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2003
Grachev, AM, Severinghaus JP.  2003.  Determining the thermal diffusion factor for Ar-40/Ar-36 in air to aid paleoreconstruction of abrupt climate change. Journal of Physical Chemistry A. 107:4636-4642.   10.1021/jp027817u   AbstractWebsite

The thermal diffusion factor (alpha(T)) of Ar-40/Ar-36 in air has been measured in the laboratory for the first time. The mean values of alpha(T) x 10(3) that we find at -30.0 degreesC are 9.85 +/- 0.04 for air and 11.25 +/- 0.03 for pure argon. The latter value is more precise than the data found in the literature. The temperature dependence of the thermal diffusion factor in air in the range -60 to -10 degreesC can be described by an empirical equation alpha(T) x 10(3) = 26.08 - 3952/ (+/-1%), where is the effective average temperature. Results of this study are valuable for reconstruction of magnitudes of abrupt climate change events recorded in Greenland ice cores. For one abrupt warming event similar to15,000 years ago, near the end of the last glacial period, these results yield a warming of 11 +/- 3 degreesC over several decades or less. Theoretical calculations are not yet able to provide the needed accuracy, and the experimental results for the thermal diffusion factor in air should be used for paleoenvironmental studies.

Grachev, AM, Severinghaus JP.  2003.  Laboratory determination of thermal diffusion constants for N-29(2)/N-28(2) in air at temperatures from-60 to 0 degrees C for reconstruction of magnitudes of abrupt climate changes using the ice core fossil-air paleothermometer. Geochimica Et Cosmochimica Acta. 67:345-360.   10.1016/s0016-7037(02)01115-8   AbstractWebsite

Rapid temperature change causes fractionation of isotopic gaseous species in air in firn (snow) by thermal diffusion, producing a signal that is preserved in trapped air bubbles as the snow forms ice. Using a model of heat penetration and gas diffusion in the firn, as well as the values of appropriate thermal diffusion constants, it is possible to reconstruct the magnitude of a particular paleoclimate change. Isotopic nitrogen in air serves as a convenient tracer for such paleoreconstruction, because the ratio N-29(2)/N-28(2) has stayed extremely constant in the atmosphere for greater than or equal to10(6) years. However, prior to this work no data were available for thermal diffusion of N-29(2)/N-28(2) in air, but only in pure N-2. We devised a laboratory experiment allowing fractionation of gases by thermal diffusion in a small, tightly controlled temperature difference. A mass spectrometer was employed in measuring the resulting fractionations yielding measurement precision greater than was attainable by earlier thermal diffusion investigators. Our laboratory experiments indicate that the value of the thermal diffusion sensitivity (Omega) for N-29(2)/N-28(2) in air is +(14.7 +/- 0.5) X 10(-3) per mil/degreesC when the average temperature is -30.0degreesC. The corresponding value for N-29(2)/N-28(2) in pure N-2 that we find is +(15.3 +/- 0.4) X 10(-3) per mil/degreesC at -30.6degreesC, in agreement with the previously available literature data within their large range of uncertainty. We find that an empirical equation, Omega = (8.656/T-K - 1232/T-K(2)) +/- 3% per mil/degreesC, describes the slight variation of the sensitivity values for N-29(2)/N-28(2) in air with temperature in the range of -60 to 0degreesC. A separate set of experiments also described in this paper rules out adsorption as a candidate for producing additional temperature change-driven fractionation of N-29(2)/N-28(2) in the firn air. The combined newly obtained data constitute a calibration of the fossil-air paleothermometer with respect to isotopic nitrogen and will serve to improve the estimates of the magnitudes of past abrupt climate changes recorded in ice cores. Copyright (C) 2003 Elsevier Science Ltd.