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2018
Nevison, C, Munro D, Lovenduski N, Cassar N, Keeling R, Krummel P, Tjiputra J.  2018.  Net community production in the Southern Ocean: Insights from comparing atmospheric potential oxygen to satellite ocean color algorithms and ocean models. Geophysical Research Letters. 45:10549-10559.   10.1029/2018gl079575   AbstractWebsite

The contribution of oceanic net community production (NCP) to the observed seasonal cycle in atmospheric potential oxygen (APO) is estimated at Cape Grim, Tasmania. The resulting APO(NCP) signal is compared to satellite and ocean model-based estimates of POC export and NCP across the Southern Ocean. The satellite products underestimate the amplitude of the observed APONCP seasonal cycle by more than a factor of 2. Ocean models suggest two reasons for this underestimate: (1) Current satellite products substantially underestimate the magnitude of NCP in early spring. (2) Seasonal O-2 outgassing is supported in large part by storage of carbon in DOC and living biomass. More DOC observations are needed to help evaluate this latter model prediction. Satellite products could be improved by developing seasonally dependent relationships between remote sensing chlorophyll data and in situ NCP, recognizing that the former is a measure of mass, the latter of flux. Plain Language Summary Phytoplankton in the surface ocean transform carbon dioxide into organic carbon while also producing oxygen. A fraction of the carbon is exported into the deep ocean, while the oxygen is emitted to the atmosphere. The carbon export rate influences how much carbon dioxide the ocean can absorb. The rate is commonly estimated using satellite-based phytoplankton color measured in the surface ocean, but such estimates involve many uncertain steps and assumptions. Small but detectible seasonal cycles in atmospheric oxygen have been used as an independent method for evaluating satellite-based estimates of organic carbon export. In this study, we evaluate eight satellite-derived carbon export estimates based on their ability to reproduce the observed seasonal cycle of atmospheric oxygen measured at a southeastern Australia site. All underpredict the seasonal oxygen cycle by at least a factor of 2, in part because they fail to capture the carbon and oxygen produced in early springtime and also because they focus on large particles of carbon that are heavy enough to sink while neglecting the dissolved fraction of organic carbon. Our study suggests that satellite estimates could be improved by a better understanding of seasonal variations in the relationship between phytoplankton productivity and carbon export.

2017
Keeling, RF, Graven HD, Welp LR, Resplandy L, Bi J, Piper SC, Sun Y, Bollenbacher A, Meijer HAJ.  2017.  Atmospheric evidence for a global secular increase in carbon isotopic discrimination of land photosynthesis. Proceedings of the National Academy of Sciences of the United States of America. 114:10361-10366.   10.1073/pnas.1619240114   AbstractWebsite

A decrease in the C-13/C-12 ratio of atmospheric CO2 has been documented by direct observations since 1978 and from ice core measurements since the industrial revolution. This decrease, known as the C-13-Suess effect, is driven primarily by the input of fossil fuel-derived CO2 but is also sensitive to land and ocean carbon cycling and uptake. Using updated records, we show that no plausible combination of sources and sinks of CO2 from fossil fuel, land, and oceans can explain the observed C-13-Suess effect unless an increase has occurred in the C-13/C-12 isotopic discrimination of land photosynthesis. A trend toward greater discrimination under higher CO2 levels is broadly consistent with tree ring studies over the past century, with field and chamber experiments, and with geological records of C-3 plants at times of altered atmospheric CO2, but increasing discrimination has not previously been included in studies of long-term atmospheric 13C/12C measurements. We further show that the inferred discrimination increase of 0.014 +/- 0.007% ppm(-1) is largely explained by photorespiratory and mesophyll effects. This result implies that, at the global scale, land plants have regulated their stomatal conductance so as to allow the CO2 partial pressure within stomatal cavities and their intrinsic water use efficiency to increase in nearly constant proportion to the rise in atmospheric CO2 concentration.

