Partitioning of boron among melt, brine and vapor in the system haplogranite–H2O–NaCl at 800 °C and 100 MPa

Fluid-saturated experiments were conducted to investigate the partitioning of boron among haplogranitic melt, aqueous vapor and brine at 800 °C and 100 MPa. Experiments were carried out in cold-seal pressure vessels for 1 to 21 days, and utilized powdered synthetic subaluminous haplogranite glass doped with 1000 ppm B (crystalline H₃BO₃) and variable amounts of NaCl and H₂O at a fluid/haplogranite mass RATIO=1:1. Run-product glasses were analyzed for boron concentration by secondary ion mass spectrometry (SIMS) and for major elements and chlorine by electron microprobe. The composition of the coexisting fluid was calculated by mass balance. Boron partition coefficients between aqueous vapor and hydrous granitic melt range from 3.1 to 6.3, and demonstrate a clear preference of boron for the vapor over the hydrous melt. Partition coefficients between brine and hydrous granitic melt vary from 0.45 to 1.1, suggesting that boron has no preference for the brine or the melt. The bulk fluid–melt partition coefficients for low-salinity and high-salinity experiments are D_B^(vapor/melt)=4.6±1.3 and D_B^(brine/melt)=0.91±0.49, respectively. The corresponding vapor–brine partition coefficient is 5.0±3.1, demonstrating that boron partitions preferentially into the vapor over the brine at the conditions of this study. The preferential incorporation of boron in the aqueous vapor is controlled by borate speciation and solution mechanism. The dominant borate species in aqueous fluids, H₃BO₃^o, is highly soluble in aqueous vapor (X_B2O3=0.187); however, B₂O₃ is immiscible in NaCl liquid. Consequently, concentrations of boron in aqueous vapor are significantly higher than in the coexisting brine. Furthermore, Na–B complexing in the melt at high chlorine fluid contents stabilizes boron in the melt thereby contributing to the non-preferential partitioning of boron between brine and melt. The commonly observed association of tourmalinization (boron metasomatism), brecciation and ore deposition in nature is consistent with the preferential partitioning of boron into aqueous vapor of magmatic-hydrothermal systems predicted by this study.     

Coupling an equation of state and Henry's Law to model the phase equilibria of gases and brines: Examples in the N2–H2O–NaCl system

We propose a thermodynamic model for the mixing of gases in aqueous sodium chloride solutions valid to high pressures, high temperatures, and high ionic strength solutions. Our model couples Henry's Law with any equation of state to reproduce experimental data in the aqueous-rich liquid and gas-rich vapor region. In our model, the chemical potential of the solute in the brine is related to the chemical potential of the solute in pure water through salting-out coefficients. The model reproduces all crucial phenomena of binary (gas–water) and pseudo-binary (gas–water–salt) vapor–liquid mixtures below their critical point. We applied the model to reproduce the phase behavior of nitrogen in water and NaCl brines. Results and discussions are shown.