Linking the lithogenic, atmospheric, and biogenic cycles of silicate, carbonate, and organic carbon in the ocean

Abstract

Geochemical theory describes long term cycling of atmospheric CO2 between the atmosphere and rocks at the Earth surface in terms of rock weathering and precipitation of sedimentary minerals. Chemical weathering of silicate rocks takes up atmospheric CO2, releases cations and HCO3− to water, and precipitates SiO2, while CaCO3 precipitation consumes Ca2+ and HCO3− and releases one mole of CO2 to the atmosphere for each mole of CaCO3 precipitated. At steady state, according to this theory, the CO2 uptake and release should equal one another. In contradiction to this theory, carbonate precipitation in the present surface ocean releases only about 0.6 mol of CO2 per mole of carbonate precipitated. This is a result of the buffer effect described by Ψ, the molar ratio of net CO2 gas evasion to net CaCO3 precipitation from seawater in pCO2 equilibrium with the atmosphere. This asymmetry in CO2 flux between weathering and precipitation would quickly exhaust atmospheric CO2, posing a conundrum in the classical weathering and precipitation cycle. While often treated as a constant, Ψ actually varies as a function of salinity, pCO2, and temperature. Introduction of organic C reactions into the weathering-precipitation couplet largely reconciles the relationship. ψ in the North Pacific Ocean central gyre rises from 0.6 to 0.9, as a consequence of organic matter oxidation in the water column. ψ records the combined effect of CaCO3 and organic reactions and storage of dissolved inorganic carbon in the ocean, as well as CO2 gas exchange between the ocean and atmosphere. Further, in the absence of CaCO3 reactions, Ψ would rise to 1.0. Similarly, increasing atmospheric pCO2 over time, which leads to ocean acidification, alters the relationship between organic and inorganic C reactions and carbon storage in the ocean. Thus, the carbon reactions and ψ can cause large variations in oceanic carbon storage with little exchange with the atmosphere.