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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.

Wagner, TJW, Dell RW, Eisenman I, Keeling RF, Padman L, Severinghaus JP.  2018.  Wave inhibition by sea ice enables trans-Atlantic ice rafting of debris during Heinrich events. Earth and Planetary Science Letters. 495:157-163.   10.1016/j.epsl.2018.05.006   AbstractWebsite

The last glacial period was punctuated by episodes of massive iceberg calving from the Laurentide Ice Sheet, called Heinrich events, which are identified by layers of ice-rafted debris (IRD) in ocean sediment cores from the North Atlantic. The thickness of these IRD layers declines more gradually with distance from the iceberg sources than would be expected based on present-day iceberg drift and decay. Here we model icebergs as passive Lagrangian particles driven by ocean currents, winds, and sea surface temperatures. The icebergs are released in a comprehensive climate model simulation of the last glacial maximum (LGM), as well as a simulation of the modern climate. The two simulated climates result in qualitatively similar distributions of iceberg meltwater and hence debris, with the colder temperatures of the LGM having only a relatively small effect on meltwater spread. In both scenarios, meltwater flux falls off rapidly with zonal distance from the source, in contrast with the more uniform spread of IRD in sediment cores. To address this discrepancy, we propose a physical mechanism that could have prolonged the lifetime of icebergs during Heinrich events. The mechanism involves a surface layer of cold and fresh meltwater formed from, and retained around, large densely packed armadas of icebergs. This leads to wintertime sea ice formation even in relatively low latitudes. The sea ice in turn shields the icebergs from wave erosion, which is the main source of iceberg ablation. We find that sea ice could plausibly have formed around the icebergs during four months each winter. Allowing for four months of sea ice in the model results in a simulated IRD distribution which approximately agrees with the distribution of IRD in sediment cores. (C) 2018 Elsevier B.V. All rights reserved.

Graven, HD, Stephens BB, Guilderson TP, Campos TL, Schimel DS, Campbell JE, Keeling RF.  2009.  Vertical profiles of biospheric and fossil fuel-derived CO2 and fossil fuel CO2: CO ratios from airborne measurements of Δ14C, CO2 and CO above Colorado, USA. Tellus Series B-Chemical and Physical Meteorology. 61:536-546.   10.1111/j.1600-0889.2009.00421.x   AbstractWebsite

Measurements of Delta C-14 in atmospheric CO2 are an effective method of separating CO2 additions from fossil fuel and biospheric sources or sinks of CO2. We illustrate this technique with vertical profiles of CO2 and Delta C-14 analysed in whole air flask samples collected above Colorado, USA in May and July 2004. Comparison of lower tropospheric composition to cleaner air at higher altitudes (>5 km) revealed considerable additions from respiration in the morning in both urban and rural locations. Afternoon concentrations were mainly governed by fossil fuel emissions and boundary layer depth, also showing net biospheric CO2 uptake in some cases. We estimate local industrial CO2: CO emission ratios using in situ measurements of CO concentration. Ratios are found to vary by 100% and average 57 mole CO2:1 mole CO, higher than expected from emissions inventories. Uncertainty in CO2 from different sources was +/- 1.1 to +/- 4.1 ppm for addition or uptake of -4.6 to 55.8 ppm, limited by Delta 14C measurement precision and uncertainty in background Delta C-14 and CO2 levels.

Le Quere, C, Aumont O, Bopp L, Bousquet P, Ciais P, Francey R, Heimann M, Keeling CD, Keeling RF, Kheshgi H, Peylin P, Piper SC, Prentice IC, Rayner PJ.  2003.  Two decades of ocean CO2 sink and variability. Tellus Series B-Chemical and Physical Meteorology. 55:649-656.   10.1034/j.1600-0889.2003.00043.x   AbstractWebsite

