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Staudigel, H, Albarede F, Blichert-Toft J, Edmond J, McDonough B, Jacobsen SB, Keeling R, Langmuir CH, Nielsen RL, Plank T, Rudnick R, Shaw HF, Shirey S, Veizer J, White W.  1998.  Geochemical Earth Reference Model (GERM): description of the initiative. Chemical Geology. 145:153-159.   10.1016/S0009-2541(97)00141-1   Abstract

The Geochemical Earth Reference Model (GERM) initiative is a grass root effort with the goals of establishing a community consensus on a chemical characterization of the Earth, its major reservoirs, and the flu?;es between them. The GERM initiative will provide a review of available scientific constraints for: (1) the composition of all major chemical reservoirs of the present-day Earth, from core to atmosphere; (2) present-day fluxes between reservoirs; (3) the Earth's chemical and isotopic evolution since accretion; and (4) the chemical and isotopic evolution of seawater as a record of global tectonics and climate, Even though most of the constraints for the GERM will be drawn from chemical data sets, some data will have to come from other disciplines, such as geophysics, nuclear physics, and cosmochemistry. GERM also includes a diverse chemical and physical data base and computer codes that are useful for our understanding of how the Earth works as a dynamic chemical and physical system. The GERM initiative is developed in an open community discussion on the World Wide Web (http://www-ep.es.llnl.gov/germ/germ-home.html) that is moderated by editors with responsibilities for different reservoirs, fluxes, data bases, and other scientific or technical aspects. These editors have agreed to lay out an initial, strawman GERM for their respective sections and to moderate community discussions leading to a first, preliminary consensus. The development of the GERM began with an initial workshop in Lyon, France in March, 1996. Since then, the GERM has continued to be developed on the Internet, punctuated by workshops and special sessions at professional meetings. A second GERM workshop will be held in La Jolla, CA USA on March 10-13, 1998. (C) 1998 Elsevier Science B.V. All nights reserved.

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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.

Severinghaus, JP, Keeling RF, Miller BR, Weiss RF, Deck B, Broecker WS.  1997.  Feasibility of using sand dunes as archives of old air. Journal of Geophysical Research-Atmospheres. 102:16783-16792.   10.1029/97jd00525   AbstractWebsite

Large unaltered samples of the atmosphere covering the past century would complement the history of atmospheric gases obtained from bubbles in ice cores, enabling measurement of geochemically important species such as O-2, (CH4)-C-14, and (CO)-C-14. Sand dunes are a porous media with interstitial air in diffusive contact with the atmosphere, somewhat analogous to the unconsolidated layer of firn atop glaciers. Recent studies have demonstrated the value of firn as an archive of old air [Battle et al., 1996; Bender et al., 1994a]. Unlike firn, sand dunes are incompressible and so remain permeable to greater depths and may extend the firn record into the past century. To evaluate the feasibility of using sand dunes as archives of old air, we drilled 60 m deep test holes in the Algodones Dunes, Imperial Valley, California. The main objective was to see if the air in a sand dune is as old as predicted by a diffusion model, or if the dune is rapidly flushed by advective pumping during windstorms and barometric pressure changes. We dated the air with chlorofluorocarbons and krypton-85, anthropogenic tracers whose atmospheric concentrations are known and have been increasing rapidly in the past half century. These tracer data match the pure diffusion model well, showing that advection in this dune is negligible compared to diffusion as a transport mechanism and that the mean age of the air at 61 m depth is similar to 10 years. Dunes therefore do contain old air. However, dunes appear to suffer from two serious drawbacks as archives. Microbial metabolism is evident in elevated CO2 and N2O and depressed CH4 and O-2 concentrations in this dune, corrupting the signals of interest in this and probably most dunes. Second, isotopic analyses of N-2 and O-2 from the dune show that fractionation of the gases occurs due to diffusion of water vapor, complicating the interpretation of the O-2 signal beyond the point of viability for an air archive. Sand dunes may be useful for relatively inert gases with large atmospheric concentration changes such as chlorofluorocarbons.

