Ralph F. Keeling

The influence of Antarctic sea ice on glacial-interglacial CO2 variations

Ice-core measurements indicate that atmospheric CO2 concentrations during glacial periods were consistently about 80 parts per million lower than during interglacial periods. Previous explanations for this observation have typically had difficulty accounting for either the estimated glacial O2 concentrations in the deep sea, 13C/12C ratios in Antarctic surface waters, or the depth of calcite saturation; also lacking is an explanation for the strong link between atmospheric CO2 and Antarctic air temperature. There is growing evidence that the amount of deep water upwelling at low latitudes is significantly overestimated in most ocean general circulation models and simpler box models previously used to investigate this problem. Here we use a box model with deep-water upwelling confined to south of 55 °S to investigate the glacial–interglacial linkages between Antarctic air temperature and atmospheric CO2 variations. We suggest that low glacial atmospheric CO2 levels might result from reduced deep-water ventilation associated with either year-round Antarctic sea-ice coverage, or wintertime coverage combined with ice-induced stratification during the summer. The model presented here reproduces 67 parts per million of the observed glacial–interglacial CO2 difference, as a result of reduced air–sea gas exchange in the Antarctic region, and is generally consistent with the additional observational constraints.

Oceanic 13C/12C observations: A new window on ocean CO2 uptake

Equations are developed describing the rate of change of carbon isotopic ratios in the atmosphere and oceans in terms of δ13C quantities. The equations enable one to perform calculations directly with δ and ϵ quantities commonly reported in the literature. The main cause of the change occurring today is the combustion of fossil fuel carbon with lower δ13C values. The course of this isotopic anomaly in atmosphere and oceans can provide new constraints on the carbon budgets of these reservoirs. Recently published δ13C isotopic data of total inorganic carbon in the oceans [Quay et al., 1992] appear to lead to incompatible results with respect to the uptake of fossil fuel CO2 by the oceans if two different approaches to the data are taken. Consideration of the air-sea isotopic disequilibrium leads to an uptake estimate of only a few tenths of a gigaton C (Gt, for 1015 g) per year, whereas the apparent change in the ocean δ13C inventory leads to an estimate of more than 2 Gt C yr−1. Both results are very uncertain with presently available data. The isotopic ratio has the advantage that the signal-to-noise ratio for the measurement of the uptake of the isotopic signal by the oceans is better than for the uptake of total carbon, The drawback is that isotopic exchange with carbon reservoirs that are difficult to characterize introduces uncertainty into the isotopic budget. The accuracy requirements for the measurements are high, demanding careful standardization at all stages.

The change in oceanic O 2 inventory associated with recent global warming

Oceans general circulation models predict that global warming may cause a decrease in the oceanic O2 inventory and an associated O2 outgassing. An independent argument is presented here in support of this prediction based on observational evidence of the oceans biogeochemical response to natural warming. On time scales from seasonal to centennial, natural O2 flux/heat flux ratios are shown to occur in a range of 2 to 10 nmol of O2 per joule of warming, with larger ratios typically occurring at higher latitudes and over longer time scales. The ratios are several times larger than would be expected solely from the effect of heating on the O2 solubility, indicating that most of the O2 exchange is biologically mediated through links between heating and stratification. The change in oceanic O2 inventory through the 1990s is estimated to be 0.3 ± 0.4 × 1014 mol of O2 per year based on scaling the observed anomalous long-term ocean warming by natural O2 flux/heating ratios and allowing for uncertainty due to decadal variability. Implications are discussed for carbon budgets based on observed changes in atmospheric O2/N2 ratio and based on observed changes in ocean dissolved inorganic carbon.

Global oceanic and land biotic carbon sinks from the Scripps atmospheric oxygen flask sampling network

Measurements of atmospheric O2/N2 ratio and CO2 concentration are presented over the period 1989–2003 from the Scripps Institution of Oceanography global flask sampling network.Aformal 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 O2 and N2 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 × 1014 mol O2 yr-1 and 0.20 × 1014 mol N2 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.

What atmospheric oxygen measurements can tell us about the global carbon cycle

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.

