Diel cycles of isoprenoids in the emissions of Norway spruce, four Scots pine chemotypes, and in Boreal forest ambient air during HUMPPA-COPEC-2010

Abstract. Branch enclosure based emission rates of monoterpenes and sesquiterpenes from four Scots pines (Pinus sylvestris) and one Norway spruce (Picea abies), as well as the ambient mixing ratios of monoterpenes were determined during the HUMPPA-COPEC 2010 summer campaign. Differences in chemical composition and in emission strength were observed between the different trees, which confirmed that they represented different chemotypes. The chemotypes of Scots pine can be classified according to species with high, no and intermediate content of Δ-3-carene. The "non-Δ-3-carene" chemotype was found to be the strongest emitter of monoterpenes. From this chemotype, β-myrcene, a very reactive monoterpene, was the dominant species accounting for more than 32 % of the total emission rates of isoprenoids followed by β-phellandrene (~27%). Myrcene fluxes ranged from 0.8 to 24 μg g⁻¹ (dw) h⁻¹. α-Farnesene was the dominant sesquiterpene species, with average emission rates of 318 ng g⁻¹ (dw) h⁻¹. In the high Δ-3-carene chemotype, more than 48% of the total monoterpene emission was Δ-3-carene. The average Δ-3-carene emission rate (from chemotype 3), circa 609 ng g⁻¹ (dw) h⁻¹ reported here is consistent with the previously reported summer season value. Daily maximum temperatures varied between 20 and 35 °C during the measurements. The monoterpene emissions from spruce were dominated by limonene (35%), β-phellandrene (15%), α-pinene (14%) and eucalyptol (9%). Total spruce monoterpene emissions ranged from 0.55 up to 12.2 μg g⁻¹ (dw) h⁻¹. Overall the total terpene flux (monoterpenes + sesquiterpenes) from all studied tree species varied from 230 ng g⁻¹ (dw) h⁻¹ up to 66 μg g⁻¹ (dw) h⁻¹. Total ambient monoterpenes (including α-pinene, Δ-3-carene, β-pinene and β-myrcene) measured during the campaign varied in mixing ratio from a few pptv to over one ppbv. The most abundant biogenic VOC measured above the canopy were α-pinene and Δ-3-carene, and these two compounds together contributed more than 50% of the total monoterpenes. The ambient data reflect the emission rate, atmospheric reactivity and tree type abundance. The diel cycles of isoprenoid mixing ratios showed high levels during the night-time which is consistent with continued low nocturnal emission and a low and stable boundary layer. The chirality of α-pinene was dominated by (+)-enantiomers both in the direct emission and in the atmosphere. The two highest emitters showed no enantiomeric preference for α-pinene emissions, whereas the two lowest emitting pines emitted more (+)-enantiomer. The spruce emissions were dominated by (−)-enantiomer. The exceptionally hot temperatures in the summer of 2010 led to relatively strong emissions of monoterpenes, greater diversity in chemical composition and high ambient mixing ratios.