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Najjar, RG, Keeling RF.  1997.  Analysis of the mean annual cycle of the dissolved oxygen anomaly in the World Ocean. Journal of Marine Research. 55:117-151.   10.1357/0022240973224481   AbstractWebsite

A global climatology of the dissolved oxygen anomaly (the excess over saturation) is created with monthly resolution in the upper 500 m of the ocean. The climatology is based on dissolved oxygen, temperature and salinity data archived at the National Oceanographic Data Center. Examination of this climatology reveals statistically significant annual cycles throughout the upper 500 m of the World Ocean, though seasonal variations are most coherent in the North Atlantic, where data density is greatest. Vertical trends in the phase and amplitude of the annual cycle are noted. The cycle in surface waters is characterized by a summer maximum and a winter minimum, consistent with warming and high rates of photosynthesis during the summer, and cooling and entrainment of oxygen-depleted water during the winter. In low and middle latitudes, the amplitude increases with depth and the maximum occurs later in the year, a trend consistent with the seasonal accumulation of oxygen associated with the shallow oxygen maximum. At a depth that varies between about 30 and 130 m, the phase of the annual cycle undergoes an abrupt shift. We call this depth the oxygen nodal depth. Below the nodal depth, the annual cycle is characterized by an early-spring maximum and a late-fall minimum, consistent with a cycle dominated by respiration during the spring and summer and replenishment of oxygen from the atmosphere by ventilation during the fall and winter. Below the nodal depth, the amplitude of the annual cycle generally decreases with depth, indicative of decreasing respiration and ventilation rates, or less seasonality in both processes. We postulate that the nodal depth in middle and high latitudes corresponds closely to the summertime compensation depth, where photosynthesis and net community respiration are equal. With this interpretation of the nodal depth and a simple model of the penetration of light in the water column, a compensation light intensity of 1 W m(-2) (4 mu E m(-2) s(-1)) is deduced, at the low end of independent estimates. Horizontal trends in the phase and amplitude of the annual cycle are also noted. We find that the nodal depth decreases toward the poles in both hemispheres and is generally greater in the Southern Hemisphere, patterns found to be consistent with light-based estimates of the compensation depth. The amplitude of the annual cycle in the oxygen anomaly increases monotonically with latitude, and higher latitudes lag lower latitudes. In the North Atlantic and North Pacific, the amplitude of the annual cycle tends to increase from east to west at all depths and latitudes, as expected considering that physical forcing has greater seasonal variability in the west. The tropics and the North Indian Ocean have features that distinguish them from other regions. Below about 75 m, these waters have pronounced annual cycles of the oxygen anomaly that areshown to be caused mainly by wind-driven adiabatic displacements of the thermocline. A semiannual cycle of the oxygen anomaly is found in the surface waters of the North Indian Ocean, consistent with the known semiannual cycle of surface heat flux in this region.

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, 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.

Graven, H, Fischer ML, Lueker T, Jeong S, Guilderson TP, Keeling RF, Bambha R, Brophy K, Callahan W, Cui X, Frankenberg C, Gurney KR, LaFranchi BW, Lehman SJ, Michelsen H, Miller JB, Newman S, Paplawsky W, Parazoo NC, Sloop C, Walker SJ.  2018.  Assessing fossil fuel CO2 emissions in California using atmospheric observations and models. Environmental Research Letters. 13   10.1088/1748-9326/aabd43   AbstractWebsite

Analysis systems incorporating atmospheric observations could provide a powerful tool for validating fossil fuel CO2 (ffCO(2)) emissions reported for individual regions, provided that fossil fuel sources can be separated from other CO2 sources or sinks and atmospheric transport can be accurately accounted for. We quantified ffCO(2) by measuring radiocarbon (C-14) in CO2, an accurate fossil-carbon tracer, at nine observation sites in California for three months in 2014-15. There is strong agreement between the measurements and ffCO(2) simulated using a high-resolution atmospheric model and a spatiotemporally-resolved fossil fuel flux estimate. Inverse estimates of total in-state ffCO(2) emissions are consistent with the California Air Resources Board's reported ffCO(2) emissions, providing tentative validation of California's reported ffCO(2) emissions in 2014-15. Continuing this prototype analysis system could provide critical independent evaluation of reported ffCO(2) emissions and emissions reductions in California, and the system could be expanded to other, more data-poor regions.

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

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

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).