Precise atmospheric oxygen measurements with a paramagnetic oxygen analyzer

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

Thermal fractionation of air in polar firn by seasonal temperature gradients

Air withdrawn from the top 5-15 m of the polar snowpack (firn) shows anomalous enrichment of heavy gases during summer, including inert gases. Following earlier work, we ascribe this to thermal diffusion, the tendency of a gas mixture to separate in a temperature gradient, with heavier molecules migrating toward colder regions. Summer warmth creates a temperature gradient in the top few meters of the firn due to the thermal inertia of the underlying firn and causes gas fractionation by thermal diffusion. Here we explore and quantify this process further in order to (1) correct for bias caused by thermal diffusion in firn air and ice core air isotope records, (2) help calibrate a new technique for measuring temperature change in ice core gas records based on thermal diffusion [Severinghaus et al., 1998], and (3) address whether air in polar snow convects during winter and, if so, whether it creates a rectification of seasonality that could bias the ice core record. We sampled air at 2-m-depth intervals from the top 15 m of the firn at two Antarctic sites, Siple Dome and South Pole, including a winter sampling at the pole. We analyzed 15N/14N, 40Ar/36Ar, 40Ar/38Ar, 18O/16O of O2, O2/N2, 84Kr/36Ar, and 132Xe/36Ar. The results show the expected pattern of fractionation and match a gas diffusion model based on first principles to within 30%. Although absolute values of thermal diffusion sensitivities cannot be determined from the data with precision, relative values of different gas pairs may. At Siple Dome, δ40Ar/4 is 66 ± 2% as sensitive to thermal diffusion as δ15N, in agreement with laboratory calibration; δ18O/2 is 83 ± 3%, and δ84Kr/48 is 33 ± 3% as sensitive as δ15N. The corresponding figures for summer South Pole are 64 ± 2%, 81 ± 3%, and 34 ± 3%. Accounting for atmospheric change, the figure for δO2/N2/4 is 90 ± 3% at Siple Dome. Winter South Pole shows a strong depletion of heavy gases as expected. However, the data do not fit the model well in the deeper part of the profile and yield a systematic drift with depth in relative thermal diffusion sensitivities (except for Kr, constant at 34 ± 4%), suggesting the action of some other process that is not currently understood. No evidence for wintertime convection or a rectifier effect is seen

Studies of the terrestrial O{sub 2} and carbon cycles in sand dune gases and in biosphere 2

Molecular oxygen in the atmosphere is coupled tightly to the terrestrial carbon cycle by the processes of photosynthesis, respiration, and burning. This dissertation examines different aspects of this coupling in four chapters. Chapter 1 explores the feasibility of using air from sand dunes to reconstruct atmospheric O{sub 2} composition centuries ago. Such a record would reveal changes in the mass of the terrestrial biosphere, after correction for known fossil fuel combustion, and constrain the fate of anthropogenic CO{sub 2}

Reply to Comment on "Cosmic rays, carbon dioxide, and climate"

In our analysis [Rahmstorf et al., 2004], we arrived at two main conclusions: the data of Shaviv and Veizer [2003] do not show a significant correlation of cosmic ray flux (CRF) and climate, and the authors' estimate of climate sensitivity to CO2 based on a simple regression analysis is questionable. After careful consideration of Shaviv and Veizer's comment, we want to uphold and reaffirm these conclusions. Concerning the question of correlation, we pointed out that a correlation arose only after several adjustments to the data, including shifting one of the four CRF peaks and stretching the time scale. To calculate statistical significance, we first need to compute the number of independent data points in the CRF and temperature curves being correlated, accounting for their autocorrelation. A standard estimate [Quenouille, 1952] of the number of effective data points is urn:x-wiley:00963941:media:eost14930:eost14930-math-0001 where N is the total number of data points and r1, r2 are the autocorrelations of the two series. For the curves of Shaviv and Veizer [2003], the result is NEFF = 4.8. This is consistent with the fact that these are smooth curves with four humps, and with the fact that for CRF the position of the four peaks is determined by four spiral arm crossings or four meteorite clusters, respectively; that is, by four independent data points. The number of points that enter the calculation of statistical significance of a linear correlation is (NEFF− 2), since any curves based on only two points show perfect correlation; at least three independent points are needed for a meaningful result

Where to Find 1.5 Million Yr Old Ice for the IPICS Oldest Ice Ice Core

Abstract. The recovery of a 1.5 million yr long ice core from Antarctica represents a keystone of our understanding of Quaternary climate, the progression of glaciation over this time period and the role of greenhouse gas cycles in this pro- gression. Here we tackle the question of where such ice may still be found in the Antarctic ice sheet. We can show that such old ice is most likely to exist in the plateau area of the East Antarctic ice sheet (EAIS) without stratigraphic distur- bance and should be able to be recovered after careful pre- site selection studies. Based on a simple ice and heat flow model and glaciological observations, we conclude that po- sitions in the vicinity of major domes and saddle position on the East Antarctic Plateau will most likely have such old ice in store and represent the best study areas for dedicated reconnaissance studies in the near future. In contrast to pre- vious ice core drill site selections, however, we strongly sug- gest significantly reduced ice thickness to avoid bottom melt- ing. For example for the geothermal heat flux and accumu- lation conditions at Dome C, an ice thickness lower than but close to about 2500 m would be required to find 1.5 Myr old ice (i.e., more than 700m less than at the current EPICA Dome C drill site). Within this constraint, the resolution of an Oldest-Ice record and the distance of such old ice to the bedrock should be maximized to avoid ice flow disturbances, for example, by finding locations with minimum geothermal heat flux. As the geothermal heat flux is largely unknown for the EAIS, this parameter has to be carefully determined be- forehand. In addition, detailed bedrock topography and ice flow history has to be reconstructed for candidates of an Oldest-Ice ice coring site. Finally, we argue strongly for rapid access drilling before any full, deep ice coring activity com- mences to bring datable samples to the surface and to allow an age check of the oldest ice

Kinetic Fractionation of Gases by Deep Air Convection in Polar Firn

A previously unrecognized type of gas fractiona- tion occurs in firn air columns subjected to intense convec- tion. It is a form of kinetic fractionation that depends on the fact that different gases have different molecular diffusivi- ties. Convective mixing continually disturbs diffusive equi- librium, and gases diffuse back toward diffusive equilibrium under the influence of gravity and thermal gradients. In near- surface firn where convection and diffusion compete as gas transport mechanisms, slow-diffusing gases such as krypton (Kr) and xenon (Xe) are more heavily impacted by convec- tion than fast diffusing gases such as nitrogen (N2) and ar- gon (Ar), and the signals are preserved in deep firn and ice. We show a simple theory that predicts this kinetic effect, and the theory is confirmed by observations using a newly- developed Kr and Xe stable isotope system in air samples from the Megadunes field site on the East Antarctic plateau. Numerical simulations confirm the effect’s magnitude at this site. A main purpose of this work is to support the devel- opment of a proxy indicator of past convection in firn, for use in ice-core gas records. To this aim, we also show with the simulations that the magnitude of the kinetic effect is fairly insensitive to the exact profile of convective strength, if the overall thickness of the convective zone is kept constant. These results suggest that it may be feasible to test for the existence of an extremely deep (∼30–40 m) convective zone, which has been hypothesized for glacial maxima, by future ice-core measurements