Atmospheric CO2 has increased at a nearly identical average rate of 3.3 and 3.2 Pg C yr(-1) for the decades of the 1980s and the 1990s, in spite of a large increase in fossil fuel emissions from 5.4 to 6.3 Pg C yr(-1). Thus, the sum of the ocean and land CO2 sinks was 1 Pg C yr(-1) larger in the 1990s than in to the 1980s. Here we quantify the ocean and land sinks for these two decades using recent atmospheric inversions and ocean models. The ocean and land sinks are estimated to be, respectively, 0.3 (0.1 to 0.6) and 0.7 (0.4 to 0.9) Pg C yr(-1) larger in the 1990s than in the 1980s. When variability less than 5 yr is removed, all estimates show a global oceanic sink more or less steadily increasing with time, and a large anomaly in the land sink during 1990-1994. For year-to-year variability, all estimates show 1/3 to 1/2 less variability in the ocean than on land, but the amplitude and phase of the oceanic variability remain poorly determined. A mean oceanic sink of 1.9 Pg C yr(-1) for the 1990s based on O-2 observations corrected for ocean outgassing is supported by these estimates, but an uncertainty on the mean value of the order of +/-0.7 Pg C yr(-1) remains. The difference between the two decades appears to be more robust than the absolute value of either of the two decades.

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.

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.

Newman, S, Xu XM, Gurney KR, Hsu YK, Li KF, Jiang X, Keeling R, Feng S, O'Keefe D, Patarasuk R, Wong KW, Rao P, Fischer ML, Yung YL.  2016.  Toward consistency between trends in bottom-up CO2 emissions and top-down atmospheric measurements in the Los Angeles megacity. Atmospheric Chemistry and Physics. 16:3843-3863. AbstractWebsite

Large urban emissions of greenhouse gases result in large atmospheric enhancements relative to background that are easily measured. Using CO2 mole fractions and delta C-14 and delta C-13 values of CO2 in the Los Angeles megacity observed in inland Pasadena (2006-2013) and coastal Palos Verdes peninsula (autumn 2009-2013), we have determined time series for CO2 contributions from fossil fuel combustion (C-ff) for both sites and broken those down into contributions from petroleum and/or gasoline and natural gas burning for Pasadena. We find a 10 % reduction in Pasadena C-ff during the Great Recession of 2008-2010, which is consistent with the bottom-up inventory determined by the California Air Resources Board. The isotopic variations and total atmospheric CO2 from our observations are used to infer seasonality of natural gas and petroleum combustion. The trend of CO2 contributions to the atmosphere from natural gas combustion is out of phase with the seasonal cycle of total natural gas combustion seasonal patterns in bottom-up inventories but is consistent with the seasonality of natural gas usage by the area's electricity generating power plants. For petroleum, the inferred seasonality of CO2 contributions from burning petroleum is delayed by several months relative to usage indicated by statewide gasoline taxes. Using the high-resolution Hestia-LA data product to compare C-ff from parts of the basin sampled by winds at different times of year, we find that variations in observed fossil fuel CO2 reflect seasonal variations in wind direction. The seasonality of the local CO2 excess from fossil fuel combustion along the coast, on Palos Verdes peninsula, is higher in autumn and winter than spring and summer, almost completely out of phase with that from Pasadena, also because of the annual variations of winds in the region. Variations in fossil fuel CO2 signals are consistent with sampling the bottom-up Hestia-LA fossil CO2 emissions product for sub-city source regions in the LA megacity domain when wind directions are considered.

Stephens, BB, Keeling RF, Heimann M, Six KD, Murnane R, Caldeira K.  1998.  Testing global ocean carbon cycle models using measurements of atmospheric O2 and CO2 concentration. Global Biogeochemical Cycles. 12:213-230.   10.1029/97gb03500   AbstractWebsite