Enhanced seasonal exchange of CO2 by northern ecosystems since 1960.

Downs and Ups Every spring, the concentration of CO2 in the atmosphere of the Northern Hemisphere decreases as terrestrial vegetation grows, and every fall, CO2 rises as vegetation dies and rots. Climate change has destabilized the seasonal cycle of atmospheric CO2 such that Graven et al. (p. 1085, published online 8 August; see the Perspective by Fung) have found that the amplitude of the seasonal cycle has exceeded 50% at some latitudes. The only way to explain this increase is if extratropical land ecosystems are growing and shrinking more than they did half a century ago, as a result of changes in the structure and composition of northern ecosystems. The amplitude of the seasonal cycle of carbon dioxide in high northern latitudes has increased by 50% since 1960. [Also see Perspective by Fung] 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° to 90°N but by less than 25% for 10° to 45°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.

Testing global ocean carbon cycle models using measurements of atmospheric O2 and CO2 concentration

We present a method for testing the performance of global ocean carbon cycle models using measurements of atmospheric O2 and CO2 concentration. We combine these measurements to define a tracer, atmospheric potential oxygen (APO ≈ O2 + 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, O2, 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, O2, and N2 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 O2 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.

Interannual variability in the oxygen isotopes of atmospheric CO2 driven by El Nino

The stable isotope ratios of atmospheric CO2 (18O/16O and 13C/12C) have been monitored since 1977 to improve our understanding of the global carbon cycle, because biosphere–atmosphere exchange fluxes affect the different atomic masses in a measurable way. Interpreting the 18O/16O variability has proved difficult, however, because oxygen isotopes in CO2 are influenced by both the carbon cycle and the water cycle. Previous attention focused on the decreasing 18O/16O ratio in the 1990s, observed by the global Cooperative Air Sampling Network of the US National Oceanic and Atmospheric Administration Earth System Research Laboratory. This decrease was attributed variously to a number of processes including an increase in Northern Hemisphere soil respiration; a global increase in C4 crops at the expense of C3 forests; and environmental conditions, such as atmospheric turbulence and solar radiation, that affect CO2 exchange between leaves and the atmosphere. Here we present 30 years’ worth of data on 18O/16O in CO2 from the Scripps Institution of Oceanography global flask network and show that the interannual variability is strongly related to the El Niño/Southern Oscillation. We suggest that the redistribution of moisture and rainfall in the tropics during an El Niño increases the 18O/16O ratio of precipitation and plant water, and that this signal is then passed on to atmospheric CO2 by biosphere–atmosphere gas exchange. We show how the decay time of the El Niño anomaly in this data set can be useful in constraining global gross primary production. Our analysis shows a rapid recovery from El Niño events, implying a shorter cycling time of CO2 with respect to the terrestrial biosphere and oceans than previously estimated. Our analysis suggests that current estimates of global gross primary production, of 120 petagrams of carbon per year, may be too low, and that a best guess of 150–175 petagrams of carbon per year better reflects the observed rapid cycling of CO2. Although still tentative, such a revision would present a new benchmark by which to evaluate global biospheric carbon cycling models.

Seasonal variations in the atmospheric O2/N2 ratio in relation to the kinetics of air-sea gas exchange

Observations of seasonal variations in the atmospheric O2/N2 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 O2 on the O2/N2 cycles thus allowing the residual component of the cycles due to oceanic exchanges of O2 and N2 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 O2/N2 cycles is presented consisting of the TM2 atmospheric tracer transport model [Heimann, 1995] driven at the lower boundary by O2 fluxes derived from observed O2 saturation anomalies in surface waters and by N2 fluxes derived from the net air-sea heat flux. The model is optimized to fit the observed atmospheric O2/N2 cycles by adjusting the air-sea gas-exchange velocity, which relates O2 anomaly to O2 flux. The optimum fit corresponds to spatially and temporally averaged exchange velocities of 24±6 cm/hr for the oceans north of 31°N and 29±12 cm/hr for the oceans south of 31° 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 O2, 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.

Mean annual cycle of the air-sea oxygen flux : A global view

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 O2 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 O2/N2 measurements.