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\begin{document}

\title{Geochemical and Photochemical Constraints on S{[}IV{]} Concentrations in
Natural Waters on Prebiotic Earth}



\author[1]{Sukrit Ranjan}%
\author[2]{Khaled Abdelazim}%
\author[2]{Gabriella G Lozano}%
\author[3]{Sangita Mandal}%
\author[4]{Cindy Y Zhou}%
\author[2]{Corinna L Kufner}%
\author[5]{Zoe R Todd}%
\author[6]{Nita Sahai}%
\author[2]{Dimitar D Sasselov}%
\affil[1]{University of Arizona}%
\affil[2]{Harvard University}%
\affil[3]{National Institute of Science Education and Research}%
\affil[4]{Boston University}%
\affil[5]{University of Washington}%
\affil[6]{University of Akron}%


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  \date{June 13, 2024}


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\begin{abstract}
Aqueous S{[}IV{]} species (HSO\textsubscript{3}\textsuperscript{-},
SO\textsubscript{3}\textsuperscript{2-}) derived from volcanogenic
atmospheric SO\textsubscript{2} are ~important to planetary habitability
through their roles in proposed origins-of-life chemistry and influence
on atmospheric sulfur haze formation, but the early cycling of S{[}IV{]}
is poorly understood. Here, we combine new laboratory constraints on
S{[}IV{]} disproportionation kinetics with a novel aqueous
photochemistry model to estimate the concentrations of S{[}IV{]} in
natural waters on prebiotic Earth. We show that S{[}IV{]}
disproportionation is slow in pH[?] 7 waters, with timescale T[?] 1 year at
room temperature, meaning that S{[}IV{]} was present in prebiotic
natural waters. However, we also show that photolysis of S{[}IV{]} by UV
light on prebiotic Earth limited {[}S{[}IV{]}{]}\textless{} 100\selectlanguage{greek}μ\selectlanguage{english}M in
global-mean steady-state. Because of photolysis, {[}S{[}IV{]}{]} was
much lower in natural waters compared to the concentrations generally
invoked in laboratory simulations of origins-of-life chemistry ([?] 10
mM), meaning further work is needed to confirm whether laboratory
S{[}IV{]}- dependent prebiotic chemistries could have functioned in
nature. {[}S{[}IV{]}{]}[?] 1\selectlanguage{greek}μ\selectlanguage{english}M in terrestrial waters for: (1)
SO\textsubscript{2} outgassing [?] 20\selectlanguage{ngerman}× modern, (2) pond depths \textless{}
10 cm, or UV-attenuating agents present in early waters or the prebiotic
atmosphere. Marine S{[}IV{]} was sub-saturated with respect to
atmospheric SO\textsubscript{2}, meaning that atmospheric
SO\textsubscript{2} ~deposition was efficient and that, within the
constraints of present knowledge, UV-attenuating sulfur hazes could only
have persisted on prebiotic Earth if sulfur emission rates were very
high (\selectlanguage{english}[?] 100x modern). Our work illustrates the synergy between planetary
science, geochemistry and synthetic organic chemistry towards
understanding the emergence and maintenance of life on early Earth.%
\end{abstract}\selectlanguage{ngerman}%



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\textbf{NOTE: MANUSCRIPT AS ACCEPTED AT AT AGU ADVANCES (09/2023).
COMMENTS AND CRITICISM SOLICITED
AT~\href{mailto:sukrit@arizona.edu}{\nolinkurl{sukrit@arizona.edu}}.~}

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