We present a method for testing the performance of global ocean carbon cycle models using measurements of atmospheric O-2 and CO2 concentration. We combine these measurements to define a tracer, atmospheric potential oxygen (APO approximate to O-2 + CO2), which is conservative with respect to terrestrial photosynthesis and respiration. We then compare observations of APO to the simulations of an atmospheric transport model which uses ocean-model air-sea fluxes and fossil fuel combustion estimates as lower boundary conditions. We present observations of the annual-average concentrations of CO2, O-2, and APO at 10 stations in a north-south transect. The observations of APO show a significant interhemispheric gradient decreasing towards the north. We use air-sea CO2, O-2, and N-2 fluxes from the Princeton ocean biogeochemistry model, the Hamburg model of the ocean carbon cycle, and the Lawrence Livermore ocean biogeochemistry model to drive the TM2 atmospheric transport model. The latitudinal variations in annual-average APO predicted by the combined models are distinctly different from the observations. All three models significantly underestimate the interhemispheric difference in APO, suggesting that they underestimate the net southward transport of the sum of O-2 and CO2 in the oceans. Uncertainties in the model-observation comparisons include uncertainties associated with the atmospheric measurements, the atmospheric transport model, and the physical and biological components of the ocean models. Potential deficiencies in the physical components of the ocean models, which have previously been suggested as causes for anomalously large heat fluxes out of the Southern Ocean, may contribute to the discrepancies with the APO observations. These deficiencies include the inadequate parameterization of subgrid-scale isopycnal eddy mixing, a lack of subgrid-scale vertical convection, too much Antarctic sea-ice formation, and an overestimation of vertical diffusivities in the main thermocline.

Volk, T, Keeling R.  1993.  Summary of workshop on interannual variations in the carbon cycle. The Global carbon cycle. ( Heimann M, Ed.).:579-581., Berlin; New York: Springer-Verlag Abstract
Betts, RA, Jones CD, Knight JR, Keeling RF, Kennedy JJ, Wiltshire AJ, Andrew RM, Aragao L.  2018.  A successful prediction of the record CO2 rise associated with the 2015/2016 El Nino. Philosophical Transactions of the Royal Society B-Biological Sciences. 373   10.1098/rstb.2017.0301   AbstractWebsite

In early 2016, we predicted that the annual rise in carbon dioxide concentration at Mauna Loa would be the largest on record. Our forecast used a statistical relationship between observed and forecast sea surface temperatures in the Nino 3.4 region and the annual CO2 rise. Here, we provide a formal verification of that forecast. The observed rise of 3.4 ppm relative to 2015 was within the forecast range of 3.15 +/- 0.53 ppm, so the prediction was successful. A global terrestrial biosphere model supports the expectation that the El Nino weakened the tropical land carbon sink. We estimate that the El Nino contributed approximately 25% to the record rise in CO2, with 75% due to anthropogenic emissions. The 2015/2016 CO2 rise was greater than that following the previous large El Nino in 1997/1998, because anthropogenic emissions had increased. We had also correctly predicted that 2016 would be the first year with monthly mean CO2 above 400 ppm all year round. We now estimate that atmospheric CO2 at Mauna Loa would have remained above 400 ppm all year round in 2016 even if the El Nino had not occurred, contrary to our previous expectations based on a simple extrapolation of previous trends. This article is part of a discussion meeting issue 'The impact of the 2015/2016 El Nino on the terrestrial tropical carbon cycle: patterns, mechanisms and implications'.

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.

Yadav, V, Duren R, Mueller K, Verhulst KR, Nehrkorn T, Kim J, Weiss RF, Keeling R, Sander S, Fischer ML, Newman S, Falk M, Kuwayama T, Hopkins F, Rafiq T, Whetstone J, Miller C.  2019.  Spatio-temporally resolved methane fluxes from the Los Angeles megacity. Journal of Geophysical Research-Atmospheres. 124:5131-5148.   10.1029/2018jd030062   AbstractWebsite

