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.

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. Hydroxyl (OH) radical reactivity (k OH ) has been measured for 18 years with different measurement techniques. In order to compare the performances of instruments deployed in the field, two campaigns were conducted performing experiments in the atmospheric simulation chamber SAPHIR at Forschungszentrum Jülich in October 2015 and April 2016. Chemical conditions were chosen either to be representative of the atmosphere or to test potential limitations of instruments. All types of instruments that are currently used for atmospheric measurements were used in one of the two campaigns. The results of these campaigns demonstrate that OH reactivity can be accurately measured for a wide range of atmospherically relevant chemical conditions (e.g. water vapour, nitrogen oxides, various organic compounds) by all instruments. The precision of the measurements (limit of detection < 1 s −1 at a time resolution of 30 s to a few minutes) is higher for instruments directly detecting hydroxyl radicals, whereas the indirect comparative reactivPublished by Copernicus Publications on behalf of the European Geosciences Union. H. Fuchs et al.: OH reactivity comparison in SAPHIRity method (CRM) has a higher limit of detection of 2 s −1 at a time resolution of 10 to 15 min. The performances of the instruments were systematically tested by stepwise increasing, for example, the concentrations of carbon monoxide (CO), water vapour or nitric oxide (NO). In further experiments, mixtures of organic reactants were injected into the chamber to simulate urban and forested environments. Overall, the results show that the instruments are capable of measuring OH reactivity in the presence of CO, alkanes, alkenes and aromatic compounds. The transmission efficiency in Teflon inlet lines could have introduced systematic errors in measurements for low-volatile organic compounds in some instruments. CRM instruments exhibited a larger scatter in the data compared to the other instruments. The largest differences to reference measurements or to calculated reactivity were observed by CRM instruments in the presence of terpenes and oxygenated organic compounds (mixing ratio of OH reactants were up to 10 ppbv). In some of these experiments, only a small fraction of the reactivity is detected. The accuracy of CRM measurements is most likely limited by the corrections that need to be applied to account for known effects of, for example, deviations from pseudo first-order conditions, nitrogen oxides or water vapour on the measurement. Methods used to derive these corrections vary among the different CRM instruments. Measurements taken with a flowtube instrument combined with the direct detection of OH by chemical ionisation mass spectrometry (CIMS) show limitations in cases of high reactivity and high NO concentrations but were accurate for low reactivity (< 15 s −1 ) and low NO (< 5 ppbv) conditions.

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. 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.

&lt;p&gt;&lt;strong&gt;Abstract.&lt;/strong&gt; The formation of organic nitrates (ON) in the gas phase and their impact on mass formation of Secondary Organic Aerosol (SOA) was investigated in a laboratory study for &lt;i&gt;&amp;#945;&lt;/i&gt;-pinene and &lt;i&gt;&amp;#946;&lt;/i&gt;-pinene photo-oxidation. Focus was the elucidation of those mechanisms that cause the often observed suppression of SOA mass formation by NO&lt;sub&gt;x&lt;/sub&gt;, and therein the role of highly oxygenated multifunctional molecules (HOM). We observed that with increasing NO&lt;sub&gt;x&lt;/sub&gt; (a) the portion of HOM organic nitrates (HOM-ON) increased, (b) the fraction of accretion products (HOM-ACC) decreased and (c) HOM-ACC contained on average smaller carbon numbers.&lt;/p&gt; &lt;p&gt;Specifically, we investigated HOM organic nitrates (HOM-ON), arising from the termination reactions of HOM peroxy radicals with NO&lt;sub&gt;x&lt;/sub&gt;, and HOM permutation products (HOM-PP), such as ketones, alcohols or hydroperoxides, formed by other termination reactions. Effective uptake coefficients &amp;#947;eff of HOM on particles were determined. HOM with more than 6 O-atoms efficiently condensed on particles (&lt;i&gt;&amp;#947;&lt;/i&gt;&lt;/sub&gt;&lt;sub&gt;eff&lt;/sub&gt;&amp;#8201;&gt;&amp;#8201;0.5 in average) and for HOM containing more than 8 O-atoms, every collision led to loss. There was no systematic difference in &lt;i&gt;&amp;#947;&lt;/i&gt;&lt;/sub&gt;&lt;sub&gt;eff&lt;/sub&gt; for HOM-ON and HOM-PP arising from the same HOM peroxy radicals. This similarity is attributed to the multifunctional character of the HOM: as functional groups in HOM arising from the same precursor HOM peroxy radical are identical, vapor pressures should not strongly depend on the character the final termination group. As a consequence, the suppressing effect of NO&lt;sub&gt;x&lt;/sub&gt; on SOA formation cannot be simply explained by replacement of terminal functional groups by organic nitrate groups.&lt;/p&gt; &lt;p&gt;The fraction of organic bound nitrate (OrgNO&lt;sub&gt;3&lt;/sub&gt;) stored in gas-phase HOM-ON appeared to be substantially higher than the fraction of particulate OrgNO&lt;sub&gt;3&lt;/sub&gt; observed by aerosol mass spectrometry. This result suggests losses of OrgNO&lt;sub&gt;3&lt;/sub&gt; for organic nitrates in particles, probably due to hydrolysis of OrgNO&lt;sub&gt;3&lt;/sub&gt; that releases HNO&lt;sub&gt;3&lt;/sub&gt; into the gas phase but leaves behind the organic rest in the particulate phase. However, the loss of HNO&lt;sub&gt;3&lt;/sub&gt; alone, could not explain the observed suppressing effect of NO&lt;sub&gt;x&lt;/sub&gt; on particle mass formation from &lt;i&gt;&amp;#945;&lt;/i&gt;-pinene and &lt;i&gt;&amp;#946;&lt;/i&gt;-pinene.&lt;/p&gt; &lt;p&gt;We therefore attributed most of the reduction in SOA mass yields with increasing NO&lt;sub&gt;x&lt;/sub&gt; to the significant suppression of gas-phase HOM-ACC which have high molecular mass and are potentially important for SOA mass formation at low NO&lt;sub&gt;x&lt;/sub&gt; conditions.&lt;/p&gt;

