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\begin{document}

\title{P/Ca in carbonates as a proxy for alkalinity and phosphate levels}



\author[1]{Miquela Ingalls}%
\author[2]{Clara Blättler}%
\author[3]{John Higgins}%
\author[1]{John S Magyar}%
\author[1]{John M. Eiler}%
\author[1]{Woodward Fischer}%
\affil[1]{California Institute of Technology}%
\affil[2]{University of Chicago}%
\affil[3]{Princeton University}%


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  \date{June 04, 2024}


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\begin{abstract}
Understanding mechanisms, rates, and drivers of carbonate formation
provides insight into the chemical evolution of Earth's oceans and
atmosphere. We paired geological observations with elemental and isotope
geochemistry to test potential proxies for calcium-to-alkalinity ratios
(Ca:ALK). Across diverse carbonate facies from Pleistocene closed-basin
lakes in Owens Valley, CA, we observed less \selectlanguage{greek}δ\selectlanguage{english}44/40Ca variation than
theoretically predicted (\textgreater{}0.75%0) for the very low Ca:ALK in
these systems. Carbonate clumped isotope disequilibria implied rapid
carbonate growth---kinetic isotope effects, combined with the diverse
carbonate minerals present, complicated the interpretation of [?]\selectlanguage{greek}δ\selectlanguage{english}44/40Ca
as a paleo-alkalinity proxy. In contrast, we observed that high
phosphate concentrations are recorded by shoreline and lake bottom
carbonates formed in eleven Pleistocene lakes at orders of magnitude
greater concentrations than marine carbonates. Because the maximum
phosphate content of water depends on Ca:ALK, we propose that carbonate
P/Ca can inform phosphate levels and thereby Ca:ALK of aqueous
environments in the carbonate record.%
\end{abstract}%



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