Forests emit large quantities of volatile organic compounds (VOCs) to the atmosphere. Their condensable oxidation products can form secondary organic aerosol, a significant and ubiquitous component of atmospheric aerosol, which is known to affect the Earth's radiation balance by scattering solar radiation and by acting as cloud condensation nuclei. The quantitative assessment of such climate effects remains hampered by a number of factors, including an incomplete understanding of how biogenic VOCs contribute to the formation of atmospheric secondary organic aerosol. The growth of newly formed particles from sizes of less than three nanometres up to the sizes of cloud condensation nuclei (about one hundred nanometres) in many continental ecosystems requires abundant, essentially non-volatile organic vapours, but the sources and compositions of such vapours remain unknown. Here we investigate the oxidation of VOCs, in particular the terpene α-pinene, under atmospherically relevant conditions in chamber experiments. We find that a direct pathway leads from several biogenic VOCs, such as monoterpenes, to the formation of large amounts of extremely low-volatility vapours. These vapours form at significant mass yield in the gas phase and condense irreversibly onto aerosol surfaces to produce secondary organic aerosol, helping to explain the discrepancy between the observed atmospheric burden of secondary organic aerosol and that reported by many model studies. We further demonstrate how these low-volatility vapours can enhance, or even dominate, the formation and growth of aerosol particles over forested regions, providing a missing link between biogenic VOCs and their conversion to aerosol particles. Our findings could help to improve assessments of biosphere-aerosol-climate feedback mechanisms, and the air quality and climate effects of biogenic emissions generally.

The prompt formation of highly oxidized organic compounds in the ozonolysis of cyclohexene (C6H10) was investigated by means of laboratory experiments together with quantum chemical calculations. The experiments were performed in borosilicate glass flow tube reactors coupled to a chemical ionization atmospheric pressure interface time-of-flight mass spectrometer with a nitrate ion (NO3(-))-based ionization scheme. Quantum chemical calculations were performed at the CCSD(T)-F12a/VDZ-F12//ωB97XD/aug-cc-pVTZ level, with kinetic modeling using multiconformer transition state theory, including Eckart tunneling corrections. The complementary investigation methods gave a consistent picture of a formation mechanism advancing by peroxy radical (RO2) isomerization through intramolecular hydrogen shift reactions, followed by sequential O2 addition steps, that is, RO2 autoxidation, on a time scale of seconds. Dimerization of the peroxy radicals by recombination and cross-combination reactions is in competition with the formation of highly oxidized monomer species and is observed to lead to peroxides, potentially diacyl peroxides. The molar yield of these highly oxidized products (having O/C > 1 in monomers and O/C > 0.55 in dimers) from cyclohexene ozonolysis was determined as (4.5 ± 3.8)%. Fully deuterated cyclohexene and cis-6-nonenal ozonolysis, as well as the influence of water addition to the system (either H2O or D2O), were also investigated in order to strengthen the arguments on the proposed mechanism. Deuterated cyclohexene ozonolysis resulted in a less oxidized product distribution with a lower yield of highly oxygenated products and cis-6-nonenal ozonolysis generated the same monomer product distribution, consistent with the proposed mechanism and in agreement with quantum chemical modeling.

Abstract. It has been postulated that secondary organic particulate matter plays a pivotal role in the early growth of newly formed particles in forest areas. The recently detected class of extremely low volatile organic compounds (ELVOC) provides the missing organic vapors and possibly contributes a significant fraction to atmospheric SOA (secondary organic aerosol). The sequential rearrangement of peroxy radicals and subsequent O 2 addition results in ELVOC which are highly oxidized multifunctional molecules (HOM). Key for efficiency of such HOM in early particle growth is that their formation is induced by one attack of the oxidant (here O 3 ), followed by an autoxidation process involving molecular oxygen. Similar mechanisms were recently observed and predicted by quantum mechanical calculations e.g., for isoprene. To assess the atmospheric importance and therewith the potential generality, it is crucial to understand the formation pathway of HOM.To elucidate the formation path of HOM as well as necessary and sufficient structural prerequisites of their formation we studied homologous series of cycloalkenes in comparison to two monoterpenes. We were able to directly observe highly oxidized multifunctional peroxy radicals with 8 or 10 O atoms by an Atmospheric Pressure interface High Resolution Time of Flight Mass Spectrometer (APi-TOF-MS) equipped with a NO − 3 -chemical ionization (CI) source. In the case of O 3 acting as an oxidant, the starting peroxy radical is formed on the so-called vinylhydroperoxide path. HOM peroxy radicals and their termination reactions with other peroxy radicals, including dimerization, allowed for analyzing the observed mass spectra and narrowing down the likely formation path. As consequence, we propose that HOM are multifunctional percarboxylic acids, with carbonyl, hydroperoxy, or hydroxy groups arising from the termination steps. We figured that aldehyde groups facilitate the initial rearrangement steps. In simple molecules like cycloalkenes, autoxidation was limited to both terminal C atoms and two further C atoms in the respective α positions. In more complex molecules containing tertiary H atoms or small, constrained rings, even higher oxidation degrees were possible, either by simple H shift of the tertiary H atom or by initialization of complex ring-opening reactions.

