Monoterpene Emissions Research Articles

Ozone-triggered surface uptake and stress volatile emissions in Nicotiana tabacum 'Wisconsin'.

Ozone is a strong oxidant and a key stress elicitor. The immediate and longer term impacts of ozone are poorly understood in species with emission of both de novo synthesized and stored volatiles, such a tobacco (Nicotiana tabacum), which has terpene-containing glandular trichomes on the leaf surface. In this study, we exposed N. tabacum 'Wisconsin' leaves to acute ozone doses of 0 (control), 400, 600, 800, and 1000 ppb for 30 min and studied the effects of ozone exposure on ozone uptake, gas-exchange characteristics, and emissions of lipoxygenase pathway volatiles, monoterpenes, and sesquiterpenes. Foliage emissions of lipoxygenase pathway volatiles were quantitatively related to the severity of ozone exposure, but the stress dose vs. emission relationship was weaker for terpenoids. Analysis of leaf terpene content and composition indicated that several monoterpenes and sesquiterpenes were not stored in leaves and were synthesized de novo upon ozone exposure. The highest degree of elicitation for each compound was observed immediately after ozone treatment and it declined considerably during recovery. Leaf ozone uptake was dominated by non-stomatal deposition, and the emissions of total lipoxygenase pathway volatiles and mono- and sesquiterpenes were positively correlated with non-stomatal ozone deposition. Overall, this study demonstrates remarkably high ozone resistance of the studied tobacco cultivar and indicates that ozone's effects on volatile emissions primarily reflect modifications in the release of stored volatiles and reaction of ozone with the leaf surface structure.

Oak gall wasp infections of Quercus robur leaves lead to profound modifications in foliage photosynthetic and volatile emission characteristics.

Oak trees (Quercus) are hosts of diverse gall-inducing parasites, but the effects of gall formation on the physiology and biochemistry on host oak leaves is poorly understood. The influence of infection by four species from two widespread gall wasp genera, Neuroterus (N.anthracinus and N.albipes) and Cynips (C.divisa and C.quercusfolii), on foliage morphology, chemistry, photosynthetic characteristics, constitutive isoprene, and induced volatile emissions in Q. robur was investigated. Leaf dry mass per unit area (MA ), net assimilation rate per area (AA ), stomatal conductance (gs ), and constitutive isoprene emissions decreased with the severity of infection by all gall wasp species. The reduction in AA was mainly determined by reduced MA and to a lower extent by lower content of leaf nitrogen and phosphorus in gall-infected leaves. The emissions of lipoxygenase pathway volatiles increased strongly with increasing infection severity for all 4 species with the strongest emissions in major vein associated species, N.anthracinus. Monoterpene and sesquiterpene emissions were strongly elicited in N.albipes and Cynips species, but not in N.anthracinus. These results provide valuable information for diagnosing oak infections using ambient air volatile fingerprints and for predicting the impacts of infections on photosynthetic productivity and whole tree performance.

Diurnal regulation of the floral scent emission by light and circadian rhythm in the Phalaenopsis orchids

BackgroundPhalaenopsis bellina and its closely related species, P. violacea, emit linalool, geraniol and their derivatives as the predominant monoterpenes at the full-bloom stages. Geranyl diphosphate synthase (PbGDPS) is the key enzyme that converts precursors for monoterpene biosynthesis. Besides the monoterpenes being synthesized in concert with floral development stages, we noticed that the scent emission of P. bellina and P. violacea was detected mainly in the daytime.ResultsThe monoterpenes of P. violacea flowers displayed a diurnal emission pattern, which was regulated by an internal oscillator in the treatment of constant light. In contrast, constant dark diminished the scent emission levels, indicating that light also affects monoterpene emission in P. violacea. Further treating P. violacea with various light wavelengths showed that the monoterpene emission was greatest in white light condition. Other Phalaenopsis hybrids, including P. I-Hsin Venus ‘KHM2212’ and P. Meidarland Bellina Age ‘LM128’, responded differently to various light wavelengths but most of them still showed the highest scent emission under the whole spectra of light. A great number of light-responsive, HY5-interacting, and circadian-responsive elements was enriched on the promoters of both structural genes and transcription factors for monoterpene biosynthesis. Furthermore, several putative genes encoding components involved in light and circadian signaling pathways were also identified in the transcriptome of P. bellina flowers at consecutive stages (from the anthesis day to day 7 post anthesis).ConclusionsTaken together, both circadian clock and light factors had positive effects on orchid floral scent emission, and the regulation resided on the control of both structural genes and transcription factors for monoterpene biosynthesis.

