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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]

Liquid–liquid immiscibility has crucial influences on geological processes, such as magma degassing and formation of ore deposits. Sulfate, as an important component, associates with many kinds of deposits. Two types of immiscibility, including (i) fluid–melt immiscibility between an aqueous solution and a sulfate melt, and (ii) fluid–fluid immiscibility between two aqueous fluids with different sulfate concentrations, have been identified for sulfate–water systems. In this study, we investigated the immiscibility behaviors of a sulfate‐ and quartz‐saturated Na2SO4–SiO2–H2O system at elevated temperature, to explore the phase relationships involving both types of immiscibility. The fluid–melt immiscibility appeared first when the Na2SO4–SiO2–H2O sample was heated to ∼270°C, and then fluid–fluid immiscibility emerged while the sample was further heated to ∼450°C. At this stage, the coexistence of one water‐saturated sulfate melt and two aqueous fluids with distinct sulfate concentrations was observed. The three immiscible phases remain stable over a wide pressure–temperature range, and the appearance temperature of the fluid–fluid immiscibility increases with the increased pressure. Considering that sulfate components occur extensively in carbonatite‐related deposits, the fluid–fluid immiscibility can result in significant sulfate fractionation and provides implications for understanding the formation of carbonatite‐related rare earth deposits. [ABSTRACT FROM AUTHOR]

In situ Raman spectra of aqueous K2WO4-HCl, K2WO4-HCl-NaCl, and K2WO4-CO2-NaCl solutions were collected at elevated temperature (T , 100–400°C) and constant pressure (P) of 30 MPa. The stretching vibration band of the W=O bond ( v 1 ) was analyzed to reveal the species of tungsten (W) responsible for the hydrothermal transport of W during mineralization. Results showed that monomeric tungstates with v 1 (W=O) bands at ~930 and 950 cm-1 are the dominant W species in weakly alkaline (room temperature, pH = 7.7) to near-neutral (room temperature, pH = 7.2) solutions under the investigated T ‐ P conditions. Overall, the stability of polymeric tungstate species with v 1 (W=O) bands at ~965–995 cm-1 decreases with rising temperature and was not detected at ≥300°C in moderately acidic solution (room temperature, pH = 4.9). However, increased fluid acidity and salinity obviously enlarged the temperature stability field of polymeric tungstate species. In highly acidic solution (room temperature, pH = 1.4), polymeric tungstates are the only stable W species even at 400°C. In the presence of 1.9 mol/kg NaCl, polymeric tungstate(s) can persist to at least 350°C in moderately acidic solution. Considering that 300–350°C is the major W-mineralizing T range and W-mineralizing fluid is generally characterized by a moderately acidic nature, we propose that, in addition to monomeric tungstates, polymeric tungstates can also be important W species in some natural geological fluids that are responsible for the mineralization of W. Future studies of the W mineralization mechanism should take this issue into account. [ABSTRACT FROM AUTHOR]