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Atmospheric Measurement Techniques An interactive open-access journal of the European Geosciences Union
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Discussion papers | Copyright
https://doi.org/10.5194/amt-2018-324
© Author(s) 2018. This work is distributed under
the Creative Commons Attribution 4.0 License.

Research article 15 Oct 2018

Research article | 15 Oct 2018

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This discussion paper is a preprint. It is a manuscript under review for the journal Atmospheric Measurement Techniques (AMT).

Large volume sample system for measuring sulfur isotopic compositions of carbonyl sulfide

Kazuki Kamezaki1, Shohei Hattori1, Enno Bahlmann2, and Naohiro Yoshida1,3 Kazuki Kamezaki et al.
  • 1Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, G1-17, 4259 Nagatsuta-cho, Midori-ku, Yokohama 226-8502, Japan
  • 2Leibniz Centre for Tropical Marine Research, Fahrenheitstraße 6, 28359 Bremen, Germany
  • 3Earth-Life Science Institute, Tokyo Institute of Technology, 2-12-1-IE-1 Ookayama, Meguro-ku, Tokyo 152-8550, Japan

Abstract. Knowledge related to sulfur isotopic composition of carbonyl sulphide (OCS or COS), the most abundant atmospheric sulfur species, remains scarce. Earlier method developed for sulfur isotopic analysis for OCS using S+ fragmentation is inapplicable for ambient air samples because of the large samples required (approx. 500L of 500pmolmol−1 OCS). To overcome this difficulty, herein we present a new sampling system for collecting approx. 10nmol of OCS from ambient air coupled with a purification system. Salient system features are (i) accommodation of samples up to 500L (= approx. 10nmol) of air at 5Lmin−1, (ii) portability of 7 inch tubes (approx. 1cm3) for preserving samples, and (iii) purification OCS from other compounds such as CO2. We tested the OCS collection efficiency of the systems and sulfur isotopic fractionation during sampling. Results show precision (1σ) of δ33S(OCS), δ34S(OCS), and Δ33S(OCS) values, respectively, as 0.4‰, 0.2‰, and 0.4‰. Additionally, this report presents diurnal variation of δ34S(OCS) values collected from ambient air at Suzukakedai campus of Tokyo Institute of Technology located in Yokohama, Japan. The observed OCS concentrations and δ34S(OCS) values were, respectively, 447–520pmolmol−1 and from 10.4‰ to 10.7‰. No significant difference was found between values obtained during the day and night. The observed δ34S(OCS) values in ambient air differed greatly from previously reported values ((4.9±0.3)‰) for compressed air collected at Kawasaki, Japan, presumably because of sampling conditions and collection processes for that sample. Consequently, previous values of δ34S(OCS)=(4.9±0.3)‰ were not representative samples for a global signal. When considering (10.5±0.4)‰ is postulated as the global signal of δ34S(OCS), this revised δ34S(OCS) value is consistent with previous estimation based on terrestrial and oceanic sulfur sources. The δ34S(OCS) value explains the reported δ34S(OCS) values for background stratospheric sulfate. The system presented herein is useful for application of δ34S(OCS) for investigation of OCS sources and sinks in the troposphere to elucidate its cycle and its contribution to background stratospheric sulfate.

Kazuki Kamezaki et al.
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Kazuki Kamezaki et al.
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Knowledge related to sulfur isotopic composition of carbonyl sulfide (OCS or COS), the most abundant atmospheric sulfur species, remains scarce. We present a new sampling system for collecting approx. 10 nmol of OCS from ambient air coupled with a purification system. The system presented herein is useful for application of sulfur isotopic compositions for investigation of OCS sources and sinks in the troposphere to elucidate its cycle and its contribution to background stratospheric sulfate.
Knowledge related to sulfur isotopic composition of carbonyl sulfide (OCS or COS), the most...
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