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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.

Marcott, SA, Bauska TK, Buizert C, Steig EJ, Rosen JL, Cuffey KM, Fudge TJ, Severinghaus JP, Ahn J, Kalk ML, McConnell JR, Sowers T, Taylor KC, White JWC, Brook EJ.  2014.  Centennial-scale changes in the global carbon cycle during the last deglaciation. Nature. 514:616-+.   10.1038/nature13799   AbstractWebsite

Global climate and the concentration of atmospheric carbon dioxide (CO2) are correlated over recent glacial cycles(1,2). The combination of processes responsible for a rise in atmospheric CO2 at the last glacial termination(1,3) (23,000 to 9,000 years ago), however, remains uncertain(1-3). Establishing the timing and rate of CO2 changes in the past provides critical insight into the mechanisms that influence the carbon cycle and helps put present and future anthropogenic emissions in context. Here we present CO2 and methane (CH4) records of the last deglaciation from a new high-accumulation West Antarctic ice core with unprecedented temporal resolution and precise chronology. We show that although low-frequency CO2 variations parallel changes in Antarctic temperature, abrupt CO2 changes occur that have a clear relationship with abrupt climate changes in the Northern Hemisphere. A significant proportion of the direct radiative forcing associated with the rise in atmospheric CO2 occurred in three sudden steps, each of 10 to 15 parts per million. Every step took place in less than two centuries and was followed by no notable change in atmospheric CO2 for about 1,000 to 1,500 years. Slow, millennial-scale ventilation of Southern Ocean CO2-rich, deep-ocean water masses is thought to have been fundamental to the rise in atmospheric CO2 associated with the glacial termination(4), given the strong covariance of CO2 levels and Antarctic temperatures(5). Our data establish a contribution from an abrupt, centennial-scale mode of CO2 variability that is not directly related to Antarctic temperature. We suggest that processes operating on centennial timescales, probably involving the Atlantic meridional overturning circulation, seem to be influencing global carbon-cycle dynamics and are at present not widely considered in Earth system models.

McConnell, JR, Burke A, Dunbar NW, Kohler P, Thomas JL, Arienzo MM, Chellman NJ, Maselli OJ, Sigl M, Adkins JF, Baggenstos D, Burkhart JF, Brook EJ, Buizert C, Cole-Dai J, Fudge TJ, Knorr G, Graf HF, Grieman MM, Iverson N, McGwire KC, Mulvaney R, Paris G, Rhodes RH, Saltzman ES, Severinghaus JP, Steffensen JP, Taylor KC, Winckler G.  2017.  Synchronous volcanic eruptions and abrupt climate change similar to 17.7 ka plausibly linked by stratospheric ozone depletion. Proceedings of the National Academy of Sciences of the United States of America. 114:10035-10040.   10.1073/pnas.1705595114   AbstractWebsite

Glacial-state greenhouse gas concentrations and Southern Hemisphere climate conditions persisted until similar to 17.7 ka, when a nearly synchronous acceleration in deglaciation was recorded in paleoclimate proxies in large parts of the Southern Hemisphere, with many changes ascribed to a sudden poleward shift in the Southern Hemisphere westerlies and subsequent climate impacts. We used high-resolution chemical measurements in the West Antarctic Ice Sheet Divide, Byrd, and other ice cores to document a unique, similar to 192-y series of halogen-rich volcanic eruptions exactly at the start of accelerated deglaciation, with tephra identifying the nearby Mount Takahe volcano as the source. Extensive fallout from these massive eruptions has been found >2,800 km from Mount Takahe. Sulfur isotope anomalies and marked decreases in ice core bromine consistent with increased surface UV radiation indicate that the eruptions led to stratospheric ozone depletion. Rather than a highly improbable coincidence, circulation and climate changes extending from the Antarctic Peninsula to the subtropics-similar to those associated with modern stratospheric ozone depletion over Antarctica-plausibly link the Mount Takahe eruptions to the onset of accelerated Southern Hemisphere deglaciation similar to 17.7 ka.

Mitchell, LE, Buizert C, Brook EJ, Breton DJ, Fegyveresi J, Baggenstos D, Orsi A, Severinghaus J, Alley RB, Albert M, Rhodes RH, McConnell JR, Sigl M, Maselli O, Gregory S, Ahn J.  2015.  Observing and modeling the influence of layering on bubble trapping in polar firn. Journal of Geophysical Research-Atmospheres. 120:2558-2574.   10.1002/2014jd022766   AbstractWebsite

Interpretation of ice core trace gas records depends on an accurate understanding of the processes that smooth the atmospheric signal in the firn. Much work has been done to understand the processes affecting air transport in the open pores of the firn, but a paucity of data from air trapped in bubbles in the firn-ice transition region has limited the ability to constrain the effect of bubble closure processes. Here we present high-resolution measurements of firn density, methane concentrations, nitrogen isotopes, and total air content that show layering in the firn-ice transition region at the West Antarctic Ice Sheet (WAIS) Divide ice core site. Using the notion that bubble trapping is a stochastic process, we derive a new parameterization for closed porosity that incorporates the effects of layering in a steady state firn modeling approach. We include the process of bubble trapping into an open-porosity firn air transport model and obtain a good fit to the firn core data. We find that layering broadens the depth range over which bubbles are trapped, widens the modeled gas age distribution of air in closed bubbles, reduces the mean gas age of air in closed bubbles, and introduces stratigraphic irregularities in the gas age scale that have a peak-to-peak variability of 10 years at WAIS Divide. For a more complete understanding of gas occlusion and its impact on ice core records, we suggest that this experiment be repeated at sites climatically different from WAIS Divide, for example, on the East Antarctic plateau.