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Keeling, RF, Kortzinger A, Gruber N.  2010.  Ocean deoxygenation in a warming world. Annual Review of Marine Science. 2:199-229., Palo Alto: Annual Reviews   10.1146/annurev.marine.010908.163855   Abstract

Ocean warming and increased stratification of the upper ocean caused by global climate change will likely lead to declines in dissolved O(2) in the ocean interior (ocean deoxygenation) with implications for ocean productivity, nutrient cycling, carbon cycling, and marine habitat. Ocean models predict declines of 1 to 7% in the global ocean O(2) inventory over the next century, with declines continuing for a thousand years or more into the future. An important consequence may be an expansion in the area and volume of so-called oxygen minimum zones, where O(2) levels are too low to support many macrofauna and profound changes in biogeochemical cycling occur. Significant deoxy enation has occurred over the past 50 years in the North Pacific and tropical oceans, suggesting larger changes are looming. The potential for larger O(2) declines in the future suggests the need for all improved observing system for tracking ocean O(2) changes.

Keeling, RF, Severinghaus JP.  2000.  Atmospheric oxygen measurements and the carbon cycle. The carbon cycle (Global Change Insititute, Proceedings on the Carbon Cycle). ( Wigley TML, Schimel D, Eds.).:134-140., New York: Cambridge University Press Abstract
Keeling, RF.  1988.  Measuring correlations between atmospheric oxygen and carbon dioxide mole fractions: A preliminary study in urban air. Journal of Atmospheric Chemistry. 7:153-176.   10.1007/bf00048044   AbstractWebsite

On 25 and 26 October 1986 the air in Cambridge, Massachusetts was monitored for O2 and CO2 mole fraction. O2 concentrations were detected from changes in the relative refractivity of dried air between two lines of 198Hg at 2537.269 and 4359.562 Å using dual-wavelength interferometry. Changes in oxygen mole fraction were resolved with two-minute time resolution to a precision of ±2.0 ppm. Changes in O2 were shown to be strongly anticorrelated with changes in CO2 as expected for combustion processes. The demonstrated instrumental capabilities are appropriate for measuring changes in O2 mole fraction in background air which could be of importance to a broad range of biogeochemical studies.

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.

Keeling, RF, Piper SC, Heimann M.  1996.  Global and hemispheric CO2 sinks deduced from changes in atmospheric O2 concentration. Nature. 381:218-221.   10.1038/381218a0   AbstractWebsite

THE global budget for sources and sinks of anthropogenic CO2 has been found to be out of balance unless the oceanic sink is supplemented by an additional 'missing sink', plausibly associated with land biota(1,25). A similar budgeting problem has been found for the Northern Hemisphere alone(2,3), suggesting that northern land biota may be the sought-after sink, although this interpretation is not unique(2-5); to distinguish oceanic and land carbon uptake, the budgets rely variously, and controversially, on ocean models(2,6,7), (CO2)-C-13/(CO2)-C-12 data(2,4,5), sparse oceanic observations of p(CO2) (ref. 3) or C-13/C-12 ratios of dissolved inorganic carbon, (4,5,8) or single-latitude trends in atmospheric O-2 as detected from changes in O-2/N-2 ratio.(9,10). Here we present an extensive O-2/N-2 data set which shows simultaneous trends in O-2/N-2 in both northern and southern hemispheres and allows the O-2/N-2 gradient between the two hemispheres to be quantified. The data are consistent with a budget in which, for the 1991-94 period, the global oceans and the northern land biota each removed the equivalent of approximately 30% of fossil-fuel CO2 emissions, while the tropical land biota as a whole were not a strong source or sink.