Secondary organic aerosol contributes to the atmospheric particle burden with implications for air quality and climate. Biogenic volatile organic compounds emitted from plants are important secondary organic aerosol precursors with isoprene emissions dominating globally. However, its yield of particle mass from oxidation is generally modest compared to that of other terpenoids. Here we show that isoprene, carbon monoxide and methane can suppress the instantaneous mass and the overall mass yield derived from monoterpenes in mixtures. We find that isoprene scavenges hydroxyl radicals preventing reaction with monoterpenes and the resulting isoprene peroxy radicals scavenge highly oxygenated monoterpene products. These effects reduced the yield of low-volatility products that would otherwise form secondary organic aerosol. Global model calculations indicate that oxidant and product scavenging can operate effectively in the real atmosphere. Highly reactive, modest aerosol yield compounds are not necessarily net producers and their oxidation can suppress both particle number and mass.

Atmospheric aerosols impact climate by scattering and absorbing solar radiation and by acting as ice and cloud condensation nuclei. Biogenic secondary organic aerosols (BSOAs) comprise an important component of atmospheric aerosols. Biogenic volatile organic compounds (BVOCs) emitted by vegetation are the source of BSOAs. Pathogens and insect attacks, heat waves and droughts can induce stress to plants that may impact their BVOC emissions, and hence the yield and type of formed BSOAs, and possibly their climatic effects. This raises questions of whether stress-induced changes in BSOA formation may attenuate or amplify effects of climate change. In this study we assess the potential impact of stress-induced BVOC emissions on BSOA formation for tree species typical for mixed deciduous and Boreal Eurasian forests. We studied the photochemical BSOA formation for plants infested by aphids in a laboratory setup under well-controlled conditions and applied in addition heat and drought stress. The results indicate that stress conditions substantially modify BSOA formation and yield. Stress-induced emissions of sesquiterpenes, methyl salicylate, and C₁₇-BVOCs increase BSOA yields. Mixtures including these compounds exhibit BSOA yields between 17 and 33%, significantly higher than mixtures containing mainly monoterpenes (4–6% yield). Green leaf volatiles suppress SOA formation, presumably by scavenging OH, similar to isoprene. By classifying emission types, stressors and BSOA formation potential, we discuss possible climatic feedbacks regarding aerosol effects. We conclude that stress situations for plants due to climate change should be considered in climate–vegetation feedback mechanisms

Abstract. Climate change will induce extended heat waves to parts of the vegetation more frequently. High temperatures may act as stress (thermal stress) on plants changing emissions of biogenic volatile organic compounds (BVOCs). As BVOCs impact the atmospheric oxidation cycle and aerosol formation, it is important to explore possible alterations of BVOC emissions under high temperature conditions. Applying heat to European beech, Palestine oak, Scots pine, and Norway spruce in a laboratory setup either caused the well-known exponential increases of BVOC emissions or induced irreversible changes of BVOC emissions. Considering only irreversible changes of BVOC emissions as stress impacts, we found that high temperatures decreased the de novo emissions of monoterpenes, sesquiterpenes and phenolic BVOC. This behaviour was independent of the tree species and whether the de novo emissions were constitutive or induced by biotic stress.In contrast, application of thermal stress to conifers amplified the release of monoterpenes stored in resin ducts of conifers and induced emissions of green leaf volatiles. In particular during insect attack on conifers, the plants showed de novo emissions of sesquiterpenes and phenolic BVOCs, which exceeded constitutive monoterpene emissions from pools. The heat-induced decrease of de novo emissions was larger than the increased monoterpene release caused by damage of resin ducts. For insect-infested conifers the net effect of thermal stress on BVOC emissions could be an overall decrease.Global change-induced heat waves may put hard thermal stress on plants. If so, we project that BVOC emissions increase is more than predicted by models only in areas predominantly covered with conifers that do not emit high amounts of sesquiterpenes and phenolic BVOCs. Otherwise overall effects of high temperature stress will be lower increases of BVOC emissions than predicted by algorithms that do not consider stress impacts.