Nutrient-rich plants emit a less intense blend of volatile isoprenoids.

The emission of isoprenoids (e.g. isoprene and monoterpenes) by plants plays an important defensive role against biotic and abiotic stresses. Little is known, however, about the functional traits linked to species-specific variability in the types and rates of isoprenoids emitted and about possible co-evolution of functional traits with isoprenoid emission type (isoprene emitter, monoterpene emitter or both). We combined data for isoprene and monoterpene emission rates per unit dry mass with key functional traits (foliar nitrogen (N) and phosphorus (P) concentrations, and leaf mass per area) and climate for 113 plant species, covering the boreal, wet temperate, Mediterranean and tropical biomes. Foliar N was positively correlated with isoprene emission, and foliar P was negatively correlated with both isoprene and monoterpene emission rate. Nonemitting plants generally had the highest nutrient concentrations, and those storing monoterpenes had the lowest concentrations. Our phylogenetic analyses found that the type of isoprenoid emission followed an adaptive, rather than a random model of evolution. Evolution of isoprenoids may be linked to nutrient availability. Foliar N and P are good predictors of the type of isoprenoid emission and the rate at which monoterpenes, and to a lesser extent isoprene, are emitted.

Observation of nighttime new particle formation over the French Landes forest

Improving the understanding of processes related to atmospheric particle sources is essential to better assess future climate. Especially, how biogenic volatile organic compounds (BVOCs) are involved in new particle formation (NPF) is still unclear, highlighting the need for field studies in sites that have not yet been explored. Weakly anthropised, mostly composed of maritime pines (known as strong monoterpene emitters), vast and under the influence of sea spray inputs, the Landes forest (located in the southwestern part of France) is a suitable ecosystem to explore these questions. The aim of the present work was to investigate for the first time NPF in the Landes forest, and to identify the conditions for NPF. During a field campaign conducted in July 2015, clear NPF was observed during nighttime, at a high frequency rate (37.5%), whereas only two daytime episodes were observed. Growth rates during NPF events were in the range 9.0–15.7nmh−1, and nucleation rates (J10) in the range 0.8–8 particles cm3s−1, typically in the range of reported values from rural sites. Nocturnal NPF started at sunset, lagging the reductions of temperature and ozone concentration as well as the increase of relative humidity, atmospheric stability and monoterpene concentration. We established that NPF occurred during more stratified atmosphere episodes, reflecting that NPF is more influenced by local processes at the Landes forest site (Bilos). Concentration of the sum of monoterpenes, here mainly α- and β-pinene, was observed to be maximal during NPF episodes. On the contrary, ozone concentration was lower, which may indicate a larger consumption during nights where NPF episodes occur. Results strongly suggest the contribution of BVOC oxidation to nocturnal NPF, in both nucleation and the growth stages.

