An intercomparison of aircraft instrumentation for tropospheric measurements of carbonyl sulfide, hydrogen sulfide, and carbon disulfide

Abstract

This paper reports results of NASA's Chemical Instrumentation and Test Evaluation (CITE 3) during which airborne measurements for carbonyl sulfide (COS), hydrogen sulfide (H2S), and carbon disulfide (CS2) were intercompared. Instrumentation included a gas chromatograph using flame photometric detection (COS, H2S, and CS2), a gas chromatograph using mass spectrometric detection (COS and CS2), a gas chromatograph using fluorination and subsequent SF6 detection via electron capture (COS and CS2), and the Natusch technique (H2S). The measurements were made over the Atlantic Ocean east of North and South America during flights from NASA's Wallops Flight Center, Virginia, and Natal, Brazil, in August/September 1989. Most of the intercomparisons for H2S and CS2 were at mixing ratios <25 pptv and <10 pptv, respectively, with a maximum mixing ratio of about 100 pptv and 50 pptv, respectively. Carbonyl sulfide intercomparisons were at mixing ratios between 400 and 600 pptv. Measurements were intercompared from data bases constructed from time periods of simultaneous or overlapping measurements. Agreement among the COS techniques averaged about 5%, and individual measurements were generally within 10%. For H2S and at mixing ratio >25 pptv, the instruments agreed on average to about 15%. At mixing ratios <25 pptv the agreement was about 5 pptv. For CS2 (mixing ratios <50 pptv), two techniques agreed on average to about 4 pptv, and the third exhibited a bias (relative to the other two) that varied in the range of 3–7 pptv. CS2 mixing ratios over the ocean east of Natal as measured by the gas chromatograph‐mass spectrometer technique were only a few pptv and were below the detection limits of the other two techniques. The CITE 3 data are used to estimate the current uncertainty associated with aircraft measurements of COS, H2S, and CS2 in the remote troposphere.