Activity of zero-valent sulfur in sulfidic natural waters

Ionic and molecular carriers of dissolved (filter-passing) zero-valent sulfur (S⁰) in anaerobic natural waters include polysulfides, S_n^2-, molecular S₈(aq), organic macromolecules and certain higher valent thioanions. Because S⁰ is rapidly transferred among these various carriers, its biogeochemical roles in such processes as dehalogenation of organic compounds, chelation of trace metals, and anaerobic microbial metabolism are not determined solely by one ionic or molecular species. Here, S⁰ is treated collectively as a virtual thermodynamic component, and computational as well as graphical methods for quantifying its activity (a_S0) in natural waters are presented. From a_S0, concentrations of the ionic and molecular carriers of S⁰ can be calculated easily.

Concentration ratios of any two polysulfide ions define a_S0 (Method I). Unfortunately these concentrations are often too low in nature for accurate quantification with current methods. Measurements of total divalent sulfur (ΣS^-II), zero-valent sulfur (ΣS⁰) and pH provide a more widely applicable approach (Method II). Systematic errors in ΣS⁰ measurements are the main limit to accuracy of this method at the present time. Alternative methods based on greigite solubility and potentiometry are discussed. A critical comparison of Methods I and II reveals inconsistencies at low ΣS⁰/ΣS^-II that imply errors in the thermodynamic data for HS₂^- and S₂^-. For samples having low ΣS⁰/ΣS^-II, an interim remedy is recommended: letting pK_a2 = 6.3 for all HS_n^- ions.

Newly assembled data for a_S0 in a selection of anaerobic natural waters indicate that S⁰ is always metastable in the surveyed samples with respect to disproportionation to sulfide and sulfate. In all the surveyed environments, sulfur-rich minerals, such as greigite, covellite and orpiment, are stable in preference to their sulfur-poor cohorts, mackinawite, chalcocite and realgar. The a_S0 values in the dataset span conditions favoring Hg-polysulfide complexes vs. Hg-sulfide complexes, implying that a_S0 could affect Hg-methylation rates in nature. No support is found for the common assumption that a_S0 = 1 in reducing natural waters. This paper calls attention to an urgent need for improved measurement methods, especially for total zero-valent sulfur, as well as new determinations of ionization constants for all HS_n^- species.