Temperature-dependent rate coefficients for the reactions of the hydroxyl radical with the atmospheric biogenics isoprene, alpha-pinene and delta-3-carene

Pulsed laser methods for OH generation and detection were used to study atmospheric degradation reactions for three important biogenic gases: OH + isoprene (Reaction R1), OH + α -pinene (Reaction R2) and OH + Δ-3-carene (Reaction R3). Gas-phase rate coefficients were characterized by non-Arrhenius kinetics for all three reactions. For (R1), k 1 (241–356 K)  = (1.93±0.08) × 10 −11 exp {(466±12)∕ T } cm 3  molecule −1  s −1 was determined, with a room temperature value of k 1 (297 K)  = (9.3±0.4) × 10 −11  cm 3  molecule −1  s −1 , independent of bath-gas pressure (5–200 Torr) and composition (M  =  N 2 or air). Accuracy and precision were enhanced by online optical monitoring of isoprene, with absolute concentrations obtained via an absorption cross section, σ isoprene  = (1.28±0.06) × 10 −17  cm 2  molecule −1 at λ  = 184.95 nm, determined in this work. These results indicate that significant discrepancies between previous absolute and relative-rate determinations of k 1 result in part from σ values used to derive the isoprene concentration in high-precision absolute determinations. Similar methods were used to determine rate coefficients (in 10 −11  cm 3  molecule −1  s −1 ) for (R2)–(R3): k 2 (238–357 K)  = (1.83±0.04) ×  exp {(330±6)∕ T } and k 3 (235–357 K)  = (2.48±0.14) ×  exp {(357±17)∕ T }. This is the first temperature-dependent dataset for (R3) and enables the calculation of reliable atmospheric lifetimes with respect to OH removal for e.g. boreal forest springtime conditions. Room temperature values of k 2 (296 K)  = (5.4±0.2) × 10 −11  cm 3  molecule −1  s −1 and k 3 (297 K)  = (8.1±0.3) × 10 −11  cm 3  molecule −1  s −1 were independent of bath-gas pressure (7–200 Torr, N 2 or air) and in good agreement with previously reported values. In the course of this work, 184.95 nm absorption cross sections were determined: σ  = (1.54±0.08) × 10 −17  cm 2  molecule −1 for α -pinene and (2.40±0.12) × 10 −17  cm 2  molecule −1 for Δ-3-carene.