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Battle, M, Bender M, Hendricks MB, Ho DT, Mika R, McKinley G, Fan SM, Blaine T, Keeling RF.  2003.  Measurements and models of the atmospheric Ar/N2 ratio. Geophysical Research Letters. 30   10.1029/2003gl017411   AbstractWebsite

[1] The Ar/N-2 ratio of air measured at 6 globally distributed sites shows annual cycles with amplitudes of 12 to 37 parts in 10(6). Summertime maxima reflect the atmospheric Ar enrichment driven by seasonal warming and degassing of the oceans. Paired models of air-sea heat fluxes and atmospheric tracer transport predict seasonal cycles in the Ar/N-2 ratio that agree with observations, within uncertainties.

Bender, ML, Battle M, Keeling RF.  1998.  The O2 balance of the atmosphere: A tool for studying the fate of fossil-fuel CO2. Annual Review of Energy and the Environment. 23:207-223.   10.1146/   AbstractWebsite

Carbon dioxide is a radiatively active gas whose atmospheric concentration increase is likely to affect Earth's climate. CO2 is added to the atmosphere by biomass burning and the combustion of fossil fuels. Some added CO2 remains in the atmosphere. However, substantial amounts are taken up by the oceans and land biosphere, attenuating the atmospheric increase. Atmospheric O-2 measurements provide one constraint for partitioning uptake rates between the ocean and the land biosphere. Here we review studies of atmospheric O-2 concentration variations and discuss their implications for CO2 uptake by the ocean and the land biosphere. We compare estimates of anthropogenic carbon fluxes from O-2 studies with estimates from other approaches and examine the contribution of natural ocean carbon fluxes to atmospheric O-2 variations.

Keeling, RF, Manning AC, McEvoy EM, Shertz SR.  1998.  Methods for measuring changes in atmospheric O2 concentration and their application in southern hemisphere air. Journal of Geophysical Research-Atmospheres. 103:3381-3397.   10.1029/97jd02537   AbstractWebsite

Methods are described for measuring changes in atmospheric O-2 concentration with emphasis on gas handling procedures. Cryogenically dried air samples are collected in 5 L glass flasks at ambient pressure and analyzed against reference gases derived from high-pressure aluminum tanks. Fractionation effects are minimized by avoiding pressure and flow variations throughout the gas-handling system. The overall external reproducibility is approximately +/-3.3 per meg, with systematic errors associated with collecting samples and with storing them for 1 year reduced to the level of 3 per meg or smaller. The demonstrated short-term reproducibly of air delivered from high-presure tanks is +/-1.5 per meg, with the composition changing by at most 5 per meg by surface desorption reactions as the tank is depleted to below 3500 kPa. A 9-year survey of a suite of six reference gases showed no systematic long-term trends in relative O-2 concentrations to the level of 5 per meg. Results are presented from samples collected at Cape Grim (41 degrees S), Macquarie Island (54 degrees S) and the South Pole Station (90 degrees S). From measurements spanning 1991-1995 it is found that the O-2 concentrations at the South Pole are on average 3.6+/-1.2 per meg higher than at Cape Grim. This result runs contrary to the expectation that the air at high southern latitudes should be depleted in O-2 as a result of O-2 uptake from the Southern Ocean and may require the existence of unknown O-2 sources near Antarctica or unexpected atmospheric transport patterns.

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.

Keeling, RF, Peng TH.  1995.  Transport of heat, CO2 and O2 by the Atlantic's thermohaline circulation. Philosophical Transactions of the Royal Society of London Series B-Biological Sciences. 348:133-142.   10.1098/rstb.1995.0055   AbstractWebsite

We estimate transport of heat, CO2 and O-2 by the Atlantic's thermohaline circulation using an approach based on differences in the chemical and physical characteristics of North Atlantic Deep Water (NADW), Antarctic Intermediate Water (AAIW), and the northward return flow across the equator. The characteristics of the return-flow waters are constrained by imposing conservation of phosphate in the North Atlantic as a whole. Based on a total equatorial return flow of 13 x 10(6) m(3) s(-1), we find that the Atlantic north of the equator is a source of 7.7 +/- 1.4 x 10(14) W to the atmosphere, a sink of 0.51 +/- 0.21 x 10(14) mol of O-2, and preindustrially was a sink of 0.33 +/- 0.15 x 10(14) mol of CO2. Uptake of O-2 and CO2 by the North Atlantic is driven mainly by thermal, as opposed to biological processes.