We combine sustained observations from a network of atmospheric monitoring stations with inverse modeling to uniquely obtain spatiotemporal (3-km, 4-day) estimates of methane emissions from the Los Angeles megacity and the broader South Coast Air Basin for 2015-2016. Our inversions use customized and validated high-fidelity meteorological output from Weather Research Forecasting and Stochastic Time-Inverted Lagrangian model for South Coast Air Basin and innovatively employ a model resolution matrix-based metric to disentangle the spatiotemporal information content of observations as manifested through estimated fluxes. We partially track and constrain fluxes from the Aliso Canyon natural gas leak and detect closure of the Puente Hills landfill, with no prior information. Our annually aggregated fluxes and their uncertainty excluding the Aliso Canyon leak period lie within the uncertainty bounds of the fluxes reported by the previous studies. Spatially, major sources of CH4 emissions in the basin were correlated with CH4-emitting infrastructure. Temporally, our findings show large seasonal variations in CH4 fluxes with significantly higher fluxes in winter in comparison to summer months, which is consistent with natural gas demand and anticorrelated with air temperature. Overall, this is the first study that utilizes inversions to detect both enhancement (Aliso Canyon leak) and reduction (Puente Hills) in CH4 fluxes due to the unintended events and policy decisions and thereby demonstrates the utility of inverse modeling for identifying variations in fluxes at fine spatiotemporal resolution.

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.

Fischer, ML, Parazoo N, Brophy K, Cui XG, Jeong S, Liu JJ, Keeling R, Taylor TE, Gurney K, Oda T, Graven H.  2017.  Simulating estimation of California fossil fuel and biosphere carbon dioxide exchanges combining in situ tower and satellite column observations. Journal of Geophysical Research-Atmospheres. 122:3653-3671.   10.1002/2016jd025617   AbstractWebsite

We report simulation experiments estimating the uncertainties in California regional fossil fuel and biosphere CO2 exchanges that might be obtained by using an atmospheric inverse modeling system driven by the combination of ground-based observations of radiocarbon and total CO2, together with column-mean CO2 observations from NASA's Orbiting Carbon Observatory (OCO-2). The work includes an initial examination of statistical uncertainties in prior models for CO2 exchange, in radiocarbon-based fossil fuel CO2 measurements, in OCO-2 measurements, and in a regional atmospheric transport modeling system. Using these nominal assumptions for measurement and model uncertainties, we find that flask measurements of radiocarbon and total CO2 at 10 towers can be used to distinguish between different fossil fuel emission data products for major urban regions of California. We then show that the combination of flask and OCO-2 observations yields posterior uncertainties in monthly-mean fossil fuel emissions of similar to 5-10%, levels likely useful for policy relevant evaluation of bottom-up fossil fuel emission estimates. Similarly, we find that inversions yield uncertainties in monthly biosphere CO2 exchange of similar to 6%-12%, depending on season, providing useful information on net carbon uptake in California's forests and agricultural lands. Finally, initial sensitivity analysis suggests that obtaining the above results requires control of systematic biases below approximately 0.5ppm, placing requirements on accuracy of the atmospheric measurements, background subtraction, and atmospheric transport modeling.

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.

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.

Keeling, RF, Shertz SR.  1992.  Seasonal and interannual variations in atmospheric oxygen and implications for the global carbon cycle. Nature. 358:723-727.   10.1038/358723a0   AbstractWebsite

Measurements of changes in atmospheric molecular oxygen using a new interferometric technique show that the O2 content of air varies seasonally in both the Northern and Southern Hemispheres and is decreasing from year to year. The seasonal variations provide a new basis for estimating global rates of biological organic carbon production in the ocean, and the interannual decrease constrains estimates of the rate of anthropogenic CO2 uptake by the oceans.

