title: Production of extremely low volatile organic compounds from biogenic emissions: Measured yields and atmospheric implications.
abstract: 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 O3 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.
authors.affiliation: Leibniz-Institut für Troposphärenforschung (TROPOS), 04318 Leipzig, Germany; Department of Physics, University of Helsinki, 00014 Helsinki, Finland; tuija.jokinen@helsinki.fi.
authors.forename: Tuija
authors.initials: T
authors.lastname: Jokinen
authors.affiliation: Leibniz-Institut für Troposphärenforschung (TROPOS), 04318 Leipzig, Germany;
authors.forename: Torsten
authors.initials: T
authors.lastname: Berndt
authors.affiliation: Department of Physics, University of Helsinki, 00014 Helsinki, Finland;
authors.forename: Risto
authors.initials: R
authors.lastname: Makkonen
authors.affiliation: Department of Physics, University of Helsinki, 00014 Helsinki, Finland;
authors.forename: Veli-Matti
authors.initials: VM
authors.lastname: Kerminen
authors.affiliation: Department of Physics, University of Helsinki, 00014 Helsinki, Finland;
authors.forename: Heikki
authors.initials: H
authors.lastname: Junninen
authors.affiliation: Department of Physics, University of Helsinki, 00014 Helsinki, Finland;
authors.forename: Pauli
authors.identifier: http://orcid.org/0000-0002-4625-9590
authors.initials: P
authors.lastname: Paasonen
authors.affiliation: Leibniz-Institut für Troposphärenforschung (TROPOS), 04318 Leipzig, Germany;
authors.forename: Frank
authors.initials: F
authors.lastname: Stratmann
authors.affiliation: Leibniz-Institut für Troposphärenforschung (TROPOS), 04318 Leipzig, Germany;
authors.forename: Hartmut
authors.initials: H
authors.lastname: Herrmann
authors.affiliation: Atmospheric Sciences and Global Change Division, Pacific Northwest National Laboratory, Richland, WA 99354;
authors.forename: Alex B
authors.initials: AB
authors.lastname: Guenther
authors.affiliation: Department of Physics, University of Helsinki, 00014 Helsinki, Finland; Aerodyne Research, Inc., Billerica, MA 01821.
authors.forename: Douglas R
authors.initials: DR
authors.lastname: Worsnop
authors.affiliation: Department of Physics, University of Helsinki, 00014 Helsinki, Finland;
authors.forename: Markku
authors.initials: M
authors.lastname: Kulmala
authors.affiliation: Department of Physics, University of Helsinki, 00014 Helsinki, Finland;
authors.forename: Mikael
authors.initials: M
authors.lastname: Ehn
authors.affiliation: Department of Physics, University of Helsinki, 00014 Helsinki, Finland;
authors.forename: Mikko
authors.initials: M
authors.lastname: Sipilä
mesh_terms: D000393:Air Pollutants / Q000737:chemistry*; D001272:Atmosphere; D008962:Models, Theoretical; D010126:Ozone / Q000737:chemistry; D055549:Volatile Organic Compounds / Q000138:chemical synthesis*
chemical_list: D000393:Air Pollutants; D055549:Volatile Organic Compounds; D010126:Ozone
keywords: ELVOC; autoxidation; isoprene; monoterpenes; new particle formation