Production of extremely low volatile organic compounds from biogenic emissions: Measured yields and atmospheric implications

Oxidation products of monoterpenes and isoprene have a major influence on the global secondary organic aerosol (SOA) burden and the production of atmospheric nanoparticles and cloud condensation nuclei (CCN). Here, we investigate the formation of extremely low volatility organic compounds (ELVOC) from O ₃ and OH radical oxidation of several monoterpenes and isoprene in a series of laboratory experiments. We show that ELVOC from all precursors are formed within the first minute after the initial attack of an oxidant. We demonstrate that under atmospherically relevant concentrations, species with an endocyclic double bond efficiently produce ELVOC from ozonolysis, whereas the yields from OH radical-initiated reactions are smaller. If the double bond is exocyclic or the compound itself is acyclic, ozonolysis produces less ELVOC and the role of the OH radical-initiated ELVOC formation is increased. Isoprene oxidation produces marginal quantities of ELVOC regardless of the oxidant. Implementing our laboratory findings into a global modeling framework shows that biogenic SOA formation in general, and ELVOC in particular, play crucial roles in atmospheric CCN production. Monoterpene oxidation products enhance atmospheric new particle formation and growth in most continental regions, thereby increasing CCN concentrations, especially at high values of cloud supersaturation. Isoprene-derived SOA tends to suppress atmospheric new particle formation, yet it assists the growth of sub-CCN-size primary particles to CCN. Taking into account compound specific monoterpene emissions has a moderate effect on the modeled global CCN budget. Significance Extremely low volatility organic compounds (ELVOC) are suggested to promote aerosol particle formation and cloud condensation nuclei (CCN) production in the atmosphere. We show that the capability of biogenic VOC (BVOC) to produce ELVOC depends strongly on their chemical structure and relative oxidant levels. BVOC with an endocyclic double bond, representative emissions from, e.g., boreal forests, efficiently produce ELVOC from ozonolysis. Compounds with exocyclic double bonds or acyclic compounds including isoprene, emission representative of the tropics, produce minor quantities of ELVOC, and the role of OH radical oxidation is relatively larger. Implementing these findings into a global modeling framework shows that detailed assessment of ELVOC production pathways is crucial for understanding biogenic secondary organic aeroso