Abstract. Stress-induced volatile organic compound (VOC) emissions from transgenic Grey poplar modified in isoprene emission potential were used for the investigation of photochemical secondary organic aerosol (SOA) formation. In poplar, acute ozone stress induces the emission of a wide array of VOCs dominated by sesquiterpenes and aromatic VOCs. Constitutive light-dependent emission of isoprene ranged between 66 nmol m −2 s −1 in non-transgenic controls (wild type WT) and nearly zero (<0.5 nmol m −2 s −1 ) in isoprene emission-repressed plants (line RA22), respectively. Nucleation rates of up to 3600 cm −3 s −1 were observed in our experiments. In the presence of isoprene new particle formation was suppressed compared to non-isoprene containing VOC mixtures. Compared to isoprene/monoterpene systems emitted from other plants the suppression of nucleation by isoprene was less effective for the VOC mixture emitted from stressed poplar. This is explained by the observed high efficiency of new particle formation for emissions from stressed poplar. Direct measurements of OH in the reaction chamber revealed that the steady state concentration of OH is lower in the presence of isoprene than in the absence of isoprene, supporting the hypothesis that isoprenes' suppressing effect on nucleation is related to radical chemistry. In order to test whether isoprene contributes to SOA mass formation, fully deuterated isoprene (C 5 D 8 ) was added to the stress-induced emission profile of an isoprene free poplar mutant. Mass spectral analysis showed that, despite the isoprene-induced suppression of particle formation, fractions of deuterated isoprene were incorporated into the SOA. A fractional mass yield of 2.3 % of isoprene was observed. Future emission changes due to land use and climate change may therefore affect both gas phase oxidation capacity and new particle number formation.

Abstract. Impacts of soil moisture on de-novo monoterpene (MT) emissions from Holm oak, European beech, Scots pine, and Norway spruce were studied in laboratory experiments. The volumetric water content of the soil, Θ, was used as reference quantity to parameterize the dependency of MT emissions on soil moisture and to characterize the severity of the drought. When Θ dropped from 0.4 m3 m−3 to ~ 0.2 m3 m−3 slight increases of de-novo MT emissions were observed but with further progressing drought the emissions decreased to almost zero. The increases of MT emissions observed under conditions of mild drought were explainable by increases of leaf temperature due to lowered transpirational cooling. When Θ fell below certain thresholds, MT emissions decreased simultaneously with Θ and the relationship between Θ and MT emissions was approximately linear. The thresholds of Θ (0.044–0.19 m3 m−3) were determined as well other parameters required to describe the soil moisture dependence of de-novo MT emissions for application in the Model of Emissions of Gases and Aerosols from Nature, MEGAN. A factorial approach was found appropriate to describe the impacts of Θ, temperature, and light. Temperature and Θ influenced the emissions largely independent from each other, and, in a similar manner, light intensity and Θ acted independently on de-novo MT emissions. The use of Θ as reference quantity in a factorial approach was tenable in predicting constitutive de-novo MT emissions when Θ changed on a time scale of days. Only when soil moisture changed suddenly empirical parameterization with Θ as a reference was unsuccessful.