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Keeling, CD, Piper SC, Whorf TP, Keeling RF.  2011.  Evolution of natural and anthropogenic fluxes of atmospheric CO2 from 1957 to 2003. Tellus Series B-Chemical and Physical Meteorology. 63:1-22.   10.1111/j.1600-0889.2010.00507.x   AbstractWebsite

An analysis is carried out of the longest available records of atmospheric CO(2) and its 13C/12C ratio from the Scripps Institution of Oceanography network of fixed stations, augmented by data in the 1950s and 1960s from ships and ice floes. Using regression analysis, we separate the interhemispheric gradients of CO(2) and 13C/12C into: (1) a stationary (possibly natural) component that is constant with time, and (2) a time-evolving component that increases in proportion to fossil fuel emissions. Inverse calculations using an atmospheric transport model are used to interpret the components of the gradients in terms of land and ocean sinks. The stationary gradients in CO(2) and 13C/12C are both satisfactorily explained by ocean processes, including an ocean carbon loop that transports 0.5 PgC yr-1 southwards in the ocean balanced by an atmospheric return flow. A stationary northern land sink appears to be ruled out unless its effect on the gradient has been offset by a strong rectifier effect, which seems doubtful. A growing northern land sink is not ruled out, but has an uncertain magnitude (0.3-1.7 PgC yr-1 centred on year 2003) dependent on the rate at which CO(2) from fossil fuel burning is dispersed vertically and between hemispheres.

Yver, CE, Graven HD, Lucas DD, Cameron-Smith PJ, Keeling RF, Weiss RF.  2013.  Evaluating transport in the WRF model along the California coast. Atmospheric Chemistry and Physics. 13:1837-1852.   10.5194/acp-13-1837-2013   AbstractWebsite

This paper presents a step in the development of a top-down method to complement the bottom-up inventories of halocarbon emissions in California using high frequency observations, forward simulations and inverse methods. The Scripps Institution of Oceanography high-frequency atmospheric halocarbons measurement sites are located along the California coast and therefore the evaluation of transport in the chosen Weather Research Forecast (WRF) model at these sites is crucial for inverse modeling. The performance of the transport model has been investigated by comparing the wind direction and speed and temperature at four locations using aircraft weather reports as well at all METAR weather stations in our domain for hourly variations. Different planetary boundary layer (PBL) schemes, horizontal resolutions (achieved through nesting) and two meteorological datasets have been tested. Finally, simulated concentration of an inert tracer has been briefly investigated. All the PBL schemes present similar results that generally agree with observations, except in summer when the model sea breeze is too strong. At the coarse 12 km resolution, using ERA-interim (ECMWF Re-Analysis) as initial and boundary conditions leads to improvements compared to using the North American Model (NAM) dataset. Adding higher resolution nests also improves the match with the observations. However, no further improvement is observed from increasing the nest resolution from 4 km to 0.8 km. Once optimized, the model is able to reproduce tracer measurements during typical winter California large-scale events (Santa Ana). Furthermore, with the WRF/CHEM chemistry module and the European Database for Global Atmospheric Research (EDGAR) version 4.1 emissions for HFC-134a, we find that using a simple emission scaling factor is not sufficient to infer emissions, which highlights the need for more complex inversions.

Nevison, CD, Manizza M, Keeling RF, Stephens BB, Bent JD, Dunne J, Ilyina T, Long M, Resplandy L, Tjiputra J, Yukimoto S.  2016.  Evaluating CMIP5 ocean biogeochemistry and Southern Ocean carbon uptake using atmospheric potential oxygen: Present-day performance and future projection. Geophysical Research Letters. 43:2077-2085.   10.1002/2015gl067584   AbstractWebsite

Observed seasonal cycles in atmospheric potential oxygen (APO similar to O-2+1.1 CO2) were used to evaluate eight ocean biogeochemistry models from the Coupled Model Intercomparison Project (CMIP5). Model APO seasonal cycles were computed from the CMIP5 air-sea O-2 and CO2 fluxes and compared to observations at three Southern Hemisphere monitoring sites. Four of the models captured either the observed APO seasonal amplitude or phasing relatively well, while the other four did not. Many models had an unrealistic seasonal phasing or amplitude of the CO2 flux, which in turn influenced APO. By 2100 under RCP8.5, the models projected little change in the O-2 component of APO but large changes in the seasonality of the CO2 component associated with ocean acidification. The models with poorer performance on present-day APO tended to project larger net carbon uptake in the Southern Ocean, both today and in 2100.

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.

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).

