Analysis of atmospheric sesquiterpenes: sampling losses and mitigation of ozone interferences

Atmospheric standards containing parts-per-billion levels of 14 semivolatile hydrocarbon compounds, including eight sesquiterpenes (SQTs) (longipinene, alpha-copaene, isolongifolene, alpha-cedrene, trans-caryophyllene, aromadendrene, alpha-humulene, delta-cadinene), two oxidized sesquiterpenoids (cisnerolidol, trans-nerolidol), one biogenic ketone (geranylacetone) and three aromatic compounds (1,3,5-triisopropylbenzene, diphenylmethane, nonylbenzene), were collected onto four solid adsorbent materials at increasing ozone mixing ratios (0-100 ppbv 03) for analysis by thermodesorption-gas chromatography. Substantial sampling losses of up to >90% were found for the most reactive SQT, even at the lowest ozone level investigated of 20 ppbv. Loss rates from the ozone-SQT reaction were used to derive estimates of gas-phase ozone reaction rate constants for longipinene, alpha-copaene, isolongifolene, geranylacetone, aromadendrene, delta-cadinene, cis-nerolidol, and transnerolidol. Three different ozone mitigation techniques were investigated to prevent these sampling losses. These strategies included (a) placing glass fiber filters impregnated with sodium thiosulfate (Na2S2O3) into the sampling line, (b) titration of ozone in the sampling stream with nitric oxide (NO), and (c) catalytically removing ozone with a commercially available manganese dioxide (MnO2) catalyst. All three techniques reduced ozone-mixing ratios from 100 ppbv to <0.6 ppbv at sampling flow rates of 1 L min(-1). When the Na2S2O3 filters and the NO-titration techniques were applied, SQT loss rates decreased from 25-60% to 0-5% for most SQT compounds and from >90% to approximately 10-50% for the two most reactive compounds at ozone mixing ratios of up to 100 ppbv. The commercial manganese dioxide scrubber, however, caused complete analyte losses (>98%) even at 0 ppbv ozone. These results underline the need and present applicable techniques for removal of ozone in air samples for SQT analysis by solid adsorption techniques.