2016
Jeong, SG, Newman S, Zhang JS, Andrews AE, Bianco L, Bagley J, Cui XG, Graven H, Kim J, Salameh P, LaFranchi BW, Priest C, Campos-Pineda M, Novakovskaia E, Sloop CD, Michelsen HA, Bambha RP, Weiss RF, Keeling R, Fischer ML.  2016.  Estimating methane emissions in California's urban and rural regions using multitower observations. Journal of Geophysical Research-Atmospheres. 121:13031-13049.   10.1002/2016jd025404   AbstractWebsite

We present an analysis of methane (CH4) emissions using atmospheric observations from 13 sites in California during June 2013 to May 2014. A hierarchical Bayesian inversion method is used to estimate CH4 emissions for spatial regions (0.3 degrees pixels for major regions) by comparing measured CH4 mixing ratios with transport model (Weather Research and Forecasting and Stochastic Time-Inverted Lagrangian Transport) predictions based on seasonally varying California-specific CH4 prior emission models. The transport model is assessed using a combination of meteorological and carbon monoxide (CO) measurements coupled with the gridded California Air Resources Board (CARB) CO emission inventory. The hierarchical Bayesian inversion suggests that state annual anthropogenic CH4 emissions are 2.42 +/- 0.49 Tg CH4/yr (at 95% confidence), higher (1.2-1.8 times) than the current CARB inventory (1.64 Tg CH4/yr in 2013). It should be noted that undiagnosed sources of errors or uncaptured errors in the model-measurement mismatch covariance may increase these uncertainty bounds beyond that indicated here. The CH4 emissions from the Central Valley and urban regions (San Francisco Bay and South Coast Air Basins) account for similar to 58% and 26% of the total posterior emissions, respectively. This study suggests that the livestock sector is likely the major contributor to the state total CH4 emissions, in agreement with CARB's inventory. Attribution to source sectors for subregions of California using additional trace gas species would further improve the quantification of California's CH4 emissions and mitigation efforts toward the California Global Warming Solutions Act of 2006 (Assembly Bill 32).

2014
Le Quere, C, Peters GP, Andres RJ, Andrew RM, Boden TA, Ciais P, Friedlingstein P, Houghton RA, Marland G, Moriarty R, Sitch S, Tans P, Arneth A, Arvanitis A, Bakker DCE, Bopp L, Canadell JG, Chini LP, Doney SC, Harper A, Harris I, House JI, Jain AK, Jones SD, Kato E, Keeling RF, Goldewijk KK, Kortzinger A, Koven C, Lefevre N, Maignan F, Omar A, Ono T, Park GH, Pfeil B, Poulter B, Raupach MR, Regnier P, Rodenbeck C, Saito S, Schwinger J, Segschneider J, Stocker BD, Takahashi T, Tilbrook B, van Heuven S, Viovy N, Wanninkhof R, Wiltshire A, Zaehle S.  2014.  Global carbon budget 2013. Earth System Science Data. 6:235-263.   10.5194/essd-6-235-2014   AbstractWebsite

