Quantifying sulfur speciation in magmatic-hydrothermal fluids

TL;DR

This paper critically evaluates recent claims about sulfur species in magmatic-hydrothermal fluids, emphasizing the importance of consistent thermodynamic data and correct spectral interpretation for understanding sulfur chemistry and transport.

Contribution

It demonstrates that previous conclusions about sulfur speciation were based on inconsistent data and spectral misassignments, reaffirming the validity of existing thermodynamic models.

Findings

Previous Raman data misinterpreted sulfur species

Thermodynamic data for sulfur species are consistent and reliable

Correct spectral analysis supports established sulfur speciation models

Abstract

Quantitative knowledge of sulfur speciation in the fluid phase is key to understanding sulfur degassing from magmas and its transfer along with metals by fluids across the lithosphere. Farsang and Zajacz (1) recently reported new sulfur speciation data using Raman spectroscopy measurements on aqueous H$_2$SO$_4$-NaCl(-KCl) solutions trapped as synthetic fluid inclusions in quartz at 875$^\circ$C and 2 kbar under variable redox conditions. They interpreted the data by dominant SO$_{2(aq)}$ and HS$^-$, along with subordinate H$_2$S$_{(aq)}$, whereas the di-and trisulfur radical ions, $[S_3^\bullet]^-$ and $[S_2^\bullet]^-$, reported in aqueous fluids both in nature and experiment to at least 700 $^\circ$C and 15 kbar (2-5) , were undetectable in Raman nonresonant spectra 1 . On the basis of thermochemical calculations that returned negligible HS$^-$ and large $[S_3^\bullet]^-$ concentrations at their experimental conditions, the authors claimed that the published $[S_3^\bullet]^-$ and HS$^-$ thermodynamic data were incorrect and that the major species controlling both sulfur and gold transport in hydrothermal-magmatic fluids is the HS$^-$ anion. Here I demonstrate that their conclusions stem from the use of inconsistent thermodynamic data and incorrect Raman spectra assignments. Thus, ref. 1 provides no grounds for questioning the validity of the thermodynamic properties of HS$^-$ and $[S_3^\bullet]^-$ or of their metal complexes in the fluids of the Earth's crust.