Modeling secular changes in seawater chemistry accurately requires inclusion of environmental controls on low-temperature, off-axis, hydrothermal fluxes

There are sharp rises in the Sr- and Li-isotopic composition of seawater at the Eocene-Oligocene boundary that are generally thought to be associated with Himalayan uplift and associated climatic changes and continental weathering variability. In modeling such data the norm is to hold the chemical fluxes associated with off-axis hydrothermal circulation through the oceanic crust constant while varying the river fluxes (and/or isotopic ratios). There is, however, no a priori reason to assume the chemical fluxes (or isotopic compositions) associated with off-axis hydrothermal systems should stay constant. Instead, changing environmental conditions (e.g. seawater composition and bottom water temperature) will lead to changes in these fluxes. An alternative model to explain the sharp rise in the Sr- and Li-isotopic composition of seawater at the Eocene-Oligocene boundary is cooling of the deep ocean. Decreased reaction rates in the oceanic crust, due to decreasing temperature, can be shown to lead to a decrease in the flux of unradiogenic Sr into the ocean. The magnitude matches, within uncertainty, that required to explain the increase in seawater Sr-isotopic composition [Coogan and Dosso, in review]. The story for Li is more uncertain. Two factors may lead to smaller effective fractionation factors between seawater and the (large) Li sink in the oceanic crust when bottom water is warmer: (i) higher temperature will decrease the isotopic fractionation factor; (ii) the more extensive fluid-rock reaction in the ocean crust when bottom water is warmer will make Li uptake by the oceanic crust more efficient. All other things being equal this will lead to a lower Li content of seawater. In turn, a lower Li content in seawater will mean that for a given Li-uptake rate by the crust the effective fractionation factor is smaller, due to Rayleigh distillation of Li-isotopes during fluid-rock reaction in the oceanic crust. In combination these factors predict a significant (many per mil), but poorly constrained, increase in the Li-isotopic composition of the ocean due to cooling bottom water. Models of many geochemical species, including carbon [Coogan and Gillis, 2013], should include environmentally dependent fluxes from off-axis hydrothermal systems.