Accurate assessment of anthropogenic carbon dioxide (CO2) emissions and their redistribution among the atmosphere, ocean, and terrestrial biosphere is important to better understand the global carbon cycle, support the development of climate policies, and project future climate change. Here we describe data sets and a methodology to quantify all major components of the global carbon budget, including their uncertainties, based on the combination of a range of data, algorithms, statistics and model estimates and their interpretation by a broad scientific community. We discuss changes compared to previous estimates, consistency within and among components, alongside methodology and data limitations. CO2 emissions from fossil-fuel combustion and cement production (E-FF) are based on energy statistics, while emissions from land-use change (E-LUC), mainly deforestation, are based on combined evidence from land-cover change data, fire activity associated with deforestation, and models. The global atmospheric CO2 concentration is measured directly and its rate of growth (G(ATM)) is computed from the annual changes in concentration. The mean ocean CO2 sink (S-OCEAN) is based on observations from the 1990s, while the annual anomalies and trends are estimated with ocean models. The variability in SOCEAN is evaluated for the first time in this budget with data products based on surveys of ocean CO2 measurements. The global residual terrestrial CO2 sink (S-LAND) is estimated by the difference of the other terms of the global carbon budget and compared to results of independent dynamic global vegetation models forced by observed climate, CO2 and land cover change (some including nitrogen-carbon interactions). All uncertainties are reported as +/- 1 sigma, reflecting the current capacity to characterise the annual estimates of each component of the global carbon budget. For the last decade available (2003-2012), E-FF was 8.6 +/- 0.4 GtC yr(-1), E-LUC 0.9 +/- 0.5 GtC yr(-1), G(ATM) 4.3 +/- 0.1 GtC yr(-1), S-OCEAN 2.5 +/- 0.5 GtC yr(-1), and S-LAND 2.8 +/- 0.8 GtC yr(-1). For year 2012 alone, E-FF grew to 9.7 +/- 0.5 GtC yr(-1), 2.2% above 2011, reflecting a continued growing trend in these emissions, GATM was 5.1 +/- 0.2 GtC yr(-1), S-OCEAN was 2.9 +/- 0.5 GtC yr(-1), and assuming an E-LUC of 1.0 +/- 0.5 GtC yr(-1) (based on the 2001-2010 average), S-LAND was 2.7 +/- 0.9 GtC yr(-1). G(ATM) was high in 2012 compared to the 2003-2012 average, almost entirely reflecting the high EFF. The global atmospheric CO2 concentration reached 392.52 +/- 0.10 ppm averaged over 2012. We estimate that E-FF will increase by 2.1% (1.1-3.1 %) to 9.9 +/- 0.5 GtC in 2013, 61% above emissions in 1990, based on projections of world gross domestic product and recent changes in the carbon intensity of the economy. With this projection, cumulative emissions of CO2 will reach about 535 +/- 55 GtC for 1870-2013, about 70% from E-FF (390 +/- 20 GtC) and 30% from E-LUC (145 +/- 50 GtC). This paper also documents any changes in the methods and data sets used in this new carbon budget from previous budgets (Le Quere et al., 2013). All observations presented here can be downloaded from the Carbon Dioxide Information Analysis Center (doi: 10.3334/CDIAC/GCP_2013_V2.3).

Rodgers, KB, Aumont O, Fletcher SEM, Plancherel Y, Bopp L, Montegut CD, Iudicone D, Keeling RF, Madec G, Wanninkhof R.  2014.  Strong sensitivity of Southern Ocean carbon uptake and nutrient cycling to wind stirring. Biogeosciences. 11:4077-4098.   10.5194/bg-11-4077-2014   AbstractWebsite

Here we test the hypothesis that winds have an important role in determining the rate of exchange of CO2 between the atmosphere and ocean through wind stirring over the Southern Ocean. This is tested with a sensitivity study using an ad hoc parameterization of wind stirring in an ocean carbon cycle model, where the objective is to identify the way in which perturbations to the vertical density structure of the planetary boundary in the ocean impacts the carbon cycle and ocean biogeochemistry. Wind stirring leads to reduced uptake of CO2 by the Southern Ocean over the period 2000-2006, with a relative reduction with wind stirring on the order of 0.9 Pg C yr(-1) over the region south of 45 degrees S. This impacts not only the mean carbon uptake, but also the phasing of the seasonal cycle of carbon and other ocean biogeochemical tracers. Enhanced wind stirring delays the seasonal onset of stratification, and this has large impacts on both entrainment and the biological pump. It is also found that there is a strong reduction on the order of 25-30% in the concentrations of NO3 exported in Subantarctic Mode Water (SAMW) to wind stirring. This finds expression not only locally over the Southern Ocean, but also over larger scales through the impact on advected nutrients. In summary, the large sensitivity identified with the ad hoc wind stirring parameterization offers support for the importance of wind stirring for global ocean biogeochemistry through its impact over the Southern Ocean.