The Uncertain Role of Biogenic VOC for Boundary-Layer Ozone Concentration: Example Investigation of Emissions from Two Forest Types with a Box Model

High levels of air pollution including ground level ozone significantly reduce humans’ life expectancy and cause forest damage and decreased tree growth. The French Vosges and the German Black Forest are regions well-known for having the highest tropospheric ozone concentrations at remote forested sites in Central Europe. This box model study investigates the sensitivity of atmospheric chemistry calculations of derived ozone on differently resolved forest tree composition and volatile organic compound emissions. Representative conditions were chosen for the Upper Rhine area including the Alsatian Vosges/France and the Black Forest/Germany during summer. This study aims to answer the following question: What level of input detail for Alsace and Black Forest tree mixtures is required to accurately simulate ozone formation? While the French forest in Alsace—e.g., in the Vosges—emits isoprene to a substantially higher extent than the forest at the German site, total monoterpene emissions at the two sites are rather similar. However, the individual monoterpene structures, and therefore their reactivity, differs. This causes a higher ozone production rate for Vosges forest mixture conditions than for Black Forest tree mixtures at identical NOx levels, with the difference increasing with temperature. The difference in ozone formation is analyzed in detail and the short-comings of reduced descriptions are discussed. The outcome serves as a to-do-list to allow accurate future ozone predictions influenced by the climate adaptation of forests and the change in forest species composition.

Basin-Scale Observations of Monoterpenes in the Arctic and Atlantic Oceans.

We report novel in situ speciated observations of monoterpenes (α- and β-pinene, myrcene, δ3-carene, ocimene, limonene) in seawater and air during three cruises in the Arctic and Atlantic Oceans, in/over generally oligotrophic waters. Oceanic concentrations of the individual monoterpenes ranged from below the detection limit of <1 pmol L-1 to 5 pmol L-1, with average concentrations of between 0.5 and 2.9 pmol L-1. After careful filtering for contamination, atmospheric mixing ratios varied from below the detection limit (<1 pptv) to 5 pptv, with averages of 0.05-5 pptv; these levels are up to 2 orders of magnitude lower than those reported previously. This could be at least partly due to sampling over waters with much lower biological activity than in previous studies. Unlike in previous studies, no clear relationships of the monoterpenes with biological variables were found. Based on our measured seawater concentrations and a global model simulation, we estimate total global marine monoterpene emissions of 0.16 Tg C yr-1, similar to a previous bottom-up estimate based on laboratory monoculture studies but 2 orders of magnitude lower than a previous top-down estimate of 29.5 Tg C yr-1.

Quantification of monoterpene emission sources of a conifer species in response to experimental drought.

Monoterpene (MT) emissions of conifer tree species, emitted from de novo synthesis and storage pools, play an important role in plant ecology and physiology. During drought stress both emission sources are affected differently and with conventional measuring techniques they are difficult to separate. We investigated 13C labelled MT emission of eight 3-year-old Scots pine seedlings in a drought stress experiment using a dynamic gas exchange chamber system (Tree DEMON). Monoterpene, water vapour and CO2 gas exchange were measured for a 2-day normal watering, a 11-day treatment and a 3-day re-watering period. In each period all trees were 13C labelled once for 5 h. Results showed the expected decrease of MT, water vapour and CO2 gas exchange with decreasing soil water content. However, during re-watering water vapour and CO2 gas exchange recovered fast to pre-drought levels, whereas MT increased to a lower level compared to the initial non-stressed phase. The 13C labelling showed highly variable %13C values for different MTs, which ranged compound-specific from 0.5 to 95 % for unstressed trees. Overall, around 36 ± 5 % of the total emission rate originated from de novo synthesized MTs during the 2-day prior to stress period. During full drought, the de novo fraction was reduced to 3 %. For the re-watering phase de novo emissions recovered only partly to 20 %, while pool emissions reached pre-drought conditions. Thus, emissions of de novo synthesized MTs of Scots pine are down-regulated by soil drought rather than MT emissions from pools.