Rafelski, LE, Paplawsky B, Keeling RF.  2013.  An Equilibrator System to Measure Dissolved Oxygen and Its Isotopes. Journal of Atmospheric and Oceanic Technology. 30:361-377.   10.1175/jtech-d-12-00074.1   AbstractWebsite

An equilibrator is presented that is designed to have a sufficient equilibration time even for insoluble gases, and to minimize artifacts associated with not equilibrating to the total gas tension. A gas tension device was used to balance the pressure inside the equilibrator with the total gas tension. The equilibrator has an e-folding time of 7.36 +/- 0.74 min for oxygen and oxygen isotopes, allowing changes on hourly time scales to be easily resolved. The equilibrator delivers "equilibrated" air at a flow rate of 3 mL min(-1) to an isotope ratio mass spectrometer. The high gas sampling flow rate would allow the equilibrator to be interfaced with many potential devices, but further development may be required for use at sea. This system was tested at the Scripps Institution of Oceanography pier, in La Jolla, California. A mathematical model validated with performance tests was used to assess the sensitivity of the equilibrated air composition to headspace pressure and makeup gas composition. Parameters in this model can be quantified to establish corrections under different operating conditions. For typical observed values, under the operating conditions presented here, the uncertainty in the measurement due to the equilibrator system is 2.2 per mil for delta(O-2/N-2), 1.5 per mil for delta(O-2/Ar), 0.059 per mil for delta O-18, and 0.0030 per mil for Delta O-17.

Graven, HD, Keeling RF, Piper SC, Patra PK, Stephens BB, Wofsy SC, Welp LR, Sweeney C, Tans PP, Kelley JJ, Daube BC, Kort EA, Santoni GW, Bent JD.  2013.  Enhanced seasonal exchange of CO2 by northern ecosystems since 1960. Science. 341:1085-1089.   10.1126/science.1239207   AbstractWebsite

Seasonal variations of atmospheric carbon dioxide (CO2) in the Northern Hemisphere have increased since the 1950s, but sparse observations have prevented a clear assessment of the patterns of long-term change and the underlying mechanisms. We compare recent aircraft-based observations of CO2 above the North Pacific and Arctic Oceans to earlier data from 1958 to 1961 and find that the seasonal amplitude at altitudes of 3 to 6 km increased by 50% for 45 degrees to 90 degrees N but by less than 25% for 10 degrees to 45 degrees N. An increase of 30 to 60% in the seasonal exchange of CO2 by northern extratropical land ecosystems, focused on boreal forests, is implicated, substantially more than simulated by current land ecosystem models. The observations appear to signal large ecological changes in northern forests and a major shift in the global carbon cycle.

Forkel, M, Carvalhais N, Rodenbeck C, Keeling R, Heimann M, Thonicke K, Zaehle S, Reichstein M.  2016.  Enhanced seasonal CO2 exchange caused by amplified plant productivity in northern ecosystems. Science. 351:696-699.   10.1126/science.aac4971   AbstractWebsite

Atmospheric monitoring of high northern latitudes (above 40 degrees N) has shown an enhanced seasonal cycle of carbon dioxide (CO2) since the 1960s, but the underlying mechanisms are not yet fully understood. The much stronger increase in high latitudes relative to low ones suggests that northern ecosystems are experiencing large changes in vegetation and carbon cycle dynamics. We found that the latitudinal gradient of the increasing CO2 amplitude is mainly driven by positive trends in photosynthetic carbon uptake caused by recent climate change and mediated by changing vegetation cover in northern ecosystems. Our results underscore the importance of climate-vegetation-carbon cycle feedbacks at high latitudes; moreover, they indicate that in recent decades, photosynthetic carbon uptake has reacted much more strongly to warming than have carbon release processes.

Eddebbar, YA, Rodgers KB, Long MC, Subramanian AC, Xie SP, Keeling RF.  2019.  El Nino-like physical and biogeochemical ocean response to tropical eruptions. Journal of Climate. 32:2627-2649.   10.1175/jcli-d-18-0458.1   AbstractWebsite