2012
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.

Graven, HD, Xu X, Guilderson TP, Keeling RF, Trumbore SE, Tyler S.  2012.  Comparison of independent delta(co2)-c-14 records at Point Barrow, Alaska. Radiocarbon. 55:1541-1545.   10.2458/azu_js_rc.55.16220   AbstractWebsite

Two independent programs have collected and analyzed atmospheric CO2 samples from Point Barrow, Alaska, for radiocarbon content (Delta C-14) over the period 2003-2007. In one program, flask collection, stable isotope analysis, and CO2 extraction are performed by the Scripps Institution of Oceanography's CO2 Program and CO2 is graphitized and measured by accelerator mass spectrometry (AMS) at Lawrence Livermore National Laboratory. In the other program, the University of California, Irvine, performs flask collection, sample preparation, and AMS. Over 22 common sample dates spanning 5 yr, differences in measured Delta C-14 are consistent with the reported uncertainties and there is no significant bias between the programs.

2011
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).

2009
Keeling, RF.  2009.  Triage in the greenhouse. Nature Geoscience. 2:820-822.   10.1038/ngeo701   AbstractWebsite

The path towards mitigating global warming is going to be tortuous. capturing carbon dioxide and pumping it directly into the deep ocean to avoid atmospheric build-up is an option that has been dismissed prematurely.

2008
Hamme, RC, Keeling RF.  2008.  Ocean ventilation as a driver of interannual variability in atmospheric potential oxygen. Tellus Series B-Chemical and Physical Meteorology. 60:706-717.   10.1111/j.1600-0889.2008.00376.x   AbstractWebsite

We present observations of interannual variability on 2-5 yr timescales in atmospheric potential oxygen (APO approximate to O(2) + CO(2)) from the Scripps Institution of Oceanography global flask sampling network. Interannual variations in the tracer APO are expected to arise from air-sea fluxes alone, because APO is insensitive to exchanges with the terrestrial biosphere. These interannual variations are shown to be regionally coherent and robust to analytical artefacts. We focus on explaining a feature dominant in records from the Northern Hemisphere stations, marked by increasing APO in the late 1990s, followed by an abrupt drawdown in 2000-2001. The timing of the drawdown matches a renewal of deep convection in the North Atlantic, followed the next year by a severe winter in the western North Pacific that may have allowed ventilation of denser isopycnals than usual. We find a weak correlation between changes in the interhemispheric APO difference and El Nino indices, and the observations show no strong features of the 1997-98 El Nino. Comparisons with estimates of variations in ocean productivity and ocean heat content demonstrate that these processes are secondary influences at these timescales. We conclude that the evidence points to variability in ocean ventilation as the main driver of interannual variability in APO.

2006
Battle, M, Fletcher SEM, Bender ML, Keeling RF, Manning AC, Gruber N, Tans PP, Hendricks MB, Ho DT, Simonds C, Mika R, Paplawsky B.  2006.  Atmospheric potential oxygen: New observations and their implications for some atmospheric and oceanic models. Global Biogeochemical Cycles. 20   10.1029/2005gb002534   AbstractWebsite

