Quantifying sulfur speciation in magmatic-hydrothermal fluids

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.

💡 Research Summary

The paper under review is a critical commentary on the recent study by Farsang and Zajacz, which reported sulfur speciation in synthetic magmatic‑hydrothermal fluids using Raman spectroscopy on H₂SO₄‑NaCl(‑KCl) solutions trapped in quartz at 875 °C and 2 kbar. The original authors interpreted their non‑resonant Raman spectra as indicating that dissolved sulfur is dominated by aqueous SO₂ and the HS⁻ anion, with a minor contribution from H₂S(aq). They also claimed that the di‑ and trisulfur radical ions,