Improvements in the Quantification of End-Member Vapor Compositions in Fluid Inclusion Boiling Assemblages and Implications for Metal Transport by Low-Density Fluids

Abstract Under conditions typically found in the Earth’s crust, there is a large pressure-temperature-composition range in the H2O-NaCl system where fluids may separate into a low-salinity vapor end member and a high-salinity liquid end member. However, heterogeneous trapping is common during the formation of fluid inclusions in an immiscible fluid system, violating the fundamental assumption of homogeneous entrapment for fluid inclusion microthermometry. This has profound consequences on the composition of these fluid phases and consequently on the formation of ore deposits from hydrothermal systems. At the same time, minor mixture of the high-salinity liquid phase with the low-salinity vapor phase cannot be distinguished from the end-member vapor-rich fluid inclusions by their bubble sizes. Precise determination of the salinities of vapor-rich fluid inclusions using microthermometry is deterred by the very small proportion of the liquid phase and the limitation of the analytical precision. All this will lead to erroneous compositional data from fluid inclusion analysis. We have quantitively calculated the variations of fluid inclusion properties caused by heterogeneous entrapment during phase separation in the H2O-NaCl system and showed that the salinity, and thereby the element contents and element/Na ratios of the vapor-rich fluid inclusions, is significantly changed in heterogeneously trapped fluid inclusions. The addition of 1 vol % of the high-salinity end member to the low-salinity end member results in a salinity change from 0.99 to 4.4 wt % NaCl equiv at the phase separation condition of 800 bar and 750°C. This will have a significant impact when it comes to determining the concentration of elements transported as chlorine complexes and typically leads to an overestimation of the mass transport capability by the vapor phase. Therefore, every effort should be taken during microthermometry to find and measure the least affected vapor-rich fluid inclusions. Our numerical calculations and synthetic fluid inclusions reveal that there is a linear relationship between the salinity and element contents for fluid inclusions at different extents of heterogeneous entrapment. Therefore, linear correction to the measured lowest vapor salinity can obtain a good approximation of the element contents in the end-member vapor phase.