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.  2002.  On the freshwater forcing of the thermohaline circulation in the limit of low diapycnal mixing. Journal of Geophysical Research-Oceans. 107   10.1029/2000jc000685   AbstractWebsite

[1] A conjecture is offered on the stability characteristics of the thermohaline circulation in the limit of very low diapycnal mixing. In this limit the action of the winds on the Antarctic Circumpolar Current (ACC) can sustain a deep overturning pattern known as the "reconfigured conveyor,'' consisting of upwelling around Antarctica and sinking in the North Atlantic, as shown by the work of Toggweiler and others. It is conjectured that in this limit, northern sinking should be stabilized in an "on'' state because of the penetration of freshwater into the ocean interior via isopycnal layers that outcrop to the surface within and south of the ACC. This conjecture is supported by qualitative arguments and by a hydraulic model for the reconfigured conveyor. The hydraulic model takes into account the freshwater budgets of the Atlantic basin, Antarctic surface waters, and the remaining oceans. It also takes into account, in simple terms, wind-driven Antarctic upwelling, eddy transports and mixing within the ACC, changes in pycnocline depth, the role of temperature forcing, and advective feedbacks on salinity. The hydraulic model suggests that multiple "on/off'' states of the reconfigured conveyor are possible but only if the deep waters that form in the Northern Hemisphere are fresher than the intermediate waters that form in the vicinity of the ACC in the Southern Hemisphere, a condition that is not satisfied in the modern ocean.

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.

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.

Keeling, RF, Stephens BB.  2001.  Antarctic sea ice and the control of Pleistocene climate instability (vol 16, pg 112, 2001). Paleoceanography. 16:330-334.   10.1029/2001pa000648   AbstractWebsite

In the paper “Antarctic sea ice and the control of Pleistocene climate instability” by Ralph F. Keeling and Britton B. Stephens (Paleoceanography, 16(1), 112-131,2001), approximately 10 paragraphs from section 5 and Appendix A were inadvertently omitted. The end of the paper from section 5 through the references, including Appendix A and Figure A1, appear below.

Keeling, RF.  1991.  Mechanisms for stabilization and destabilization of a simple biosphere: catastrophe on Daisyworld. Scientists on Gaia. ( Schneider S, Boston PJ, Eds.).:118-120., Cambridge, Mass.: MIT Press Abstract
Keeling, RF, Visbeck M.  2005.  Northern ice discharges and Antarctic warming: could ocean eddies provide the link? Quaternary Science Reviews. 24:1809-1820.   10.1016/j.quascirev.2005.04.005   AbstractWebsite

A mechanism is advanced for explaining the Antarctic warm events from 90 to 30ka BP which involves meltwater-induced changes in the salinity gradient across the Antarctic Circumpolar Current (ACC) and consequent changes in the poleward heat transport by ocean eddies. Based on simple linear scale analysis, the mechanism is shown to yield warming in the Antarctic interior of roughly the magnitude seen in Antarctic ice-core records (similar to 2 degrees C) in response to ice discharges into the North Atlantic. Consistent with observations, the mechanism produces gradual Antarctic warming and cooling, as dictated by the time required for salinity anomalies to build up and dissipate across the ACC. The mechanism also allows the onset of warming or cooling to be tied to changes in Atlantic overturning, which is relevant here, not for influencing ocean heat transport directly, but for influencing the routing of meltwater from the North Atlantic into the Southern Ocean. The ideas presented here highlight the possibility that eddy processes in the ocean may play a first-order role in aspects of climate variability on millennial time scales. (c) 2005 Elsevier Ltd. All rights reserved.

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

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

Keeling, RF, 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.

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).

Keeling, RF, Stephens BB.  2001.  Antarctic sea ice and the control of Pleistocene climate instability. Paleoceanography. 16:112-131,330-334.   10.1029/2000pa000529   Abstract

A hypothesis is presented for the origin of Pleistocene climate instability, based on expansion of Antarctic sea ice and associated changes in the oceans' salinity structure. The hypothesis assumes that thermohaline overturning is dominated by the reconfigured conveyor of Toggweiler and Samuels [1993b], in which deepwater upwelling is restricted to high southern latitudes. The reconfigured conveyor is shown to be potentially stabilized in an "on" mode by precipitation at high southern latitudes and potentially destabilized into "on" and "off" modes by the counteracting influence of Antarctic sea ice. The mechanism is clarified by the use of a hydraulic analogue. We hypothesize that this mechanism accounts for dominant patterns of thermohaline overturning and climate instability between Pleistocene warm and cold periods. The hypothesis is shown to be consistent with a range of paleoceanographic evidence and to potentially account for details of observed rapid climate changes during glacial and interglacial periods, including aspects of interhemispheric timing.

