation via a relationship between river width and grid cell size, following a simplified version of the Barré de Saint‐Venant equations (Manning–Strickler equations). The too large exchange areas between model rivers and the subsurface are compensated by a grid resolution‐dependent scaling of the infiltration/exfiltration rate across river beds. We test both scaling approaches in the integrated hydrological model ParFlow. An empirical relation is used for estimating the true river width from the mean annual discharge. Our simulations show that the scaling of the roughness coefficient and the hydraulic conductivity effectively corrects overland flow velocities calculated on the coarse grid leading to a better representation of flood waves in the river channels.     

Zooplankton distribution patterns at two seamounts in the subtropical and tropical NE Atlantic

Spatial distribution patterns of zooplankton biomass in relation to local and large‐scale hydrographical and biological driving forces were studied at Ampère and Senghor, two shallow seamounts in the subtropical and tropical NE Atlantic, respectively. The study includes a first assessment of the taxonomic composition and an estimation of the respiratory carbon demand of the zooplankton community. Zooplankton was sampled during three cruises at the seamount and open ocean reference sites in May and October 2009 and in December 2010. Zooplankton standing stocks and the corresponding respiratory carbon demand were about six times higher at Senghor than at Ampère, with mean stocks of 24.7 and 4.6 g·m^?2, respectively, in the upper 1000 m. Mean respiratory carbon demand in the epipelagic zone was calculated as 61.4 mg·C·m^?2·day^?1 for Senghor and 9.6 mg·C·m^?2·day^?1 for Ampère. At neither site were differences between seamount and open ocean sites significant. However, horizontal surveys across Ampère Seamount show clear differences between day and night distributions and a reduced biomass above the summit. Across Senghor, zooplankton biomass increased from the SW to the NE flank, with the highest concentrations in the subsurface layer of the chlorophyll maximum and just above a strong oxycline. The zooplankton community at Ampère Seamount reflects the oligotrophic character of the NE Atlantic subtropical gyre, whereas the nutrient‐rich waters of the cyclonic tropical gyre at Senghor support a higher biomass. This difference in the zooplankton biomass between the two seamounts can be attributed to the large‐scale hydrographical features governing the productivity regimes rather than to regional seamount effects.