Keeling, RF, Stephens BB, Najjar RG, Doney SC, Archer D, Heimann M.  1998.  Seasonal variations in the atmospheric O2/N2 ratio in relation to the kinetics of air-sea gas exchange. Global Biogeochemical Cycles. 12:141-163.   10.1029/97gb02339   AbstractWebsite

Observations of seasonal variations in the atmospheric O-2/N-2 ratio are reported at nine baseline sites in the northern and southern hemispheres. Concurrent CO2 measurements are used to correct for the effects of land biotic exchanges of O-2 on the O-2/N-2 cycles thus allowing the residual component of the cycles due to oceanic exchanges of O-2 and N-2 to be calculated. The residual oceanic cycles in the northern hemisphere are nearly diametrically out of phase with the cycles in the southern hemisphere. The maxima in both hemispheres occur in summer. In both hemispheres, the middle-latitude sea level stations show the cycles with largest amplitudes and earliest phasing. Somewhat smaller amplitudes are observed at the high-latitude stations, and much smaller amplitudes are observed at the tropical stations. A model for simulating the oceanic component of the atmospheric O-2/N-2 cycles is presented consisting of the TM2 atmospheric tracer transport model [Heimann, 1995] driven at the lower boundary by O-2 fluxes derived from observed O-2 saturation anomalies in surface waters and by N-2 fluxes derived from the net air-sea heat flux. The model is optimized to fit the observed atmospheric O-2/N-2 cycles by adjusting the air-sea gas-exchange velocity, which relates O-2 anomaly to O-2 flux. The optimum fit corresponds to spatially and temporally averaged exchange velocities of 24+/-6 cm/hr for the oceans north of 31 degrees N and 29+/-12 cm/hr for the oceans south of 31 degrees S. These velocities agree to within the uncertainties with the gas-exchange velocities expected from the Wanninkhof [1992] formulation of the air-sea gas-exchange velocity combined with European Centre for Medium-Range Weather Forecasts winds [Gibson et al., 1997] but are larger than the exchange velocities expected from the Liss and Merlivat [1986] relation using the same winds. The results imply that the gas-exchange velocity for O-2, like that of CO2, may be enhanced in the open ocean by processes that were not systematically accounted for in the experiments used to derive the Liss and Merlivat relation.

Lueker, TJ, Walker SJ, Vollmer MK, Keeling RF, Nevison CD, Weiss RF, Garcia HE.  2003.  Coastal upwelling air-sea fluxes revealed in atmospheric observations of O2/N2, CO2 and N2O. Geophysical Research Letters. 30   10.1029/2002gl016615   AbstractWebsite

[1] We capture water column ventilation resulting from coastal upwelling in continuous records of O-2/N-2, CO2, and N2O at Trinidad, California. Our records reveal the gas exchange response time of the ocean to the upwelling and ensuing biological production. Satellite and buoy wind data allow extrapolation of our records to assess coastal upwelling air-sea fluxes of O-2 and N2O. We improve on previous regional estimates of N2O flux in coastal and continental shelf region of the western U. S. We characterize the source of N2O as being predominately from nitrification based on the O-2/N2O emissions ratio observed in our atmospheric records.

Manizza, M, Keeling RF, Nevison CD.  2012.  On the processes controlling the seasonal cycles of the air-sea fluxes of O2 and N2O: A modelling study. Tellus Series B-Chemical and Physical Meteorology. 64   10.3402/tellusb.v64i0.18429   AbstractWebsite