Resplandy, L, Keeling RF, Rodenbeck C, Stephens BB, Khatiwala S, Rodgers KB, Long MC, Bopp L, Tans PP.  2018.  Revision of global carbon fluxes based on a reassessment of oceanic and riverine carbon transport. Nature Geoscience. 11:504-+.   10.1038/s41561-018-0151-3   AbstractWebsite

Measurements of atmospheric CO2 concentration provide a tight constraint on the sum of the land and ocean sinks. This constraint has been combined with estimates of ocean carbon flux and riverine transport of carbon from land to oceans to isolate the land sink. Uncertainties in the ocean and river fluxes therefore translate into uncertainties in the land sink. Here, we introduce a heat-based constraint on the latitudinal distribution of ocean and river carbon fluxes, and reassess the partition between ocean, river and land in the tropics, and in the southern and northern extra-tropics. We show that the ocean overturning circulation and biological pump tightly link the ocean transports of heat and carbon between hemispheres. Using this coupling between heat and carbon, we derive ocean and river carbon fluxes compatible with observational constraints on heat transport. This heat-based constraint requires a 20-100% stronger ocean and river carbon transport from the Northern Hemisphere to the Southern Hemisphere than existing estimates, and supports an upward revision of the global riverine carbon flux from 0.45 to 0.78 PgC yr(-1). These systematic biases in existing ocean/river carbon fluxes redistribute up to 40% of the carbon sink between northern, tropical and southern land ecosystems. As a consequence, the magnitude of both the southern land source and the northern land sink may have to be substantially reduced.

Rahmstorf, S, Cazenave A, Church JA, Hansen JE, Keeling RF, Parker DE, Somerville RCJ.  2007.  Recent climate observations compared to projections. Science. 316:709-709.   10.1126/science.1136843   AbstractWebsite

We present recent observed climate trends for carbon dioxide concentration, global mean air temperature, and global sea level, and we compare these trends to previous model projections as summarized in the 2001 assessment report of the Intergovernmental Panel on Climate Change (IPCC). The IPCC scenarios and projections start in the year 1990, which is also the base year of the Kyoto protocol, in which almost all industrialized nations accepted a binding commitment to reduce their greenhouse gas emissions. The data available for the period since 1990 raise concerns that the climate system, in particular sea level, may be responding more quickly to climate change than our current generation of models indicates.

Resplandy, L, Keeling RF, Eddebbar Y, Brooks MK, Wang R, Bopp L, Long MC, Dunne JP, Koeve W, Oschlies A.  2018.  Quantification of ocean heat uptake from changes in atmospheric O2 and CO2 composition. Nature. 563:105-108.   10.1038/s41586-018-0651-8   Abstract

The ocean is the main source of thermal inertia in the climate system1. During recent decades, ocean heat uptake has been quantified by using hydrographic temperature measurements and data from the Argo float program, which expanded its coverage after 20072,3. However, these estimates all use the same imperfect ocean dataset and share additional uncertainties resulting from sparse coverage, especially before 20074,5. Here we provide an independent estimate by using measurements of atmospheric oxygen (O2) and carbon dioxide (CO2)—levels of which increase as the ocean warms and releases gases—as a whole-ocean thermometer. We show that the ocean gained 1.33 ± 0.20  × 1022 joules of heat per year between 1991 and 2016, equivalent to a planetary energy imbalance of 0.83 ± 0.11 watts per square metre of Earth’s surface. We also find that the ocean-warming effect that led to the outgassing of O2 and CO2 can be isolated from the direct effects of anthropogenic emissions and CO2 sinks. Our result—which relies on high-precision O2 measurements dating back to 19916—suggests that ocean warming is at the high end of previous estimates, with implications for policy-relevant measurements of the Earth response to climate change, such as climate sensitivity to greenhouse gases7 and the thermal component of sea-level rise8.

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.

Perks, HM, Charles CD, Keeling RF.  2002.  Precessionally forced productivity variations across the equatorial Pacific. Paleoceanography. 17   10.1029/2000pa000603   AbstractWebsite

[1] Measurements of combustion oxygen demand (COD) in two sediment cores provide a record of paleoproductivity driven by surface-ocean dynamics in the equatorial eastern and western Pacific for the past 400,000 years. The COD time series are well correlated with each other over this time span and show pronounced precessionally forced peaks of higher productivity during globally colder periods. The phase of this signal in the two cores is identical, to within chronological uncertainties, suggesting a common insolation forcing mechanism for the upper ocean across the equatorial Pacific. COD is also in phase with the precessionally forced component of global ice volume, as indicated by oxygen isotopes, and with atmospheric methane in the Vostok ice core. These relationships imply that the COD relative paleoproductivity index provides an important diagnostic measure of the mechanisms of tropical ocean dynamics and climate change.