The TOMCAT global chemical transport model v1.6: description of chemical mechanism and model evaluation

Abstract. This paper documents the tropospheric chemical mechanism scheme used in the TOMCAT 3-D chemical transport model. The current scheme includes a more detailed representation of hydrocarbon chemistry than previously included in the model, with the inclusion of the emission and oxidation of ethene, propene, butane, toluene and monoterpenes. The model is evaluated against a range of surface, balloon, aircraft and satellite measurements. The model is generally able to capture the main spatial and seasonal features of high and low concentrations of carbon monoxide (CO), ozone (O3), volatile organic compounds (VOCs) and reactive nitrogen. However, model biases are found in some species, some of which are common to chemistry models and some that are specific to TOMCAT and warrant further investigation. The most notable of these biases are (1) a negative bias in Northern Hemisphere (NH) winter and spring CO and a positive bias in Southern Hemisphere (SH) CO throughout the year, (2) a positive bias in NH O3 in summer and a negative bias at high latitudes during SH winter and (3) a negative bias in NH winter C2 and C3 alkanes and alkenes. TOMCAT global mean tropospheric hydroxyl radical (OH) concentrations are higher than estimates inferred from observations of methyl chloroform but similar to, or lower than, multi-model mean concentrations reported in recent model intercomparison studies. TOMCAT shows peak OH concentrations in the tropical lower troposphere, unlike other models which show peak concentrations in the tropical upper troposphere. This is likely to affect the lifetime and transport of important trace gases and warrants further investigation.

Transcriptome Sequencing Analysis Reveals a Difference in Monoterpene Biosynthesis between Scented Lilium 'Siberia' and Unscented Lilium 'Novano'.

Lilium is a world famous fragrant bulb flower with high ornamental and economic values, and significant differences in fragrance are found among different Lilium genotypes. In order to explore the mechanism underlying the different fragrances, the floral scents of Lilium ‘Sibeia’, with a strong fragrance, and Lilium ‘Novano’, with a very faint fragrance, were collected in vivo using a dynamic headspace technique. These scents were identified using automated thermal desorption—gas chromatography/mass spectrometry (ATD-GC/MS) at different flowering stages. We used RNA-Seq technique to determine the petal transcriptome at the full-bloom stage and analyzed differentially expressed genes (DEGs) to investigate the molecular mechanism of floral scent biosynthesis. The results showed that a significantly higher amount of Lilium ‘Siberia’ floral scent was released compared with Lilium ‘Novano’. Moreover, monoterpenes played a dominant role in the floral scent of Lilium ‘Siberia’; therefore, it is believed that the different emissions of monoterpenes mainly contributed to the difference in the floral scent between the two Lilium genotypes. Transcriptome sequencing analysis indicated that ~29.24 Gb of raw data were generated and assembled into 124,233 unigenes, of which 35,749 unigenes were annotated. Through a comparison of gene expression between these two Lilium genotypes, 6,496 DEGs were identified. The genes in the terpenoid backbone biosynthesis pathway showed significantly different expression levels. The gene expressions of 1-deoxy-D-xylulose 5-phosphate synthase (DXS), 1-deoxy-D-xylulose-5-phosphate reductoisomerase (DXR), 4-hydroxy-3-methylbut-2-enyl diphosphate synthase (HDS), 4-hydroxy-3-methylbut-2-enyl diphosphate reductase (HDR), isopentenyl diphosphate isomerase (IDI), and geranyl diphosphate synthase (GPS/GGPS), were upregulated in Lilium ‘Siberia’ compared to Lilium ‘Novano’, and two monoterpene synthase genes, ocimene synthase gene (OCS) and myrcene synthase gene (MYS), were also expressed at higher levels in the tepals of Lilium ‘Siberia’, which was consistent with the monoterpene release amounts. We demonstrated that the high activation levels of the pathways contributed to monoterpene biosynthesis in Lilium ‘Siberia’ resulting in high accumulations and emissions of monoterpenes, which led to the difference in fragrance between these two Lilium genotypes.

Methyl jasmonate-induced emission of biogenic volatiles is biphasic in cucumber: a high-resolution analysis of dose dependence.

