Ground air: A first approximation of the Earth's second largest reservoir of carbon dioxide gas.

It is becoming increasingly clear that a substantial reservoir of carbon exists in the unsaturated zone of aquifers, though the total size of this reservoir on a global scale remains unquantified. Here we provide the first broad estimate of the amount of carbon dioxide gas found in this terrestrial reservoir. We calculate that between 2 and 53 PgC exists as gaseous CO in aquifers worldwide, generated by the slow microbial oxidation of organic particles transported into aquifers by percolating groundwater. Importantly, this carbon reservoir is in the form of CO gas, and is therefore transferable to the Earth's atmosphere without any phase change. On a coarse scale, water table depths are partially controlled by local sea level; sea level lowering therefore allows slow carbon sequestration into the reservoir and sea level increases force rapid CO outgassing from this reservoir. High-resolution cave air pCO data demonstrate that sea level variability does affect CO outgassing rates from the unsaturated zone, and that the CO outgassing due to sea level rise currently occurs on daily (tidal) timescales. We suggest that global mean water table depth must modulate the global unsaturated zone volume and the size of this carbon reservoir, potentially affecting atmospheric CO on geological timescales.