Partitioning of Ba, La, Yb and Y between haplogranitic melts and aqueous solutions: An experimental study

Barium, lanthanum, ytterbium, and yttrium partitioning experiments between fluid-saturated haplogranitic melts and aqueous solutions were conducted at 750 to 950 °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 keV 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 ∼ 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 ∼ 0.8 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.

Research highlights
► first systematic dataset on fluid-melt partitioning of Ba, La, Y, and Yb
► first in-situ analysis of Ba, La, and Y in aqueous fluids equilibrated with silicate melts at high pressures and temperatures
► unique insights in quench processes