Methyl jasmonate (MeJA) is a key airborne elicitor activating jasmonate-dependent signaling pathways, including induction of stress-related volatile emissions, but how the magnitude and timing of these emissions scale with MeJA dose is not known. Treatments with exogenous MeJA concentrations ranging from mild (0.2 mM) to lethal (50 mM) were used to investigate quantitative relationships among MeJA dose and the kinetics and magnitude of volatile release in Cucumis sativus by combining high-resolution measurements with a proton-transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) and GC-MS. The results highlighted biphasic kinetics of elicitation of volatiles. The early phase, peaking in 0.1-1 h after the MeJA treatment, was characterized by emissions of lipoxygenase (LOX) pathway volatiles and methanol. In the subsequent phase, starting in 6-12 h and reaching a maximum in 15-25 h after the treatment, secondary emissions of LOX compounds as well as emissions of monoterpenes and sesquiterpenes were elicited. For both phases, the maximum emission rates and total integrated emissions increased with applied MeJA concentration. Furthermore, the rates of induction and decay, and the duration of emission bursts were positively, and the timing of emission maxima were negatively associated with MeJA dose for LOX compounds and terpenoids, except for the duration of the first LOX burst. These results demonstrate major effects of MeJA dose on the kinetics and magnitude of volatile response, underscoring the importance of biotic stress severity in deciphering the downstream events of biological impacts.

Nitrate radical oxidation of &amp;lt;i&amp;gt;γ&amp;lt;/i&amp;gt;-terpinene: hydroxy nitrate, total organic nitrate, and secondary organic aerosol yields

Abstract. Polyolefinic monoterpenes represent a potentially important but understudied source of organic nitrates (ONs) and secondary organic aerosol (SOA) following oxidation due to their high reactivity and propensity for multi-stage chemistry. Recent modeling work suggests that the oxidation of polyolefinic γ-terpinene can be the dominant source of nighttime ON in a mixed forest environment. However, the ON yields, aerosol partitioning behavior, and SOA yields from γ-terpinene oxidation by the nitrate radical (NO3), an important nighttime oxidant, have not been determined experimentally. In this work, we present a comprehensive experimental investigation of the total (gas + particle) ON, hydroxy nitrate, and SOA yields following γ-terpinene oxidation by NO3. Under dry conditions, the hydroxy nitrate yield = 4(+1/−3) %, total ON yield = 14(+3/−2) %, and SOA yield ≤ 10 % under atmospherically relevant particle mass loadings, similar to those for α-pinene + NO3. Using a chemical box model, we show that the measured concentrations of NO2 and γ-terpinene hydroxy nitrates can be reliably simulated from α-pinene + NO3 chemistry. This suggests that NO3 addition to either of the two internal double bonds of γ-terpinene primarily decomposes forming a relatively volatile keto-aldehyde, reconciling the small SOA yield observed here and for other internal olefinic terpenes. Based on aerosol partitioning analysis and identification of speciated particle-phase ON applying high-resolution liquid chromatography–mass spectrometry, we estimate that a significant fraction of the particle-phase ON has the hydroxy nitrate moiety. This work greatly contributes to our understanding of ON and SOA formation from polyolefin monoterpene oxidation, which could be important in the northern continental US and the Midwest, where polyolefinic monoterpene emissions are greatest.

