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Abstract Isoprene (C₅H₈) is the non-methane hydrocarbon with the highest emissions to the atmosphere. It is mainly produced by vegetation, especially broad-leaved trees, and efficiently transported to the upper troposphere in deep convective clouds, where it is mixed with lightning NO_x. Isoprene oxidation products drive rapid formation and growth of new particles in the tropical upper troposphere. However, isoprene oxidation pathways at low temperatures are not well understood. Here, in experiments at the CERN CLOUD chamber at 223 K and 243 K, we find that isoprene oxygenated organic molecules (IP-OOM) all involve two successive$${{{\rm{OH}}}}^{\bullet}$$ ${\mathrm{OH}}^{\bullet }$oxidations. However, depending on the ambient concentrations of the termination radicals ($${{{{\rm{HO}}}}_{2}}^{\bullet},\,{{{\rm{NO}}}}^{\bullet}$$ ${{\mathrm{HO}}_2}^{\bullet },{\mathrm{NO}}^{\bullet }$, and$${{{\rm{NO}}}}_{2}^{\bullet}$$ ${\mathrm{NO}}_2^{\bullet }$), vastly-different IP-OOM emerge, comprising compounds with zero, one or two nitrogen atoms. Our findings indicate high IP-OOM production rates for the tropical upper troposphere, mainly resulting in nitrate IP-OOM but with an increasing non-nitrate fraction around midday, in close agreement with aircraft observations. 

Isoprene affects new particle formation rates in environments and experiments also containing monoterpenes. 

Abstract Aircraft observations have revealed ubiquitous new particle formation in the tropical upper troposphere over the Amazon^1,2and the Atlantic and Pacific oceans^3,4. Although the vapours involved remain unknown, recent satellite observations have revealed surprisingly high night-time isoprene mixing ratios of up to 1 part per billion by volume (ppbv) in the tropical upper troposphere⁵. Here, in experiments performed with the CERN CLOUD (Cosmics Leaving Outdoor Droplets) chamber, we report new particle formation initiated by the reaction of hydroxyl radicals with isoprene at upper-tropospheric temperatures of −30 °C and −50 °C. We find that isoprene-oxygenated organic molecules (IP-OOM) nucleate at concentrations found in the upper troposphere, without requiring any more vapours. Moreover, the nucleation rates are enhanced 100-fold by extremely low concentrations of sulfuric acid or iodine oxoacids above 10⁵ cm⁻³, reaching rates around 30 cm⁻³ s⁻¹at acid concentrations of 10⁶ cm⁻³. Our measurements show that nucleation involves sequential addition of IP-OOM, together with zero or one acid molecule in the embryonic molecular clusters. IP-OOM also drive rapid particle growth at 3–60 nm h⁻¹. We find that rapid nucleation and growth rates persist in the presence of NO_xat upper-tropospheric concentrations from lightning. Our laboratory measurements show that isoprene emitted by rainforests may drive rapid new particle formation in extensive regions of the tropical upper troposphere^1,2, resulting in tens of thousands of particles per cubic centimetre. 

We present a “diagonal” Volatility Basis Set (dVBS) comparing gas-phase concentrations of oxygenated organic molecules (OOM) to their condensed-phase mass fractions. 

Biogenic vapors form new particles in the atmosphere, affecting global climate. The contributions of monoterpenes and isoprene to new particle formation (NPF) have been extensively studied. However, sesquiterpenes have received little attention despite a potentially important role due to their high molecular weight. Via chamber experiments performed under atmospheric conditions, we report biogenic NPF resulting from the oxidation of pure mixtures of β-caryophyllene, α-pinene, and isoprene, which produces oxygenated compounds over a wide range of volatilities. We find that a class of vapors termed ultralow-volatility organic compounds (ULVOCs) are highly efficient nucleators and quantitatively determine NPF efficiency. When compared with a mixture of isoprene and monoterpene alone, adding only 2% sesquiterpene increases the ULVOC yield and doubles the formation rate. Thus, sesquiterpene emissions need to be included in assessments of global aerosol concentrations in pristine climates where biogenic NPF is expected to be a major source of cloud condensation nuclei.