Abstract. In this study, the NOx dependence of secondary organic aerosol (SOA) formation from photooxidation of the biogenic volatile organic compound (BVOC) β-pinene was comprehensively investigated in the Jülich Plant Atmosphere Chamber. Consistent with the results of previous NOx studies we found increases of SOA yields with increasing [NOx] at low-NOx conditions ([NOx]0  <  30 ppb, [BVOC]0 ∕ [NOx]0  >  10 ppbC ppb−1). Furthermore, increasing [NOx] at high-NOx conditions ([NOx]0  >  30 ppb, [BVOC]0 ∕ [NOx]0  ∼  10 to  ∼  2.6 ppbC ppb−1) suppressed the SOA yield. The increase of SOA yield at low-NOx conditions was attributed to an increase of OH concentration, most probably by OH recycling in NO + HO2  →  NO2 + OH reaction. Separate measurements without NOx addition but with different OH primary production rates confirmed the OH dependence of SOA yields. After removing the effect of OH concentration on SOA mass growth by keeping the OH concentration constant, SOA yields only decreased with increasing [NOx]. Measuring the NOx dependence of SOA yields at lower [NO] ∕ [NO2] ratio showed less pronounced increase in both OH concentration and SOA yield. This result was consistent with our assumption of OH recycling by NO and to SOA yields being dependent on OH concentrations. Our results furthermore indicated that NOx dependencies vary for different NOx compositions. A substantial fraction of the NOx-induced decrease of SOA yields at high-NOx conditions was caused by NOx-induced suppression of new particle formation (NPF), which subsequently limits the particle surface where low volatiles condense. This was shown by probing the NOx dependence of SOA formation in the presence of seed particles. After eliminating the effect of NOx-induced suppression of NPF and NOx-induced changes of OH concentrations, the remaining effect of NOx on the SOA yield from β-pinene photooxidation was moderate. Compared to β-pinene, the SOA formation from α-pinene photooxidation was only suppressed by increasing NOx. However, basic mechanisms of the NOx impacts were the same as that of β-pinene.

Abstract. The impact of nitrogen oxides (NOx = NO + NO2) on new particle formation (NPF) and on photochemical ozone production from real plant volatile organic compound (BVOC) emissions was studied in a laboratory setup. At high NOx conditions ([BVOC] / [NOx] < 7, [NOx] > 23 ppb) new particle formation was suppressed. Instead, photochemical ozone formation was observed resulting in higher hydroxyl radical (OH) and lower nitrogen monoxide (NO) concentrations. When [NO] was reduced back to levels below 1 ppb by OH reactions, NPF was observed. Adding high amounts of NOx caused NPF to be slowed by orders of magnitude compared to analogous experiments at low NOx conditions ([NOx] ~300 ppt), although OH concentrations were higher. Varying NO2 photolysis enabled showing that NO was responsible for suppression of NPF. This suggests that peroxy radicals are involved in NPF. The rates of NPF and photochemical ozone production were related by power law dependence with an exponent approaching −2. This exponent indicated that the overall peroxy radical concentration must have been similar when NPF occurred. Thus, permutation reactions of first-generation peroxy radicals cannot be the rate limiting step in NPF from monoterpene oxidation. It was concluded that permutation reactions of higher generation peroxy-radical-like intermediates limit the rate of new particle formation. In contrast to the strong effects on the particle numbers, the formation of particle mass was substantially less sensitive to NOx concentrations. If at all, yields were reduced by about an order of magnitude only at very high NOx concentrations.