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Keeling, RF, Manning AC, Dubey MK.  2011.  The atmospheric signature of carbon capture and storage. Philosophical Transactions of the Royal Society a-Mathematical Physical and Engineering Sciences. 369:2113-2132.   10.1098/rsta.2011.0016   AbstractWebsite

Compared with other industrial processes, carbon capture and storage (CCS) will have an unusual impact on atmospheric composition by reducing the CO(2) released from fossil-fuel combustion plants, but not reducing the associated O(2) loss. CO(2) that leaks into the air from below-ground CCS sites will also be unusual in lacking the O(2) deficit normally associated with typical land CO(2) sources, such as from combustion or ecosystem exchanges. CCS may also produce distinct isotopic changes in atmospheric CO(2). Using simple models and calculations, we estimate the impact of CCS or leakage on regional atmospheric composition. We also estimate the possible impact on global atmospheric composition, assuming that the technology is widely adopted. Because of its unique signature, CCS may be especially amenable to monitoring, both regionally and globally, using atmospheric observing systems. Measurements of the O(2)/N(2) ratio and the CO(2) concentration in the proximity of a CCS site may allow detection of point leaks of the order of 1000 ton CO(2) yr(-1) from a CCS reservoir up to 1km from the source. Measurements of O(2)/N(2) and CO(2) in background air from a global network may allow quantification of global and hemispheric capture rates from CCS to the order of +/- 0.4 PgCyr(-1).

Rodenbeck, C, Le Quere C, Heimann M, Keeling RF.  2008.  Interannual variability in oceanic biogeochemical processes inferred by inversion of atmospheric O2/N2 and CO2 data. Tellus Series B-Chemical and Physical Meteorology. 60:685-705.   10.1111/j.1600-0889.2008.00375.x   AbstractWebsite

Atmospheric measurements of O(2)/N(2) and CO(2) at up to nine sites have been used to infer the interannual variations in oceanic O(2) exchange with an inverse method. The method distinguishes the regional contributions of three latitudinal bands, partly the individual contributions of the North Pacific and the North Atlantic also. The interannual variations of the inferred O(2) fluxes in the tropical band correlate significantly with the El Nino/Southern Oscillation. Tropical O(2) variations appear to be dominated by the ventilation of the O(2) minimum zone from variations in Pacific equatorial upwelling. The interannual variations of the northern and southern extratropical bands are of similar amplitude, though the attribution to mechanisms is less clear. The interannual variations estimated by the inverse method are larger than those estimated by the current generation of global ocean biogeochemistry models, especially in the North Atlantic, suggesting that the representation of biological processes plays a role. The comparison further suggests that O(2) variability is a more stringent test to validate models than CO(2) variability, because the processes driving O(2) variability combine in the same direction and amplify the underlying climatic signal.

Keeling, RF, Manning AC, Paplawsky WJ, Cox AC.  2007.  On the long-term stability of reference gases for atmospheric O2/N2 and CO2 measurements. Tellus Series B-Chemical and Physical Meteorology. 59:3-14.   10.1111/j.1600-0889.2006.00228.x   AbstractWebsite

Measurements of changes in the atmospheric O-2/N-2 ratio have typically relied on compressed air derived from high-pressure tanks as the reference material against which atmospheric changes are assessed. The validity of this procedure is examined here in the context of the history of 18 O-2/N-2 reference tanks compared over a 12-yr time-frame. By considering differences in tank sizes, material types, and by performing additional tests, the long-term stability of the delivered gas is evaluated with respect to surface reactions, leakage, regulator effects, and thermal diffusion and gravimetric fractionation. Results are also reported for the stability of CO2 in these tanks. The results emphasize the importance of orienting tanks horizontally within a thermally insulated enclosure to reduce thermal and gravimetric fractionation of both O-2/N-2 and CO2 concentrations, and they emphasize the importance of avoiding elastomeric O-rings at the head-valve base. With the procedures documented here, the long-term drift in O-2/N-2 appears to be zero to within approximately +/- 0.4 per meg yr(-1), which projects to an uncertainty of +/- 0.16 Pg C yr(-1) (1 sigma) in O-2-based global carbon budgets.