The oceanic response to recent tropical eruptions is examined in Large Ensemble (LE) experiments from two fully coupled global climate models, the Community Earth System Model (CESM) and the Geophysical Fluid Dynamics Laboratory Earth System Model (ESM2M), each forced by a distinct volcanic forcing dataset. Following the simulated eruptions of Agung, El Chichon, and Pinatubo, the ocean loses heat and gains oxygen and carbon, in general agreement with available observations. In both models, substantial global surface cooling is accompanied by El Nino-like equatorial Pacific surface warming a year after the volcanic forcing peaks. A mechanistic analysis of the CESM and ESM2M responses to Pinatubo identifies remote wind forcing from the western Pacific as a major driver of this El Nino-like response. Following eruption, faster cooling over the Maritime Continent than adjacent oceans suppresses convection and leads to persistent westerly wind anomalies over the western tropical Pacific. These wind anomalies excite equatorial downwelling Kelvin waves and the upwelling of warm subsurface anomalies in the eastern Pacific, promoting the development of El Nino conditions through Bjerknes feedbacks a year after eruption. This El Nino-like response drives further ocean heat loss through enhanced equatorial cloud albedo, and dominates global carbon uptake as upwelling of carbon-rich waters is suppressed in the tropical Pacific. Oxygen uptake occurs primarily at high latitudes, where surface cooling intensifies the ventilation of subtropical thermocline waters. These volcanically forced ocean responses are large enough to contribute to the observed decadal variability in oceanic heat, carbon, and oxygen.

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Adachi, Y, Kawamura K, Armi L, Keeling RF.  2006.  Diffusive separation of the lower atmosphere. Science (Washington). 311:1429-1429.: American Association for the Advancement of Science, 1200 New York Avenue, NW Washington DC 20005 USA, [mailto:membership@aaas.org], [URL:http://www.aaas.org]   10.1126/science.1121312   AbstractWebsite

The separation of atmospheric constituents by gravity has been proposed theoretically for almost two centuries. However, turbulent mixing has prevented the detection of this phenomenon in the lower atmosphere. By using precise measurements of the Ar/N2 ratio of air samples taken under strong nocturnal inversions, we have detected such separation in near-surface layers. The effect is shown to be consistent with combined influence of thermal and gravimetric separation, with the thermal contribution being more important.

Lucas, DD, Yver Kwok C, Cameron-Smith P, Graven H, Bergmann D, Guilderson TP, Weiss R, Keeling R.  2015.  Designing optimal greenhouse gas observing networks that consider performance and cost. Geosci. Instrum. Method. Data Syst.. 4:121-137.: Copernicus Publications   10.5194/gi-4-121-2015   AbstractWebsite
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Welp, LR, Keeling RF, Weiss RF, Paplawsky W, Heckman S.  2013.  Design and performance of a Nafion dryer for continuous operation at CO2 and CH4 air monitoring sites. Atmos. Meas. Tech.. 6:1217-1226.: Copernicus Publications   10.5194/amt-6-1217-2013   AbstractWebsite

In preparation for routine deployment in a network of greenhouse gas monitoring stations, we have designed and tested a simple method for drying ambient air to near or below 0.2% (2000 ppm) mole fraction H2O using a Nafion dryer. The inlet system was designed for use with cavity ring-down spectrometer (CRDS) analyzers such as the Picarro model G2301 that measure H2O in addition to their principal analytes, in this case CO2 and CH4. These analyzers report dry-gas mixing ratios without drying the sample by measuring H2O mixing ratio at the same frequency as the main analytes, and then correcting for the dilution and peak broadening effects of H2O on the mixing ratios of the other analytes measured in moist air. However, it is difficult to accurately validate the water vapor correction in the field. By substantially lowering the amount of H2O in the sample, uncertainties in the applied water vapor corrections can be reduced by an order of magnitude or more, thus eliminating the need to determine instrument-specific water vapor correction coefficients and to verify the stability over time. Our Nafion drying inlet system takes advantage of the extra capacity of the analyzer pump to redirect 30% of the dry gas exiting the Nafion to the outer shell side of the dryer and has no consumables. We tested the Nafion dryer against a cryotrap (−97 °C) method for removing H2O and found that in wet-air tests, the Nafion reduces the CO2 dry-gas mixing ratios of the sample gas by as much as 0.1 ± 0.01 ppm due to leakage across the membrane. The effect on CH4 was smaller and varied within ± 0.2 ppb, with an approximate uncertainty of 0.1 ppb. The Nafion-induced CO2 bias is partially offset by sending the dry reference gases through the Nafion dryer as well. The residual bias due to the impact of moisture differences between sample and reference gas on the permeation through the Nafion was approximately −0.05 ppm for CO2 and varied within ± 0.2 ppb for CH4. The uncertainty of this partial drying method is within the WMO compatibility guidelines for the Northern Hemisphere, 0.1 ppm for CO2 and 2 ppb for CH4, and is comparable to experimentally determining water vapor corrections for each instrument but less subject to concerns of possible drift in these corrections.

