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. Knowledge related to sulfur isotope ratios of carbonyl sulfide (OCS or COS),the most abundant atmospheric sulfur species, remains scarce. An earliermethod developed for sulfur isotopic analysis for OCS using S + fragmentation by an isotope ratio mass spectrometer is inapplicable forambient air samples because of the large samples required (approx. 500 L of500 pmol mol −1 OCS). To overcome this difficulty, herein we present anew sampling system for collecting approximately 10 nmol of OCS from ambientair coupled with a purification system. Salient system features are(i) accommodation of samples up to 500 L (approx. 10 nmol) of air at5 L min −1 ; (ii) portability of adsorption tubes ( 1∕4  in. (0.64 cm)outer diameter, 17.5 cm length, approximately 1.4 cm 3 volume) forpreserving the OCS amount and δ34 S(OCS) values at − 80  ∘ Cfor up to 90 days and 14 days; and (iii) purification OCS from othercompounds such as CO2 . We tested the OCS collection efficiency ofthe systems and sulfur isotopic fractionation during sampling. Results showprecision (1 σ ) of δ34 S(OCS) values as 0.4 ‰ foroverall procedures during measurements for atmospheric samples. Additionally,this report presents diurnal variation of δ34 S(OCS) valuescollected from ambient air at the Suzukakedai campus of the Tokyo Instituteof Technology located in Yokohama, Japan. The observed OCS concentrations and δ34 S(OCS) values were, respectively, 447–520 pmol mol −1 andfrom 10.4 ‰ to 10.7 ‰ with a lack of diurnal variation. Theobserved δ34 S(OCS) values in ambient air differed greatly frompreviously reported values of δ34 S(OCS)  =  ( 4.9±0.3 ) ‰ for compressed air collected at Kawasaki, Japan, presumablybecause of degradation of OCS in cylinders and collection processes for thatsample. The difference of atmospheric δ34 S(OCS) values between10.5 ‰ in Japan (this study) and ∼13  ‰ recentlyreported in Israel or the Canary Islands indicates that spatial and temporalvariation of δ34 S(OCS) values is expected due to a link betweenanthropogenic activities and OCS cycles. The system presented herein isuseful for application of δ34 S(OCS) for investigation of OCSsources and sinks in the troposphere to elucidate its cycle.

atmospheric measurement techniques

Large-volume air sample system for measuring &amp;lt;sup&amp;gt;34&amp;lt;/sup&amp;gt;S∕&amp;lt;sup&amp;gt;32&amp;lt;/sup&amp;gt;S isotope ratio of carbonyl sulfide