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Perks, HM, Keeling RF.  1998.  A 400 kyr record of combustion oxygen demand in the western equatorial Pacific: Evidence for a precessionally forced climate response. Paleoceanography. 13:63-69.   10.1029/97pa02892   AbstractWebsite

We have developed a combustion analysis technique for sediments which measures the amount of O-2 consumed by the reduced species. We have measured this quantity, which we call "combustion oxygen demand (COD)," on a carbonate-rich sediment core from the Ontong-Java Plateau in the western equatorial Pacific back to marine oxygen isotope stage 11. The precision of the COD technique is +/-6.3 mu mol O-2 g(-1), which corresponds to similar to+/-0.0076% wt C-org, assuming oxidation of organic carbon dominates the signal. The COD time series is characterized by values which are about twice as high during glacials as during interglacials, the largest shift occurring from 401 mu mol O-2 g(-1) in midstage 6 to 144 mu mol O-2 g(-1) at 5e, and is coherent with the oxygen isotope curve of Globigerinoides sacculifer in the same core at the Milankovitch frequencies of 100 and 41 kyr, Pronounced variations in the 19-23 kyr band suggest that the climate of the western equatorial Pacific is sensitive to precessional forcing, a response not apparent from other records obtained in this region.

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
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).

Verhulst, KR, Karion A, Kim J, Salameh PK, Keeling RF, Newman S, Miller J, Sloop C, Pongetti T, Rao P, Wong C, Hopkins FM, Yadav V, Weiss RF, Duren RM, Miller CE.  2017.  Carbon dioxide and methane measurements from the Los Angeles Megacity Carbon Project - Part 1: calibration, urban enhancements, and uncertainty estimates. Atmospheric Chemistry and Physics. 17:8313-8341.   10.5194/acp-17-8313-2017   AbstractWebsite

We report continuous surface observations of carbon dioxide (CO2) and methane (CH4) from the Los Angeles (LA) Megacity Carbon Project during 2015. We devised a calibration strategy, methods for selection of background air masses, calculation of urban enhancements, and a detailed algorithm for estimating uncertainties in urban-scale CO2 and CH4 measurements. These methods are essential for understanding carbon fluxes from the LA megacity and other complex urban environments globally. We estimate background mole fractions entering LA using observations from four "extra-urban" sites including two "marine" sites located south of LA in La Jolla (LJO) and offshore on San Clemente Island (SCI), one "continental" site located in Victorville (VIC), in the high desert northeast of LA, and one "continental/mid-troposphere" site located on Mount Wilson (MWO) in the San Gabriel Mountains. We find that a local marine background can be established to within similar to 1 ppm CO2 and similar to 10 ppb CH4 using these local measurement sites. Overall, atmospheric carbon dioxide and methane levels are highly variable across Los Angeles. "Urban" and "suburban" sites show moderate to large CO2 and CH4 enhancements relative to a marine background estimate. The USC (University of Southern California) site near downtown LA exhibits median hourly enhancements of similar to 20 ppm CO2 and similar to 150 ppb CH4 during 2015 as well as similar to 15 ppm CO2 and similar to 80 ppb CH4 during mid-afternoon hours (12:00-16:00 LT, local time), which is the typical period of focus for flux inversions. The estimated measurement uncertainty is typically better than 0.1 ppm CO2 and 1 ppb CH4 based on the repeated standard gas measurements from the LA sites during the last 2 years, similar to Andrews et al. (2014). The largest component of the measurement uncertainty is due to the single-point calibration method; however, the uncertainty in the background mole fraction is much larger than the measurement uncertainty. The background uncertainty for the marine background estimate is similar to 10 and similar to 15% of the median mid-afternoon enhancement near downtown LA for CO2 and CH4, respectively. Overall, analytical and background uncertainties are small relative to the local CO2 and CH4 enhancements; however, our results suggest that reducing the uncertainty to less than 5% of the median mid-afternoon enhancement will require detailed assessment of the impact of meteorology on background conditions.

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.

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

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

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

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

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

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

Lueker, TJ, Walker SJ, Vollmer MK, Keeling RF, Nevison CD, Weiss RF, Garcia HE.  2003.  Coastal upwelling air-sea fluxes revealed in atmospheric observations of O2/N2, CO2 and N2O. Geophysical Research Letters. 30   10.1029/2002gl016615   AbstractWebsite

[1] We capture water column ventilation resulting from coastal upwelling in continuous records of O-2/N-2, CO2, and N2O at Trinidad, California. Our records reveal the gas exchange response time of the ocean to the upwelling and ensuing biological production. Satellite and buoy wind data allow extrapolation of our records to assess coastal upwelling air-sea fluxes of O-2 and N2O. We improve on previous regional estimates of N2O flux in coastal and continental shelf region of the western U. S. We characterize the source of N2O as being predominately from nitrification based on the O-2/N2O emissions ratio observed in our atmospheric records.

Graven, HD, Xu X, Guilderson TP, Keeling RF, Trumbore SE, Tyler S.  2012.  Comparison of independent delta(co2)-c-14 records at Point Barrow, Alaska. Radiocarbon. 55:1541-1545.   10.2458/azu_js_rc.55.16220   AbstractWebsite

Two independent programs have collected and analyzed atmospheric CO2 samples from Point Barrow, Alaska, for radiocarbon content (Delta C-14) over the period 2003-2007. In one program, flask collection, stable isotope analysis, and CO2 extraction are performed by the Scripps Institution of Oceanography's CO2 Program and CO2 is graphitized and measured by accelerator mass spectrometry (AMS) at Lawrence Livermore National Laboratory. In the other program, the University of California, Irvine, performs flask collection, sample preparation, and AMS. Over 22 common sample dates spanning 5 yr, differences in measured Delta C-14 are consistent with the reported uncertainties and there is no significant bias between the programs.

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

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

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

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

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

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

Welp, LR, Keeling RF, Weiss RF, Paplawsky W, Heckman S.  2013.  Design and performance of a Nafion dryer for continuous operation at CO2 and CH4 air monitoring sites. Atmos. Meas. Tech.. 6:1217-1226.: Copernicus Publications   10.5194/amt-6-1217-2013   AbstractWebsite

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

Lucas, DD, Yver Kwok C, Cameron-Smith P, Graven H, Bergmann D, Guilderson TP, Weiss R, Keeling R.  2015.  Designing optimal greenhouse gas observing networks that consider performance and cost. Geosci. Instrum. Method. Data Syst.. 4:121-137.: Copernicus Publications   10.5194/gi-4-121-2015   AbstractWebsite
Adachi, Y, Kawamura K, Armi L, Keeling RF.  2006.  Diffusive separation of the lower atmosphere. Science (Washington). 311:1429-1429.: American Association for the Advancement of Science, 1200 New York Avenue, NW Washington DC 20005 USA, [], [URL:]   10.1126/science.1121312   AbstractWebsite

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