Direct H2S, HS− and pH Measurements of High‐Temperature Hydrothermal Vent Fluids With In Situ Raman Spectroscopy.

Hydrothermal H2S is an important energy source for hydrothermal ecosystems. However, it is difficult to obtain accurate hydrogen sulfide concentrations in high‐temperature hydrothermal fluids because they are highly susceptible to oxidation and compositional variability with mixing. In this study, a new in situ approach for measuring H2S, HS− and pH in hydrothermal fluids was developed and applied to the detections of Okinawa Trough hydrothermal activities. The in situ total H2S concentrations in the Jade and Biwako fluids were determined to be 31.4 and 76.7 mmol/kg, respectively. The in situ measured pH of the Jade fluids was determined to be 6.3, which has exceeded that of a neutral fluid at a specific temperature and pressure, indicating that the pH of Jade fluids is weakly alkaline. The pH transition of hydrothermal fluids from alkaline to acidic may be attributed to the thermal decomposition of organic matter and sulfide precipitation. Plain Language Summary: Hydrogen sulfide is one of the important gases released from hydrothermal systems, but it is difficult to measure its concentration accurately because it is highly susceptible to oxidation and compositional variability with mixing. The in situ pH of hydrothermal fluids is also a challenging parameter to obtain, as it is significantly affected by factors such as temperature variation and mineral precipitation. Traditional methods of sampling followed by laboratory analysis inevitably result in changes in hydrogen sulfide concentration and pH. Furthermore, conventional chemical sensors and pH electrodes cannot withstand the high‐temperature extreme environment of hydrothermal vents, making it impossible to directly obtain these parameters at the high‐temperature vent orifice. Here, we developed a new method for in situ measurement of the H2S‐HS− ionization equilibrium system based on Raman spectroscopy and used it to determine the H2S concentration and in situ pH of hydrothermal fluids in the Okinawa Trough. Key Points: The first in situ measured pH of high‐temperature hydrothermal vent fluids at arc‐back arc basins was reportedA new approach to obtain in situ H2S/HS− concentration and in situ pH of high temperature hydrothermal vent fluids was establishedThe pH transition of hydrothermal fluids from alkaline to acidic should attributes to the precipitation of sulfide minerals [ABSTRACT FROM AUTHOR]