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Rafelski, LE, Paplawsky B, Keeling RF.  2015.  Continuous measurements of dissolved O-2 and oxygen isotopes in the Southern California coastal ocean. Marine Chemistry. 174:94-102.   10.1016/j.marchem.2015.05.011   AbstractWebsite

Dissolved O-2/N-2, O-2/Ar, O-2 saturation and delta O-18 were measured continuously near the surface ocean at the Scripps Institution of Oceanography pier in La Jolla, California, for five weeks. The data showed diurnal cycles, in O-2 and delta O-18, with amplitudes of 19 mmol m(-3) and 1.1%., respectively. The diurnal cycles are well described by a box model that includes photosynthesis, respiration, air-sea gas exchange, and mixing. The timing of the cycles can be explained using a photosynthesis rate proportional to photosynthetically active radiation, and the shapes of the cycles can be explained by mixing with a subsurface layer of water that is supersaturated in O-2. Based on the diurnal cycles in O-2 and delta O-18, the average maximum daily photosynthesis rate was 3.7-4.7 mmol O-2 m(-3) h(-1), which is supported by the light-saturated photosynthesis rate estimated from the measured chlorophyll concentration. In the future, these continuous measurement techniques could be used at different locations and depths to improve the understanding of variability in oceanic primary production. (C) 2015 Elsevier B.V. All rights reserved.

Resplandy, L, Keeling RF, Stephens BB, Bent JD, Jacobson A, Rodenbeck C, Khatiwala S.  2016.  Constraints on oceanic meridional heat transport from combined measurements of oxygen and carbon. Climate Dynamics. 47:3335-3357.   10.1007/s00382-016-3029-3   AbstractWebsite

Despite its importance to the climate system, the ocean meridional heat transport is still poorly quantified. We identify a strong link between the northern hemisphere deficit in atmospheric potential oxygen (APO = O + 1.1 CO) and the asymmetry in meridional heat transport between northern and southern hemispheres. The recent aircraft observations from the HIPPO campaign reveal a northern APO deficit in the tropospheric column of 10.4 1.0 per meg, double the value at the surface and more representative of large-scale air-sea fluxes. The global northward ocean heat transport asymmetry necessary to explain the observed APO deficit is about 0.7-1.1 PW, which corresponds to the upper range of estimates from hydrographic sections and atmospheric reanalyses.

Graven, H, Allison CE, Etheridge DM, Hammer S, Keeling RF, Levin I, Meijer HAJ, Rubino M, Tans PP, Trudinger CM, Vaughn BH, White JWC.  2017.  Compiled records of carbon isotopes in atmospheric CO2 for historical simulations in CMIP6. Geoscientific Model Development. 10:4405-4417.   10.5194/gmd-10-4405-2017   AbstractWebsite

The isotopic composition of carbon (Delta C-14 and delta C-13) in atmospheric CO2 and in oceanic and terrestrial carbon reservoirs is influenced by anthropogenic emissions and by natural carbon exchanges, which can respond to and drive changes in climate. Simulations of C-14 and C-13 in the ocean and terrestrial components of Earth system models (ESMs) present opportunities for model evaluation and for investigation of carbon cycling, including anthropogenic CO2 emissions and uptake. The use of carbon isotopes in novel evaluation of the ESMs' component ocean and terrestrial biosphere models and in new analyses of historical changes may improve predictions of future changes in the carbon cycle and climate system. We compile existing data to produce records of Delta C-14 and delta C-13 in atmospheric CO2 for the historical period 1850-2015. The primary motivation for this compilation is to provide the atmospheric boundary condition for historical simulations in the Coupled Model Intercomparison Project 6 (CMIP6) for models simulating carbon isotopes in the ocean or terrestrial biosphere. The data may also be useful for other carbon cycle modelling activities.

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.

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.

Stephens, BB, Wofsy SC, Keeling RF, Tans PP.  2000.  The CO2 budget and rectification airborne study. Inverse methods in global biogeochemical cycles. ( Kasibhatla P, Ed.).:311-324., Washington, DC: American Geophysical Union Abstract

The CD-ROM contains the code and data files for the Exercises outlined in the paper by Rayner, et at., (p. 81-106).

