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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.

Nevison, CD, Keeling RF, Weiss RF, Popp BN, Jin X, Fraser PJ, Porter LW, Hess PG.  2005.  Southern Ocean ventilation inferred from seasonal cycles of atmospheric N2O and O2/N2 at Cape Grim, Tasmania. Tellus Series B-Chemical and Physical Meteorology. 57:218-229.   10.1111/j.1600-0889.2005.00143.x   AbstractWebsite

The seasonal cycle of atmospheric N(2)O is derived from a 10-yr observational record at Cape Grim, Tasmania (41 degrees S, 145 degrees E). After correcting for thermal and stratospheric influences, the observed atmospheric seasonal cycle is consistent with the seasonal outgassing of microbially produced N(2)O from the Southern Ocean, as predicted by an ocean biogeochemistry model coupled to an atmospheric transport model (ATM). The model-observation comparison suggests a Southern Ocean N(2)O source of similar to 0.9 Tg N yr(-1) and is the first study to reproduce observed atmospheric seasonal cycles in N(2)O using specified surface sources in forward ATM runs. However, these results are sensitive to the thermal and stratospheric corrections applied to the atmospheric N(2)O data. The correlation in subsurface waters between apparent oxygen utilization (AOU) and N(2)O production (approximated as the concentration in excess of atmospheric equilibrium Delta N(2)O) is exploited to infer the atmospheric seasonal cycle in O(2)/N(2) due to ventilation of O(2)-depleted subsurface waters. Subtracting this cycle from the observed, thermally corrected seasonal cycle in atmospheric O(2)/N(2) allows the residual O(2)/N(2) signal from surface net community production to be inferred. Because N(2)O is only produced in subsurface ocean waters, where it is correlated to O(2) consumption, atmospheric N(2)O observations provide a methodology for distinguishing the surface production and subsurface ventilation signals in atmospheric O(2)/N(2), which have previously been inseparable.