[ 1] Measurements of atmospheric O(2)/N(2) ratios and CO(2) concentrations can be combined into a tracer known as atmospheric potential oxygen (APO approximate to O(2)/N(2) + CO(2)) that is conservative with respect to terrestrial biological activity. Consequently, APO reflects primarily ocean biogeochemistry and atmospheric circulation. Building on the work of Stephens et al. ( 1998), we present a set of APO observations for the years 1996 - 2003 with unprecedented spatial coverage. Combining data from the Princeton and Scripps air sampling programs, the data set includes new observations collected from ships in the low-latitude Pacific. The data show a smaller interhemispheric APO gradient than was observed in past studies, and different structure within the hemispheres. These differences appear to be due primarily to real changes in the APO field over time. The data also show a significant maximum in APO near the equator. Following the approach of Gruber et al. ( 2001), we compare these observations with predictions of APO generated from ocean O(2) and CO(2) flux fields and forward models of atmospheric transport. Our model predictions differ from those of earlier modeling studies, reflecting primarily the choice of atmospheric transport model (TM3 in this study). The model predictions show generally good agreement with the observations, matching the size of the interhemispheric gradient, the approximate amplitude and extent of the equatorial maximum, and the amplitude and phasing of the seasonal APO cycle at most stations. Room for improvement remains. The agreement in the interhemispheric gradient appears to be coincidental; over the last decade, the true APO gradient has evolved to a value that is consistent with our time-independent model. In addition, the equatorial maximum is somewhat more pronounced in the data than the model. This may be due to overly vigorous model transport, or insufficient spatial resolution in the air-sea fluxes used in our modeling effort. Finally, the seasonal cycles predicted by the model of atmospheric transport show evidence of an excessive seasonal rectifier in the Aleutian Islands and smaller problems elsewhere.

Manning, AC, Keeling RF.  2006.  Global oceanic and land biotic carbon sinks from the Scripps atmospheric oxygen flask sampling network. Tellus Series B-Chemical and Physical Meteorology. 58:95-116.   10.1111/j.1600-0889.2006.00175.x   AbstractWebsite

Measurements of atmospheric O-2/N-2 ratio and CO2 concentration are presented over the period 1989-2003 from the Scripps Institution of Oceanography global flask sampling network. A formal framework is described for making optimal use of these data to estimate global oceanic and land biotic carbon sinks. For the 10-yr period from 1990 to 2000, the oceanic and land biotic sinks are estimated to be 1.9 +/- 0.6 and 1.2 +/- 0.8 Pg C yr(-1), respectively, while for the 10-yr period from 1993 to 2003, the sinks are estimated to be 2.2 +/- 0.6 and 0.5 +/- 0.7 Pg C yr(-1), respectively. These estimates, which are also compared with earlier results, make allowance for oceanic O-2 and N-2 outgassing based on observed changes in ocean heat content and estimates of the relative outgassing per unit warming. For example, for the 1993-2003 period we estimate outgassing of 0.45 x 10(14) mol O-2 yr(-1) and 0.20 x 10(14) mol N-2 yr(-1), which results in a correction of 0.5 Pg C yr(-1) on the oceanic and land biotic carbon sinks. The basis for this oceanic outgassing correction is reviewed in the context of recent model estimates. The main contributions to the uncertainty in the global sinks averages are from the estimates for oceanic outgassing and the estimates for fossil fuel combustion. The oceanic sink of 2.2 Pg C yr(-1) for 1993-2003 is consistent, within the uncertainties, with the integrated accumulation of anthropogenic CO2 in the ocean since 1800 as recently estimated from oceanic observations, assuming the oceanic sink varied over time as predicted by a box-diffusion model.

2005
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.

2003
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.

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.

2000
Najjar, RG, Keeling RF.  2000.  Mean annual cycle of the air-sea oxygen flux: A global view. Global Biogeochemical Cycles. 14:573-584.   10.1029/1999gb900086   AbstractWebsite

A global monthly-mean climatology of the air-sea oxygen flux is presented and discussed. The climatology is based on the ocean oxygen climatology of Najjar and Keeling [1997] and wind speeds derived from a meteorological analysis center. Seasonal variations are characterized by outgassing of oxygen during spring and summer and ingassing of oxygen during fall and winter, a pattern consistent with thermal and biological forcing of the air-sea oxygen flux. The annual mean flux pattern is characterized by ingassing at high latitudes and the tropics and outgassing in middle latitudes. The air-sea oxygen flux is shown to exhibit patterns that agree well with patterns seen in a marine primary productivity climatology, in model generated air-sea O-2 fluxes, in estimates of remineralization in the shallow aphotic zone based on seasonal oxygen variations, in observed seasonal nutrient-temperature relationships, and in independent estimates of meridional oxygen transport in the Atlantic ocean. We also find that extratropical mixed layer new production during the spring-summer period, computed from biological seasonal net outgassing of oxygen, is equivalent to the production of 4.5-5.6 Gt C, much lower than previous estimates based on atmospheric O-2/N-2 measurements.