Rafelski, LE, Piper SC, Keeling RF.  2009.  Climate effects on atmospheric carbon dioxide over the last century. Tellus Series B-Chemical and Physical Meteorology. 61:718-731.   10.1111/j.1600-0889.2009.00439.x   AbstractWebsite

The buildup of atmospheric CO(2) since 1958 is surprisingly well explained by the simple premise that 57% of the industrial emissions (fossil fuel burning and cement manufacture) has remained airborne. This premise accounts well for the rise both before and after 1980 despite a decrease in the growth rate of fossil fuel CO(2) emissions, which occurred at that time, and by itself should have caused the airborne fraction to decrease. In contrast, the buildup prior to 1958 was not simply proportional to cumulative fossil fuel emissions, and notably included a period during the 1940s when CO(2) growth stalled despite continued fossil fuel emissions. Here we show that the constancy of the airborne fraction since 1958 can be in part explained by decadal variations in global land air temperature, which caused a warming-induced release of CO(2) from the land biosphere to the atmosphere. We also show that the 1940s plateau may be related to these decadal temperature variations. Furthermore, we show that there is a close connection between the phenomenology producing CO(2) variability on multidecadal and El Nino timescales.

Tanhua, T, Keeling RF.  2012.  Changes in column inventories of carbon and oxygen in the Atlantic Ocean. Biogeosciences. 9:4819-4833.   10.5194/bg-9-4819-2012   AbstractWebsite

Increasing concentrations of dissolved inorganic carbon (DIC) in the interior ocean are expected as a direct consequence of increasing concentrations of CO2 in the atmosphere. This extra DIC is often referred to as anthropogenic carbon (C-ant), and its inventory, or increase rate, in the interior ocean has previously been estimated by a multitude of observational approaches. Each of these methods is associated with hard to test assumptions since C-ant cannot be directly observed. Results from a simpler concept with fewer assumptions applied to the Atlantic Ocean are reported on here using two large data collections of carbon relevant bottle data. The change in column inventory on decadal time scales, i.e. the storage rate, of DIC, respiration compensated DIC and oxygen is calculated for the Atlantic Ocean. We report storage rates and the confidence intervals of the mean trend at the 95% level (CI), reflecting the mean trend but not considering potential biasing effects of the spatial and temporal sampling. For the whole Atlantic Ocean the mean trends for DIC and oxygen are non-zero at the 95% confidence level: DIC: 0.86 (CI: 0.72-1.00) and oxygen: -0.24 (CI: -0.41-(-0.07)) mol m(-2) yr(-1). For oxygen, the whole Atlantic trend is dominated by the subpolar North Atlantic, whereas for other regions the O-2 trends are not significant. The storage rates are similar to changes found by other studies, although with large uncertainty. For the subpolar North Atlantic the storage rates show significant temporal and regional variation of all variables. This seems to be due to variations in the prevalence of subsurface water masses with different DIC and oxygen concentrations leading to sometimes different signs of storage rates for DIC compared to published C-ant estimates. This study suggest that accurate assessment of the uptake of CO2 by the oceans will require accounting not only for processes that influence C-ant but also additional processes that modify CO2 storage.

Keeling, RF, Garcia HE.  2002.  The change in oceanic O2 inventory associated with recent global warming. Proceedings of the National Academy of Sciences of the United States of America. 99:7848-7853.   10.1073/pnas.122154899   AbstractWebsite

Oceans general circulation models predict that global warming may cause a decrease in the oceanic O-2 inventory and an associated O-2 outgassing. An independent argument is presented here in support of this prediction based on observational evidence of the ocean's biogeochemical response to natural warming. On time scales from seasonal to centennial, natural O-2 flux/heat flux ratios are shown to occur in a range of 2 to 10 nmol of O-2 per joule of warming, with larger ratios typically occurring at higher latitudes and overlongertime scales. The ratios are several times larger than would be expected solely from the effect of heating on the O-2 solubility, indicating that most of the O-2 exchange is biologically mediated through links between heating and stratification. The change in oceanic O-2 inventory through the 1990s is estimated to be 0.3 +/- 0.4 X 10(14) mol of O-2 per year based on scaling the observed anomalous long-term ocean warming by natural O-2 flux/heating ratios and allowing for uncertainty due to decadal variability. Implications are discussed for carbon budgets based on observed changes in atmospheric O-2/N-2 ratio and based on observed changes in ocean dissolved inorganic carbon.