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Barium, lanthanum, ytterbium, and yttrium partitioning experiments between fluid-saturated haplogranitic melts and aqueous solutions were conducted at 750 to 950 degrees C and 0.2 to 1 GPa to investigate the effects of melt and fluid composition, pressure, and temperature. Partition coefficients were determined using different experimental methods. On one hand quenched experiments were performed, and on the other hand, trace element contents in the aqueous fluid were determined directly using a hydrothermal diamond-anvil cell and synchrotron radiation X-ray fluorescence microanalysis of K-lines. The latter required a high excitation energy of 50 key due to the high energies necessary to excite the K-lines of the studied elements. The data from these two techniques showed good agreement for chloridic solutions, whereas quenching had a significant effect on results of the experiments with only water in the case of Ba. In Cl-free experiments, lanthanum and yttrium, trace element contents were even below detection limit in the quenched fluids, whereas small concentrations were detected in comparable in-situ experiments. This distinct difference is likely due to back reactions between fluid and melt upon cooling. The partitioning data of all elements show no dependence on the temperature and only small dependence on pressure. In contrast, the partitioning is strongly influenced by the composition of the starting fluid and melt. For chloridic fluids, there was a sharp increase in the Ba, La, Y and Yb partition coefficients with the alumina saturation index (ASI). The Ba partition coefficient increased from 0.002 at an ASI of 0.8 to 0.55 at an ASI of 1.07. At higher ASI, it decreased slightly to 0.2 at an ASI of similar to 1.3. Likewise, it was one to two orders of magnitude higher in chloridic fluids compared to those found in H2O experiments. Fluid-melt partition coefficients of La and Y increased from 0.002 at an ASI of similar to 0.8 to similar to 0.1 at an ASI of 1.2. In the same ASI range, the Yb partition coefficient increased to a maximum value of 0.02. Even at high salinities all elements fractionate into the melt. The compositional dependence of the partitioning data imply that both melt composition and fluid composition have a strong influence on trace element behavior and that complexation of Ba. REE and Y tin the fluid is not only controlled by the presence of Cl- in the fluid. Instead, interaction of these elements with major melt components dissolved in the fluid is very likely.
Trace element concentrations in aqueous fluids in equilibrium with haplogranitic melt were determined in situ at elevated P-T conditions using hydrothermal diamond-anvil cells and synchrotron-radiation XRF microanalyses. Time- resolved analyses showed that the Rb and Sr concentrations in the fluids became constant in less than 2000 s at all temperatures (500 to 780 degrees C). Although fluid-melt equilibration was very rapid, the change in the concentration of both elements in the fluid with temperature was fairly small (a slight increase for Rb and a slight decrease for Sr). This permitted partitioning data for Rb and Sr between haplogranitic melt and H2O or NaCl+KCl+HCl aqueous solutions at 750 degrees C and 200 to 700 MPa to be obtained from EMP analyses of the quenched melt and the in situ SR-XRF analyses of the equilibrated fluid. The resulting D-Rb(f/m) and D-Sr(f/m) were 0.01 +/- 0.002 and 0.006 +/- 0.001 for water as starting fluid, and increased to 0.47 +/- 0.08 and 0.23 +/- 0.03 for 3.56 m (NaCl+KCl)+0.04 in HCl at pressures of 224 to 360 MPa. In the experiments with H2O as starting fluid, the partition coefficients increased with pressure, i.e. D- Rb(f/m) from 0.01 +/- 0.002 to 0.22 +/- 0.02 and D-Sr(f/m) from 0.006 0.001 to 0.02 +/- 0.005 with a change in pressure from 360 to 700 MPa. At pressures to 360 MPa, the Rb/Sr ratio in the fluid was found to be independent of the initial salt concentration (Rb/Sr = 1.45 +/- 0.6). This ratio increased to 7.89 +/- 1.95 at 700 MPa in experiments with chloride free fluids, which indicates different changes in the Rb and Sr speciation with pressure.