Monoterpene emissions contribute to thermotolerance in Cinnamomum camphora

High temperature promoted monoterpene emission from Cinnamomum camphora , and monoterpenes scavenged ROS and protected photosynthesis to improve thermotolerance in plants. High temperature impacts plant growth and development with a reduction in photosynthetic rate and an increase in reactive oxygen species (ROS) levels. To reveal the effects of monoterpene emissions on improving plant thermotolerance, the emissions of monoterpenes from Cinnamomum camphora under high-temperature stress and oxygenated monoterpenes under H2O2 stress were analyzed. ROS metabolism and photosynthetic abilities under high-temperature stress after monoterpene synthesis was blocked by fosmidomycin were also investigated. High temperature promoted the emission of monoterpenes as well as two oxygenated monoterpenes, eucalyptol and α-terpineol. In addition, seven new oxygenated monoterpenes occurred at 45 °C. Similar results were also found under H2O2 stress, suggesting that ROS induced by high temperature may oxidize monoterpenes to generate oxygenated forms. Fosmidomycin treatment caused an increase in ROS and thiobarbituric acid reactive substance content, even though antioxidant enzyme activities were also higher. However, no changes occurred in antioxidant carotenoids synthesized from the same precursors as monoterpenes, indicating that monoterpenes can serve as antioxidant agents in the cells. In addition, fosmidomycin caused a decline in photosynthesis under high temperature, due to the decrease of quantum yield and electron transport rate. Therefore, monoterpenes play an important role in plant thermotolerance by scavenging ROS and protecting photosystems.

Impact of LULCC on the emission of BVOCs during the 21st century

Land-use and land-cover change (LULCC) is one of the key drivers of anthropogenic climate change. In addition to greenhouse gases such as CO2 or CH4, LULCC affects also the emission of other carbon trace gases such as biogenic volatile organic compounds (BVOCs). We investigate the impact of changing LULCC on the emission of isoprene and monoterpenes during the 21st century using seven different land-use projections, applying the dynamic vegetation modelling framework LPJ-GUESS. Climate change, and atmospheric CO2-concentration are based on the RCP2.6 scenario. The different LULCC-scenarios explore the impact of different land-based climate change mitigation strategies (such as afforestation and avoided deforestation, or bioenergy). We show that the increase of land area under crops or grassland would lead to a significant decrease of BVOC emissions, with a strong negative correlation between the fraction of managed global land area and the emission of isoprene and monoterpenes. But the choice of crops is important, especially for the bioenergy scenarios in which increasing fractional cover leads to decreasing BVOC emissions in our simulations; use of woody bioenergy crops can reverse this decrease. The strong impact of LULCC on the global and regional emission of BVOCs implies the need to include the impact of these changes in projections of atmospheric composition and air quality.

Net ecosystem fluxes and composition of biogenic volatile organic compounds over a maize field–interaction of meteorology and phenological stages

AbstractBioenergy crop production is rapidly expanding in Europe, and the potential emissions of biogenic volatile organic compounds (BVOCs) might change the chemical composition of the atmosphere, influencing in turn air quality and regional climate. The environmental impacts of bioenergy crops on air chemistry are difficult to assess due to a lack of accurate field observations. Therefore, we studied BVOC fluxes from a bioenergy maize field in North‐Eastern Germany throughout the entire reproductive growth stage of the plants. Combining automated large chambers and proton transfer reaction mass spectrometry (PTR‐MS), we successfully measured fluxes of the highly reactive hydrocarbons monoterpenes (MTs) and sesquiterpenes (SQTs), together with several other BVOCs, including alcohols, aldehydes, ketones, benzenoids, and fatty acid derivatives. Emissions of MTs and SQTs were relatively high (17.0% and 3.6% of total mean molar BVOC emission, respectively) compared to methanol emissions (17.6%). Seasonal MT and SQT fluxes were clearly associated with the flowering phase, originating mainly from the flowering tissues as shown in additional laboratory experiments. From the observations of CO2 net ecosystem exchange and evapotranspiration rates, we could exclude heat and drought stress‐induced BVOC emissions. Standard emission factors calculated for all compounds, chemical groups, and growth stages, showed that the temperature dependency of volatile terpenoid fluxes decreased distinctively with proceeding development stage. The results indicate that emissions from large‐scale bioenergy maize fields should be better differentiated and considered in regional estimates of aerosol formation. For the implementation of such relation into biogeochemical modelling, it should be considered that not only seasonal weather development but also phenological growth stages are determining the BVOC patterns and emission potentials.

Monoterpenes Support Systemic Acquired Resistance within and between Plants.

