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Manizza, M, Keeling RF, Nevison CD.  2012.  On the processes controlling the seasonal cycles of the air-sea fluxes of O2 and N2O: A modelling study. Tellus Series B-Chemical and Physical Meteorology. 64   10.3402/tellusb.v64i0.18429   AbstractWebsite

The seasonal dynamics of the air-sea gas flux of oxygen (O-2) are controlled by multiple processes occurring simultaneously. Previous studies showed how to separate the thermal component from the total O-2 flux to quantify the residual oxygen flux due to biological processes. However, this biological signal includes the effect of both net euphotic zone production (NEZP) and subsurface water ventilation. To help understand and separate these two components, we use a large-scale ocean general circulation model (OGCM), globally configured, and coupled to a biogeochemical model. The combined model implements not only the oceanic cycle of O-2 but also the cycles of nitrous oxide (N2O), argon (Ar) and nitrogen (N-2). For this study, we apply a technique to distinguish the fluxes of O-2 driven separately by thermal forcing, NEZP, and address the role of ocean ventilation by carrying separate O-2 components in the model driven by solubility, NEZP and ventilation. Model results show that the ventilation component can be neglected in summer compared to the production and thermal components polewards but not equatorward of 30 degrees in each hemisphere. This also implies that neglecting the role of ventilation in the subtropical areas would lead to overestimation of the component of O-2 flux due to NEZP by 20-30%. Model results also show that the ventilation components of air-sea O-2 and N2O fluxes are strongly anti-correlated in a ratio that reflects the subsurface tracer/tracer relationships (similar to 0.1 mmol N2O/mol O-2) as derived from observations. The results support the use of simple scaling relationships linking together the thermally driven fluxes of Ar, N-2 and O-2. Furthermore, our study also shows that for latitudes polewards of 30 degrees of both hemispheres, the Garcia and Keeling (2001) climatology, when compared to our model results, has a phasing error with the fluxes being too early by similar to 2-3 weeks.

Manning, AC, Keeling RF, Katz LE, Paplawsky WJ, McEvoy EM.  2003.  Interpreting the seasonal cycles of atmospheric oxygen and carbon dioxide concentrations at American Samoa Observatory. Geophysical Research Letters. 30   10.1029/2001gl014312   AbstractWebsite

We present seven years of atmospheric O-2/N-2 ratio and CO2 concentration data measured from flask samples collected at American Samoa. These data are unusual, exhibiting higher short-term variability, and seasonal cycles not in phase with other sampling stations. The unique nature of atmospheric data from Samoa has been noted previously from measurements of CO2, methyl chloroform, and ozone. With our O-2 data, we observe greater magnitude in the short-term variability, but, in contrast, no clear seasonal pattern to this variability. This we attribute to significant regional sources and sinks existing for O-2 in both hemispheres, and a dependence on both the latitudinal and altitudinal origins of air masses. We also hypothesize that some samples exhibit a component of "older'' air, demonstrating recirculation of air within the tropics. Our findings could be used to help constrain atmospheric transport models which are not well characterized in tropical regions.

Manning, AC, Keeling RF.  2006.  Global oceanic and land biotic carbon sinks from the Scripps atmospheric oxygen flask sampling network. Tellus Series B-Chemical and Physical Meteorology. 58:95-116.   10.1111/j.1600-0889.2006.00175.x   AbstractWebsite

Measurements of atmospheric O-2/N-2 ratio and CO2 concentration are presented over the period 1989-2003 from the Scripps Institution of Oceanography global flask sampling network. A formal 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 O-2 and N-2 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 x 10(14) mol O-2 yr(-1) and 0.20 x 10(14) mol N-2 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.

Manning, MR, Edmonds J, Emori S, Grubler A, Hibbard K, Joos F, Kainuma M, Keeling RF, Kram T, Manning AC, Meinshausen M, Moss R, Nakicenovic N, Riahi K, Rose SK, Smith S, Swart R, van Vuuren DP.  2010.  Misrepresentation of the IPCC CO2 emission scenarios. Nature Geoscience. 3:376-377.   10.1038/ngeo880   AbstractWebsite
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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.

Manning, AC, Nisbet EG, Keeling RF, Liss PS.  2011.  Greenhouse gases in the Earth system: setting the agenda to 2030. Philosophical Transactions of the Royal Society a-Mathematical Physical and Engineering Sciences. 369:1885-1890.   10.1098/rsta.2011.0076   AbstractWebsite

What do we need to know about greenhouse gases? Over the next 20 years, how should scientists study the role of greenhouse gases in the Earth system and the changes that are taking place? These questions were addressed at a Royal Society scientific Discussion Meeting in London on 22-23 February 2010, with over 300 participants.

Miller, J, Lehman S, Wolak C, Turnbull J, Dunn G, Graven H, Keeling R, Meijer HAJ, Aerts-Bijma AT, Palstra SWL, Smith AM, Allison C, Southon J, Xu XM, Nakazawa T, Aoki S, Nakamura T, Guilderson T, LaFranchi B, Mukai H, Terao Y, Uchida M, Kondo M.  2013.  Initial results of an intercomparison of ams-based atmospheric (co2)-c-14 measurements. Radiocarbon. 55:1475-1483.   10.2458/azu_js_rc.55.16382   AbstractWebsite

This article presents results from the first 3 rounds of an international intercomparison of measurements of Delta(CO2)-C-14 in liter-scale samples of whole air by groups using accelerator mass spectrometry (AMS). The ultimate goal of the intercomparison is to allow the merging of Delta(CO2)-C-14 data from different groups, with the confidence that differences in the data are geophysical gradients and not artifacts of calibration. Eight groups have participated in at least 1 round of the intercomparison, which has so far included 3 rounds of air distribution between 2007 and 2010. The comparison is intended to be ongoing, so that: a) the community obtains a regular assessment of differences between laboratories; and b) individual laboratories can begin to assess the long-term repeatability of their measurements of the same source air. Air used in the intercomparison was compressed into 2 high-pressure cylinders in 2005 and 2006 at Niwot Ridge, Colorado (USA), with one of the tanks "spiked" with fossil CO2, so that the 2 tanks span the range of Delta(CO2)-C-14 typically encountered when measuring air from both remote background locations and polluted urban ones. Three groups show interlaboratory comparability within 1 parts per thousand for ambient level Delta(CO2)-C-14. For high CO2/low Delta(CO2)-C-14 air, 4 laboratories showed comparability within 2 parts per thousand. This approaches the goals set out by the World Meteorological Organization (WMO) CO2 Measurements Experts Group in 2005. One important observation is that single-sample precisions typically reported by the AMS community cannot always explain the observed differences within and between laboratories. This emphasizes the need to use long-term repeatability as a metric for measurement precision, especially in the context of long-term atmospheric monitoring.