The seasonal dynamics of the air-sea gas flux of oxygen (O-2) are controlled by multiple processes occurring simultaneously. Previous studies showed how to separate the thermal component from the total O-2 flux to quantify the residual oxygen flux due to biological processes. However, this biological signal includes the effect of both net euphotic zone production (NEZP) and subsurface water ventilation. To help understand and separate these two components, we use a large-scale ocean general circulation model (OGCM), globally configured, and coupled to a biogeochemical model. The combined model implements not only the oceanic cycle of O-2 but also the cycles of nitrous oxide (N2O), argon (Ar) and nitrogen (N-2). For this study, we apply a technique to distinguish the fluxes of O-2 driven separately by thermal forcing, NEZP, and address the role of ocean ventilation by carrying separate O-2 components in the model driven by solubility, NEZP and ventilation. Model results show that the ventilation component can be neglected in summer compared to the production and thermal components polewards but not equatorward of 30 degrees in each hemisphere. This also implies that neglecting the role of ventilation in the subtropical areas would lead to overestimation of the component of O-2 flux due to NEZP by 20-30%. Model results also show that the ventilation components of air-sea O-2 and N2O fluxes are strongly anti-correlated in a ratio that reflects the subsurface tracer/tracer relationships (similar to 0.1 mmol N2O/mol O-2) as derived from observations. The results support the use of simple scaling relationships linking together the thermally driven fluxes of Ar, N-2 and O-2. Furthermore, our study also shows that for latitudes polewards of 30 degrees of both hemispheres, the Garcia and Keeling (2001) climatology, when compared to our model results, has a phasing error with the fluxes being too early by similar to 2-3 weeks.

Manning, AC, Keeling RF, Severinghaus JP.  1999.  Precise atmospheric oxygen measurements with a paramagnetic oxygen analyzer. Global Biogeochemical Cycles. 13:1107-1115.   10.1029/1999gb900054   AbstractWebsite

A methodology has been developed for making continuous, high-precision measurements of atmospheric oxygen concentrations by modifying a commercially available paramagnetic oxygen analyzer. Incorporating several design improvements, an effective precision of 0.2 ppm O-2 from repeated measurements over a 1-hour interval was achieved. This is sufficient to detect background changes in atmospheric O-2 to a level that constrains various aspects of the global carbon cycle. The analyzer was used to measure atmospheric O-2 in a semicontinuous fashion from air sampled from the end of Scripps Pier, La Jolla, California, and data from a 1-week period in August 1996 are shown. The data exhibit strongly anticorrelated changes in O-2 and CO2 caused by local or regional combustion of fossil fuels. During periods of steady background CO2 concentrations, however, we see additional variability in O-2 concentrations, clearly not due to local combustion and presumably due to oceanic sources or sinks of O-2. This variability suggests that in contrast to CO2, higher O-2 sampling rates, such as those provided by continuous measurement programs, may be necessary to define an atmospheric O-2 background and thus aid in validating and interpreting other O-2 data from flask sampling programs. Our results have also demonstrated that this paramagnetic analyzer and gas handling design is well suited for making continuous measurements of atmospheric O-2 and is suitable for placement at remote background air monitoring sites.

Najjar, RG, Keeling RF.  1997.  Analysis of the mean annual cycle of the dissolved oxygen anomaly in the World Ocean. Journal of Marine Research. 55:117-151.   10.1357/0022240973224481   AbstractWebsite

A global climatology of the dissolved oxygen anomaly (the excess over saturation) is created with monthly resolution in the upper 500 m of the ocean. The climatology is based on dissolved oxygen, temperature and salinity data archived at the National Oceanographic Data Center. Examination of this climatology reveals statistically significant annual cycles throughout the upper 500 m of the World Ocean, though seasonal variations are most coherent in the North Atlantic, where data density is greatest. Vertical trends in the phase and amplitude of the annual cycle are noted. The cycle in surface waters is characterized by a summer maximum and a winter minimum, consistent with warming and high rates of photosynthesis during the summer, and cooling and entrainment of oxygen-depleted water during the winter. In low and middle latitudes, the amplitude increases with depth and the maximum occurs later in the year, a trend consistent with the seasonal accumulation of oxygen associated with the shallow oxygen maximum. At a depth that varies between about 30 and 130 m, the phase of the annual cycle undergoes an abrupt shift. We call this depth the oxygen nodal depth. Below the nodal depth, the annual cycle is characterized by an early-spring maximum and a late-fall minimum, consistent with a cycle dominated by respiration during the spring and summer and replenishment of oxygen from the atmosphere by ventilation during the fall and winter. Below the nodal depth, the amplitude of the annual cycle generally decreases with depth, indicative of decreasing respiration and ventilation rates, or less seasonality in both processes. We postulate that the nodal depth in middle and high latitudes corresponds closely to the summertime compensation depth, where photosynthesis and net community respiration are equal. With this interpretation of the nodal depth and a simple model of the penetration of light in the water column, a compensation light intensity of 1 W m(-2) (4 mu E m(-2) s(-1)) is deduced, at the low end of independent estimates. Horizontal trends in the phase and amplitude of the annual cycle are also noted. We find that the nodal depth decreases toward the poles in both hemispheres and is generally greater in the Southern Hemisphere, patterns found to be consistent with light-based estimates of the compensation depth. The amplitude of the annual cycle in the oxygen anomaly increases monotonically with latitude, and higher latitudes lag lower latitudes. In the North Atlantic and North Pacific, the amplitude of the annual cycle tends to increase from east to west at all depths and latitudes, as expected considering that physical forcing has greater seasonal variability in the west. The tropics and the North Indian Ocean have features that distinguish them from other regions. Below about 75 m, these waters have pronounced annual cycles of the oxygen anomaly that areshown to be caused mainly by wind-driven adiabatic displacements of the thermocline. A semiannual cycle of the oxygen anomaly is found in the surface waters of the North Indian Ocean, consistent with the known semiannual cycle of surface heat flux in this region.

