Comprehensive Analyzer for Biogenic Volatile Organic Compounds Detected as Total Ozone Reactivity

Volatile organic compounds, VOCs, are emitted from various sources into the atmosphere. Through the reactions of VOCs with atmospheric radicals (eg. daytime OH, nighttime NO3, and all-day O3), formation of photochemical oxidants and secondary organic aerosols, SOA, are important. To investigate the mechanisms of reactions in the atmosphere and to control such secondary products effectively, it is essential to capture the behavior of VOC emission with the radical reactivity of VOCs considered. Recently, in addition to OH reactions of anthropogenic VOCs, SOA formation due to ozonolysis of biogenic VOCs (BVOCs) is one of the hottest topics in the atmospheric chemistry. It is difficult to analyze all the species individually due to the great number of VOCs. In this study, a comprehensive tool for capturing the total reactivity of BVOCs with ozone is realized utilizing a chemiluminescence ozone analyzer. A sensitive and fast-response ozone analyzer was developed based on an existing chemiluminescent NO analyzer (CLD). The CLD-O3 analyzer was used to monitor the fast variation of O3 in the sample of the VOC + O3 experiment. When O3 was added to the VOC sample, the reduction of O3 due to VOC was monitored and the O3 reactivity RO3 was determined with the reaction time considered. Dependence of the response of analyzer on the reaction time and the reactivity of sample was examined and confirmed as reasonable. As a result, VOCs can be detected at the level of ppbv (as limonene, S/N = 3). The detection limit of RO3 was 0.0002 s-1. For the test of ozone reactivity measurement of BVOCs emitted from the real vegetation, variation of ozone reactivity was significantly observed after the nursery was put into a closed chamber. In addition, just after the leaves of the plant were physically stimulated, observed reactivity increased. It was experimentally confirmed that stimulus to the leaves of the plant resulted in the increase of total BVOC emission. Consequently, it was confirmed that the analyzer be useful to investigate the real-time analysis of BVOC emission from the vegetation at the level of ppbv.