1999
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.

1998
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.

1996
Severinghaus, JP, Bender ML, Keeling RF, Broecker WS.  1996.  Fractionation of soil gases by diffusion of water vapor, gravitational settling, and thermal diffusion. Geochimica Et Cosmochimica Acta. 60:1005-1018.   10.1016/0016-7037(96)00011-7   AbstractWebsite

Air sampled from the moist unsaturated zone in a sand dune exhibits depletion in the heavy isotopes of N-2 and O-2. We propose that the depletion is caused by a diffusive flux of water vapor out of the dune, which sweeps out the other gases, forcing them to diffuse back into the dune. The heavy isotopes of N-2 and O-2 diffuse back more slowly, resulting in a steady-state depletion of the heavy isotopes in the dune interior. We predict the effect's magnitude with molecular diffusion theory and reproduce it in a laboratory simulation, finding good agreement between field, theory, and lab. The magnitude of the effect is governed by the ratio of the binary diffusivities against water vapor of a pair of gases, and increases similar to linearly with the difference between the water vapor mole fraction of the site and the advectively mixed reservoir with which it is in diffusive contact (in most cases the atmosphere). The steady-state effect is given by delta(i) = [i/j/i(0)/j(0) - 1] 10(3) parts per thousand congruent to [(1 - x(H2O)/1 - x(H2O0))((Dj-H2O/Di-H2O)-1) -1] 10(3) parts per thousand, where delta(i) is the fractional deviation in permil of the gas i/gas j ratio from the advectively mixed reservoir, x(H2O) and x(H2O0) are respectively the mole fractions of water vapor at the site and in the advectively mixed reservoir, and D-i-H2O is the binary diffusion coefficient of gas i with water vapor. The effect is independent of scale at steady state, but approaches steady state with the time constant of diffusion set by the length scale. Exploiting the mechanism, we make an experimental estimate of the relative diffusivities of O-2 and N-2 against water vapor, finding that O-2 diffuses 3.6 +/- 0.3% faster than N-2 despite its greater mass. We also confirm in the study dune the presence of two additional known processes: gravitational fractionation, heretofore seen only in the unconsolidated firn of polar ice sheets, and thermal diffusion, well described in laboratory studies but not seen previously in nature. We predict that soil gases in general will exhibit the three effects described here, the water vapor flux fractionation effect, gravitational fractionation, and thermal diffusion. However, our analysis neglects Knudsen diffusion and thus may be inapplicable to fine-grained soils.

1993
Keeling, RF, Najjar RP, Bender ML, Tans PP.  1993.  What atmospheric oxygen measurements can tell us about the global carbon cycle. Global Biogeochemical Cycles. 7:37-67.   10.1029/92gb02733   AbstractWebsite

This paper explores the role that measurements of changes in atmospheric oxygen, detected through changes in the O2/N2 ratio of air, can play in improving our understanding of the global carbon cycle. Simple conceptual models are presented in order to clarify the biological and physical controls on the exchanges of O2, CO2, N2, and Ar across the air-sea interface and in order to clarify the relationships between biologically mediated fluxes of oxygen across the air-sea interface and the cycles of organic carbon in the ocean. Predictions of large-scale seasonal variations and gradients in atmospheric oxygen are presented. A two-dimensional model is used to relate changes in the O2/N2 ratio of air to the sources of oxygen from terrestrial and marine ecosystems, the thermal ingassing and outgassing of seawater, and the burning of fossil fuel. The analysis indicates that measurements of seasonal variations in atmospheric oxygen can place new constraints on the large-scale marine biological productivity. Measurements of the north-south gradient and depletion rate of atmospheric oxygen can help determine the rates and geographical distribution of the net storage of carbon in terrestrial ecosystems.