Nevison, CD, Keeling RF, Kahru M, Manizza M, Mitchell BG, Cassar N.  2012.  Estimating net community production in the Southern Ocean based on atmospheric potential oxygen and satellite ocean color data. Global Biogeochemical Cycles. 26   10.1029/2011gb004040   AbstractWebsite

The seasonal cycle of atmospheric potential oxygen (APO similar to O-2 + 1.1 CO2) reflects three seasonally varying ocean processes: 1) thermal in- and outgassing, 2) mixed layer net community production (NCP) and 3) deep water ventilation. Previous studies have isolated the net biological seasonal signal (i.e., the sum of NCP and ventilation), after using air-sea heat flux data to estimate the thermal signal. In this study, we resolve all three components of the APO seasonal cycle using a methodology in which the ventilation signal is estimated based on atmospheric N2O data, the thermal signal is estimated based on heat flux or atmospheric Ar/N-2 data, and the production signal is inferred as a residual. The isolation of the NCP signal in APO allows for direct comparison to estimates of NCP based on satellite ocean color data, after translating the latter into an atmospheric signal using an atmospheric transport model. When applied to ocean color data using algorithms specially adapted to the Southern Ocean and APO data at three southern monitoring sites, these two independent methods converge on a similar phase and amplitude of the seasonal NCP signal in APO and yield an estimate of annual mean NCP south of 50 degrees S of 0.8-1.2 Pg C/yr, with corresponding annual mean NPP of similar to 3 Pg C/yr and a mean growing season f ratio of similar to 0.33. These results are supported by ocean biogeochemistry model simulations, in which air-sea O-2 and N2O fluxes are resolved into component thermal, ventilation and (for O-2) NCP contributions.

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.

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.

Stephens, BB, Keeling RF, Paplawsky WJ.  2003.  Shipboard measurements of atmospheric oxygen using a vacuum-ultraviolet absorption technique. Tellus Series B-Chemical and Physical Meteorology. 55:857-878.   10.1046/j.1435-6935.2003.00075.x   AbstractWebsite

We have developed an instrument for making continuous, field-based, part-per-million (ppm) level measurements of atmospheric oxygen concentration, and have implemented it on research cruises in the equatorial Pacific and Southern Oceans. The instrument detects changes in oxygen by the absorption of vacuum ultraviolet (VUV) radiation as it passes through a flowing gas stream, and has a precision comparable to existing laboratory techniques. Here we describe the VUV instrument and present atmospheric O-2 and CO2 data collected from the NOAA ship Ka' imimoana in the equatorial Pacific during April and May of 1998, and from the NSF ship Lawrence M. Gould in the Southern Ocean during October 1998. These data represent the first field-based measurements of atmospheric O-2, and significant additions to the O-2 datasets in these regions. Our boreal-springtime equatorial measurements reveal significant short-term variations in atmospheric O-2, resulting from variations in atmospheric mixing relative to the strong interhemispheric gradient. Our austral-springtime Southern Ocean observations confirm the low O-2 concentrations seen in flask samples from this region, allow the separate identification of oceanic and industrial influences on CO2, and provide evidence of a Southern Ocean source for CO2 at this time of year. These shipboard VUV observations do not provide any evidence to support coupled ocean-atmosphere model predictions of a large decreasing atmospheric O-2 gradient between equatorial and high-southern latitudes.