Langenfelds, RL, Francey RJ, Steele LP, Battle M, Keeling RF, Budd WF.  1999.  Partitioning of the global fossil CO2 sink using a 19-year trend in atmospheric O2. Geophysical Research Letters. 26:1897-1900.   10.1029/1999gl900446   AbstractWebsite

O-2/N-2 is measured in the Cape Grim Air Archive (CGAA), a suite of tanks filled with background air at Cape Grim, Tasmania (40.7 degrees S, 144.8 degrees E) between April 1978 and January 1997. Derived trends are compared with published O-2/N-2 records and assessed against limits on interannual variability of net terrestrial exchanges imposed by trends of delta(13)C in CO2. Two old samples from 1978 and 1987 and eight from 1996/97 survive critical selection criteria and give a mean 19-year trend in delta(O-2/N-2) of -16.7 +/- 0.5 per meg y(-1), implying net storage of +2.3 +/- 0.7 GtC (10(15) g carbon) yr(-1) of fossil fuel CO2 in the oceans and +0.2 +/- 0.9 GtC yr(-1) in the terrestrial biosphere. The uptake terms are consistent for both O-2/N-2 and delta(13)C tracers if the mean C-13 isotopic disequilibrium flux, combining terrestrial and oceanic contributions, is 93 +/- 15 GtC parts per thousand yr(-1).

Keeling, RF, Visbeck M.  2001.  Palaeoceanography - Antarctic stratification and glacial CO2. Nature. 412:605-606.   10.1038/35088129   AbstractWebsite

One way of accounting for lowered atmospheric carbon dioxide concentrations during Pleistocene glacial periods is by invoking the Antarctic stratification hypothesis, which links the reduction in CO2 to greater stratification of ocean surface waters around Antarctica1, 2. As discussed by Sigman and Boyle3, this hypothesis assumes that increased stratification in the Antarctic zone (Fig. 1) was associated with reduced upwelling of deep waters around Antarctica, thereby allowing CO2 outgassing to be suppressed by biological production while also allowing biological production to decline, which is consistent with Antarctic sediment records4. We point out here, however, that the response of ocean eddies to increased Antarctic stratification can be expected to increase, rather than reduce, the upwelling rate of deep waters around Antarctica. The stratification hypothesis may have difficulty in accommodating eddy feedbacks on upwelling within the constraints imposed by reconstructions of winds and Antarctic-zone productivity in glacial periods.

Lueker, TJ, Keeling RF, Dubey MK.  2001.  The oxygen to carbon dioxide ratios observed in emissions from a wildfire in Northern California. Geophysical Research Letters. 28:2413-2416.   10.1029/2000gl011860   AbstractWebsite

At Trinidad, California we observed elevated CO2 concentrations and concomitant lowered O-2 levels coincident with forest fires 70 kin distant (from 10/8/99 to 10/21/99). The precision of our O-2 data, 1 mu mol O-2 /mol dry air, revealed the reduction of atmospheric oxygen resulting from the combustion of biomass, and the stoichiometric ratios (-O-2/CO2) of the wildfire emissions. Estimates of daily -O-2/CO2 ratios were obtained by regression of CO2 against corresponding O-2 data (R-2, 0.86 to 0.96). Daily -O-2/CO2 ratios changed from 1.15 to 1.41 on a particularly smoky day that coincided with elevated levels of CH4 and increased CH4/CO2 ratios. The change to a higher ratio during smoky conditions illustrates the association between changing emissions and -O-2/CO2 ratios, possibly due to changing wildfire dynamics.