This study investigates the role of volatile organic compounds in systemic acquired resistance (SAR), a salicylic acid (SA)-associated, broad-spectrum immune response in systemic, healthy tissues of locally infected plants. Gas chromatography coupled to mass spectrometry analyses of SAR-related emissions of wild-type and non-SAR-signal-producing mutant plants associated SAR with monoterpene emissions. Headspace exposure of Arabidopsis thaliana to a mixture of the bicyclic monoterpenes α-pinene and β-pinene induced defense, accumulation of reactive oxygen species, and expression of SA- and SAR-related genes, including the SAR regulatory AZELAIC ACID INDUCED1 (AZI1) gene and three of its paralogs. Pinene-induced resistance was dependent on SA biosynthesis and signaling and on AZI1 Arabidopsis geranylgeranyl reductase1 mutants with reduced monoterpene biosynthesis were SAR-defective but mounted normal local resistance and methyl salicylate-induced defense responses, suggesting that monoterpenes act in parallel with SA The volatile emissions from SAR signal-emitting plants induced defense in neighboring plants, and this was associated with the presence of α-pinene, β-pinene, and camphene in the emissions of the "sender" plants. Our data suggest that monoterpenes, particularly pinenes, promote SAR, acting through ROS and AZI1, and likely function as infochemicals in plant-to-plant signaling, thus allowing defense signal propagation between neighboring plants.

Seasonal and interannual variations in whole-ecosystem BVOC emissions from a subtropical plantation in China

Measurements of BVOC emissions, ozone concentration and environmental parameters were carried out from May 2013 to January 2016 in a subtropical Pinus plantation in China. Isoprene and monoterpene emissions were measured using a relaxed eddy accumulation (REA) system and a gradient technique on an above-canopy tower. In 2013, isoprene comprised 21.2% of total terpenoid emissions, while α-pinene, camphene, β-pinene and limonene constituting 51.5%, 2.4%, 9.1%, and 13.0% of total emissions, respectively. Monoterpenes together were the dominant VOCs measured contributing 71.6%. α-pinene, camphene, β-pinene and limonene constituted 67.7%, 3.2%, 11.9%, 17.2% of total monoterpene emissions. Isoprene and monoterpene emissions displayed strong diurnal variations, with lower emissions in the morning and late evening, and the highest emissions around noon. BVOC peak emissions typically occurred a few hours after the noon PAR peak. Isoprene and monoterpene emissions varied with season and were the highest in summer, contributing more than half of the total annual emission, and the lowest emissions were in winter. Evident interannual variations of isoprene, monoterpenes and total BVOCs were observed. Compared to 2013, annual BVOC emissions decreased in 2015, associated with decreases of PAR, Temperature, water vapor, and an increase of all substances in gas, liquid and solid phases in the atmospheric column (e.g., S/Q, the ratio of solar scattered radiation to global radiation). Ozone concentration showed clear diurnal variation with PAR, higher around noon and lower in the early morning and late evening. Generally, there were no evident correlations between ozone concentrations and BVOC emissions, or the vertical gradients of ozone concentrations and BVOC concentrations. Under all sky conditions (including cloudy skies), no strong correlations at a high confidence level or very similar variation patterns were observed between any two following parameters, BVOC emissions, PAR, temperature, water vapor, and S/Q. The major factors controlling BVOC emissions were PAR and temperature but biomass burning smoke and phenology (pine florescence) may also play a role. The mean emission factors at standard conditions determined using the MEGAN model emission algorithms and empirical model of BVOC emissions were 0.71 and 1.19 mg m−2 h−1 for isoprene and 1.39 and 1.65 mg m−2 h−1 for total monoterpenes, respectively.