Rubidium and strontium partitioning experiments between haplogranitic melts and aqueous fluids (water or 1.16- 3.56 m (NaCl + KCl) +/- HCl) were conducted at 750-950 degrees C and 0.2-1.4 GPa to investigate the effects of melt and fluid composition, pressure, and temperature. In addition, we studied if the applied technique (rapid and slow quench, and in-situ determination of trace element concentration in the fluid) has a bearing on the obtained data. There is good agreement of the data from different techniques for chloridic solutions, whereas back reactions between fluid and Melt upon cooling have a significant effect on results from the experiments with water. The Rb fluid-melt partition coefficient shows no recognizable dependence on melt composition and temperature. For chloridic Solutions, it is similar to 0.4, independent of pressure. In experiments with water, it is one to two orders of magnitude lower and increases with pressure. The strontium fluid-melt partition coefficient does not depend on temperature. It increases slightly with pressure in Cl free experiments. In chloridic fluids, there is a sharp increase in the Sr partition coefficient with the alumina saturation index (ASI) from 0.003 at an ASI of 0.8 to a maximum of 0.3 at an ASI of 1.05. At higher ASI, it decreases slightly to 0.2 at an ASI of 1.6. It is one to two orders of magnitude higher in chloridic fluids compared to those found in H2O experiments. The Rb/Sr ratio in non-chloridic solutions in equilibrium with metaluminous melts increases with pressure, whereas the Rb/Sr ratio in chloridic fluids is independent of pressure and decreases with fluid salinity. The obtained fluid-melt partition coefficients are in good agreement with data from natural cogenetic fluid and melt inclusions. Numerical modeling shows that although the Rb/Sr ratio in the residual melt is particularly sensitive to the degree of fractional crystallization, exsolution of a fluid phase, and associated fluid-melt partitioning is not a significant factor controlling Rb and Sr concentrations in the residual melt during crystallization of most granitoids.
Zircon (ZrSiO4), hafnon (HfSiO4) and five intermediate compositions were synthesized from a Pb silicate melt. The resulting crystals were 20-300 mu m in size and displayed sector and growth zoning. Raman spectra were acquired at locations in the sample for which preceding electron microprobe (EMP) analyses revealed sufficient compositional homogeneity. The dataset documents shifts of Raman bands with changing composition. In this study, bands that have previously not been reported were found for the intermediate compositions and for pure hafnon, in particular at wavenumbers less than 200 cm(-1). For these external modes, the dataset provides new insight into the compositional dependence of their frequencies. Density-functional theory calculations support the observations and are used for a detailed interpretation of the spectra. The pitfalls of the EMP analysis along the zircon-hafnon join are highlighted.
We present a new autoclave that enables in situ characterization of hydrothermal fluids at high pressures and high temperatures at synchrotron x-ray radiation sources. The autoclave has been specifically designed to enable x-ray absorption spectroscopy in fluids with applications to mineral solubility and element speciation analysis in hydrothermal fluids in complex compositions. However, other applications, such as Raman spectroscopy, in high-pressure fluids are also possible with the autoclave. First experiments were run at pressures between 100 and 600 bars and at temperatures between 25 degrees C and 550 degrees C, and preliminary results on scheelite dissolution in fluids of different compositions show that the autoclave is well suited to study the behavior of ore-forming metals at P-T conditions relevant to the Earth's crust.
The analytical evaluation of diurnal temperature variation in riverbed sediments provides detailed information on exchange fluxes between rivers and groundwater. The underlying assumption of the stationary, one-dimensional vertical flow field is frequently violated in natural systems where subsurface water flow often has a significant horizontal component. In this paper, we present a new methodology for identifying the geometry of the subsurface flow field using vertical temperature profiles. The statistical analyses are based on model optimisation and selection and are used to evaluate the shape of vertical amplitude ratio profiles. The method was applied to multiple profiles measured around in-stream geomorphological structures in a losing reach of a gravel bed river. The predominant subsurface flow field was systematically categorised in purely vertical and horizontal (hyporheic, parafluvial) components. The results highlight that river groundwater exchange flux at the head, crest and tail of geomorphological structures significantly deviated from the one-dimensional vertical flow, due to a significant horizontal component. The geometry of the subsurface water flow depended on the position around the geomorphological structures and on the river level. The methodology presented in this paper features great potential for characterising the spatial patterns and temporal dynamics of complex subsurface flow geometries by using measured temperature time series in vertical profiles. (C) 2016 Elsevier B.V. All rights reserved.
Flow patterns in conjunction with seasonal and diurnal temperature variations control ecological and biogeochemical conditions in hyporheic sediments. In particular, hyporheic temperatures have a great impact on many temperature-sensitive microbial processes. In this study, we used 3-D coupled water flow and heat transport simulations applying the HydroGeoSphere code in combination with high-resolution observations of hydraulic heads and temperatures to quantify reach-scale water and heat flux across the river-groundwater interface and hyporheic temperature dynamics of a lowland gravel bed river. The model was calibrated in order to constrain estimates of the most sensitive model parameters. The magnitude and variations of the simulated temperatures matched the observed ones, with an average mean absolute error of 0.7 degrees C and an average Nash Sutcliffe efficiency of 0.87. Our results indicate that nonsubmerged streambed structures such as gravel bars cause substantial thermal heterogeneity within the saturated sediment at the reach scale. Individual hyporheic flow path temperatures strongly depend on the flow path residence time, flow path depth, river, and groundwater temperature. Variations in individual hyporheic flow path temperatures were up to 7.9 degrees C, significantly higher than the daily average (2.8 degrees C), but still lower than the average seasonal hyporheic temperature difference (19.2 degrees C). The distribution between flow path temperatures and residence times follows a power law relationship with exponent of about 0.37. Based on this empirical relation, we further estimated the influence of hyporheic flow path residence time and temperature on oxygen consumption which was found to partly increase by up to 29% in simulations.
