OH reactivity from different tree species: Investigating the missing reactivity in a boreal forest

Abstract

In forested area, a large fraction of total hydroxyl radical (OH) reactivity remain unaccounted for. Very few studies have been looking at total OH reactivity from biogenic emissions and its variations. In the present study, we investigate the total OH reactivity from three common boreal tree species (Scots pine, Norway spruce, and Downy birch), by comparing it with the calculated reactivity from the chemically identified emissions. Total OH reactivity was measured using the Comparative 5 Reactivity Method (CRM), and the chemical composition of the emissions was quantified with two gas chromatographs coupled to mass spectrometers (GC-MSs). Dynamic branch enclosures were used and emissions from one branch of a tree at the time were measured by rotating between them periodically.Results show that birch had the highest values of total OH reactivity of the emissions (TOHRE), while pine had the lowest.The main drivers for the known reactivity of pine and spruce were monoterpenes and sesquiterpenes. For birch, emissions were 10 dominated by sesquiterpenes, even though monoterpenes and GLVs could be found too. However, calculated reactivity values remained low leading to the highest missing fraction of reactivity (>96 %), while pine and spruce had similar missing reactivity fractions between 56 % and 82 % (higher in the spring and decreasing as the summer proceeded). The high average values were driven by low reactivity periods and the fraction of missing reactivity got smaller for pine and spruce when the TOHRE values increased. Important exceptions were identified for periods when the emission profiles changed from terpenes to Green Leaf 15 Volatiles (GLVs), a family of compounds containing a 6 carbon atoms backbone with various functionalities (e.g. alcohols, aldehydes, esters) that indicate that the plant is suffering from stress. Then, very high TOHRE values were measured and the missing fraction remained high.This study found a different trend in the missing OHRE fraction of Norway spruce from spring to autumn compared to one previous study (Nölscher et al., 2013), which indicates that additional studies are required to fully understand the complexity 20 of biogenic reactive emissions. Future studies of boreal trees in situ should be conducted to confirm the findings presented.