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.

Keeling, RF, Manning AC, Paplawsky WJ, Cox AC.  2007.  On the long-term stability of reference gases for atmospheric O2/N2 and CO2 measurements. Tellus Series B-Chemical and Physical Meteorology. 59:3-14.   10.1111/j.1600-0889.2006.00228.x   AbstractWebsite

Measurements of changes in the atmospheric O-2/N-2 ratio have typically relied on compressed air derived from high-pressure tanks as the reference material against which atmospheric changes are assessed. The validity of this procedure is examined here in the context of the history of 18 O-2/N-2 reference tanks compared over a 12-yr time-frame. By considering differences in tank sizes, material types, and by performing additional tests, the long-term stability of the delivered gas is evaluated with respect to surface reactions, leakage, regulator effects, and thermal diffusion and gravimetric fractionation. Results are also reported for the stability of CO2 in these tanks. The results emphasize the importance of orienting tanks horizontally within a thermally insulated enclosure to reduce thermal and gravimetric fractionation of both O-2/N-2 and CO2 concentrations, and they emphasize the importance of avoiding elastomeric O-rings at the head-valve base. With the procedures documented here, the long-term drift in O-2/N-2 appears to be zero to within approximately +/- 0.4 per meg yr(-1), which projects to an uncertainty of +/- 0.16 Pg C yr(-1) (1 sigma) in O-2-based global carbon budgets.

Keeling, RF, 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, Blaine T, Paplawsky B, Katz L, Atwood C, Brockwell T.  2006.  Measurement of changes in atmospheric Ar/N2 ratio using a rapid-switching, single-capillary mass spectrometer system (vol 56B, pg 322, 2006). Tellus Series B-Chemical and Physical Meteorology. 58:255-255.   10.1111/j.1600-0889.2006.00190.x   AbstractWebsite
Keeling, RF, Blaine T, Paplawsky B, Katz L, Atwood C, Brockwell T.  2004.  Measurement of changes in atmospheric Ar/N2 ratio using a rapid-switching, single-capillary mass spectrometer system. Tellus Series B-Chemical and Physical Meteorology. 56:322-338.   10.1111/j.1600-0889.2004.00117.x   AbstractWebsite

The atmospheric Ar/N-2 ratio is expected to undergo very slight variations due to exchanges of Ar and N-2 across the air-sea interface, driven by ocean solubility changes. Observations of these variations may provide useful constraints on large-scale fluxes of heat across the air-sea interface. A mass spectrometer system is described that incorporates a magnet with a wide exit face, allowing a large mass spread, and incorporates an inlet with rapid (5 s) switching of sources gases through a single capillary, thus achieving high precision in the comparison of sample and reference gases. The system allows simultaneous measurement of Ar/N-2, O-2/N, and CO2/N-2 ratios. The system achieves a short-term precision in Ar/N-2 of 10 per meg for a 10 s integration, which can be averaged to achieve an internal precision of a few per meg in the comparison of reference gases. Results for Ar/N-2 are reported from flasks samples collected from nine stations in a north-to-south global network over about a 1 yr period. The imprecision on an individual flask, as estimated from replicate agreement, is 11 per meg. This imprecision is dominated by real variability between samples at the time of analysis. Seasonal cycles are marginally resolved at the extra-tropical stations with amplitudes of 5 to 15 per meg. Annual-mean values are constant between stations to within 5 per meg. The results are compared with a numerical simulation of the cycles and gradients in Ar/N-2 based on the TM2 tracer transport model in combination with air-sea Ar and N-2 fluxes derived from climatological air-sea heat fluxes. The possibility is suggested that Ar/N-2 ratios may be detectably enriched near the ground by gravimetric or thermal fractionation under conditions of strong surface inversions.

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.