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High-precision dual-inlet IRMS measurements of the stable isotopes of CO₂ and the N₂O/CO₂ ratio from polar ice core samples

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Title High-precision dual-inlet IRMS measurements of the stable isotopes of CO₂ and the N₂O/CO₂ ratio from polar ice core samples
Names Bauska, T. K. (creator)
Brook, E. J. (creator)
Mix, A. C. (creator)
Ross, A. (creator)
Date Issued 2014-11-19 (iso8601)
Note This is the publisher’s final pdf. The published article is copyrighted by the author(s) and published by Copernicus Publications on behalf of the European Geosciences Union. The published article can be found at: http://www.atmospheric-measurement-techniques.net/home.html.
Abstract An important constraint on mechanisms of past
carbon cycle variability is provided by the stable isotopic
composition of carbon in atmospheric carbon dioxide (δ¹³C-CO₂) trapped in polar ice cores, but obtaining very precise
measurements has proven to be a significant analytical challenge.
Here we describe a new technique to determine the
δ¹³C of CO₂ at very high precision, as well as measuring the
CO₂ and N₂O mixing ratios. In this method, ancient air is extracted
from relatively large ice samples (~400 g) with a dry-extraction
“ice grater” device. The liberated air is cryogenically
purified to a CO₂ and N₂O mixture and analyzed with
a microvolume-equipped dual-inlet IRMS (Thermo MAT
253). The reproducibility of the method, based on replicate
analysis of ice core samples, is 0.02‰ for δ¹³C-CO₂ and
2 ppm and 4 ppb for the CO₂ and N₂O mixing ratios, respectively
(1σ pooled standard deviation). Our experiments show
that minimizing water vapor pressure in the extraction vessel
by housing the grating apparatus in a ultralow-temperature
freezer (-60°C) improves the precision and decreases the
experimental blank of the method to -0.07 ± 0.04‰. We
describe techniques for accurate calibration of small samples
and the application of a mass-spectrometric method based on
source fragmentation for reconstructing the N₂O history of
the atmosphere. The oxygen isotopic composition of CO₂ is
also investigated, confirming previous observations of oxygen
exchange between gaseous CO₂ and solid H₂O within
the ice archive. These data offer a possible constraint on oxygen
isotopic fractionation during H₂O and CO₂ exchange below
the H₂O bulk melting temperature.
Genre Article
Access Condition http://creativecommons.org/licenses/by/3.0/us/
Identifier Bauska, T. K., Brook, E. J., Mix, A. C., & Ross, A. (2014). High-precision dual-inlet IRMS measurements of the stable isotopes of CO₂ and the N₂O/CO₂ ratio from polar ice core samples. Atmospheric Measurement Techniques, 7(11), 3825-3837. doi:10.5194/amt-7-3825-2014

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