The application of heat as a hydrological tracer has become a standard method for quantifying water fluxes between groundwater and surface water. The typical application is to estimate vertical water fluxes in the shallow subsurface beneath streams or lakes. For this purpose, time series of temperatures in the surface water and in the sediment are measured and evaluated by a vertical 1D representation of heat transport by advection and conduction. Several analytical solutions exist to calculate the vertical water flux from the measured temperatures. Although analytical solutions can be easily implemented, they are restricted to specific boundary conditions such as a sinusoidal upper temperature boundary. Numerical solutions offer higher flexibility in the selection of the boundary conditions. This, in turn, reduces the effort of data preprocessing, such as the extraction of the diurnal temperature variation from the raw data. Here, we present software to estimate water fluxes based on temperaturesFLUX-BOT. FLUX-BOT is a numerical code written in MATLAB that calculates vertical water fluxes in saturated sediments based on the inversion of measured temperature time series observed at multiple depths. FLUX-BOT applies a centred Crank-Nicolson implicit finite difference scheme to solve the one-dimensional heat advection-conduction equation. FLUX-BOT includes functions for the inverse numerical routines, functions for visualizing the results, and a function for performing uncertainty analysis. We present applications of FLUX-BOT to synthetic and to real temperature data to demonstrate its performance.
Solute concentration variability is of fundamental importance for the chemical and ecological state of streams. It is often closely related to discharge variability and can be characterized in terms of a solute export regime. Previous studies, especially in lowland catchments, report that nitrate is often exported with an accretion pattern of increasing concentrations with increasing discharge. Several modeling approaches exist to predict the export regime of solutes from the spatial relationship of discharge generating zones with solute availability in the catchment. For a small agriculturally managed lowland catchment in central Germany, we show that this relationship is controlled by the depth to groundwater table and its temporal dynamics. Principal component analysis of groundwater level time series from wells distributed throughout the catchment allowed derivation of a representative groundwater level time series that explained most of the discharge variability. Groundwater sampling revealed consistently decreasing nitrate concentrations with an increasing thickness of the unsaturated zone. The relationships of depth to groundwater table to discharge and to nitrate concentration were parameterized and integrated to successfully model catchment discharge and nitrate export on the basis of groundwater level variations alone. This study shows that intensive and uniform agricultural land use likely results in a clear and consistent concentration-depth relationship of nitrate, which can be utilized in simple approaches to predict stream nitrate export dynamics at the catchment scale. (C) 2016 Elsevier Ltd. All rights reserved.
Dynamics of solute export from catchments can be classified in terms of chemostatic and chemodynamic export regimes by an analysis of concentration-discharge relationships. Previous studies hypothesized that distinct export regimes emerge from the presence of solute mass stores within the catchment and their connectivity to the stream. However, so far a direct link of solute export to identifiable catchment characteristics is missing. Here we investigate long-term time series of stream water quality and quantity of nine neighboring catchments in Central Germany ranging from relatively pristine mountain catchments to agriculturally dominated lowland catchments, spanning large gradients in land use, geology, and climatic conditions. Given the strong collinearity of catchment characteristics we used partial least square regression analysis to quantify the predictive power of these characteristics for median concentrations and the metrics of export regime. We can show that median concentrations and metrics of the export regimes of major ions and nutrients can indeed be inferred from catchment characteristics. Strongest predictors for median concentrations were the share of arable land, discharge per area, runoff coefficient and available water capacity in the root zone of the catchments. The available water capacity in the root zone, the share of arable land being artificially drained and the topographic gradient were found to be the most relevant predictors for the metrics of export regime. These catchment characteristics can represent the size of solute mass store such as the fraction of arable land being a measure for the store of nitrate. On the other hand, catchment characteristics can be a measure for the connectivity of these solute stores to the stream such as the fraction of tile drained land in the catchments. This study demonstrates the potential of data-driven, top down analyses using simple metrics to classify and better understand dominant controls of solute export from catchments. (C) 2015 Elsevier Ltd. All rights reserved.