Herbivore-induced BVOC emissions of Scots pine under warming, elevated ozone and increased nitrogen availability in an open-field exposure

Climate change may promote the frequency of insect attacks such as outbreaks of the great web-spinning pine sawfly (Acantholyda posticalis) on Scots pine (Pinus sylvestris L.). We determined the emission rates of localized biogenic volatile organic compounds (BVOCs) from A. posticalis-fed branches, and systemic BVOCs from non-fed branches of Scots pine seedlings defoliated for two growing seasons by A. posticalis larvae. Seedlings were also exposed to warming, elevated ozone and higher nitrogen availability for three years in an open-field experiment. A. posticalis feeding increased localized emissions of total non-oxygenated monoterpenes 21-fold, total oxygenated monoterpenes 9.1-fold, total sesquiterpenes 11-fold and total green leaf volatiles 9.2-fold from insect-damaged shoots on the 7th day of feeding in June. Warming reduced the effects of herbivory on the emission rates of total non-oxygenated monoterpenes by 77%. However, the effect of herbivory on total sesquiterpene emissions was enhanced by 16-fold in combination with warming and elevated ozone. The localized emission rates of total BVOCs were linearly increased when feeding damage intensity by larvae exceeded 80%. After three weeks of continuous sawfly feeding, herbivory stress increased systemic emissions of total non-oxygenated monoterpenes 5.6-fold, total sesquiterpenes 5.6-fold and total green leaf volatiles 6.5-fold from the non-damaged branch of larvae-fed seedlings, and this effect on total non-oxygenated monoterpene emission was enhanced 8.6-fold with elevated ozone. Herbivory sporadically showed post-feeding effects still by the end of 12th week from the initiation of feeding, increasing total non-oxygenated monoterpene emissions 4.4-fold at elevated nitrogen level. Our results suggest that Scots pine, at least in seedling stage, will be a stronger source of BVOC emissions in future due to expected increase of sawfly outbreaks with climate warming and by increased herbivory interactions with abiotic climate change factors.

Air‐Sea exchange of biogenic volatile organic compounds and the impact on aerosol particle size distributions

AbstractWe report simultaneous, underway eddy covariance measurements of the vertical flux of isoprene, total monoterpenes, and dimethyl sulfide (DMS) over the Northern Atlantic Ocean during fall. Mean isoprene and monoterpene sea‐to‐air vertical fluxes were significantly lower than mean DMS fluxes. While rare, intense monoterpene sea‐to‐air fluxes were observed, coincident with elevated monoterpene mixing ratios. A statistically significant correlation between isoprene vertical flux and short wave radiation was not observed, suggesting that photochemical processes in the surface microlayer did not enhance isoprene emissions in this study region. Calculations of secondary organic aerosol production rates (PSOA) for mean isoprene and monoterpene emission rates sampled here indicate that PSOA is on average &lt;0.1 μg m−3 d−1. Despite modest PSOA, low particle number concentrations permit a sizable role for condensational growth of monoterpene oxidation products in altering particle size distributions and the concentration of cloud condensation nuclei during episodic monoterpene emission events from the ocean.

A modeling study of secondary organic aerosol formation from sesquiterpenes using the STOCHEM global chemistry and transport model

AbstractSesquiterpenes are one of the precursors of secondary organic aerosol (SOA) which can be an important global sources of organic aerosol (OA). Updating the chemistry scheme in the global chemistry transport model by incorporating an oxidation mechanism for β‐caryophyllene (representing all sesquiterpenes), adding global sesquiterpene emissions of 29 Tg/yr, and revising global monoterpene emissions up to 162 Tg/yr [Guenther et al., 2012] led to an increase of SOA burden by 95% and SOA production rate by 106% relative to the base case described in Utembe et al. [2011]. Including the emissions of sesquiterpenes resulted in increase of SOA burden of 0.11 Tg and SOA production rate of 12.9 Tg/yr relative to the base case. The highest concentrations of sesquiterpene‐derived SOA (by up to 1.2 μg/m3) were found over central Africa and South America, the regions having high levels of biogenic emissions with significant biomass burning. In the updated model simulation, the multigeneration oxidation products from sesquiterpenes and monoterpenes transported above the boundary layer and condensed to the aerosol phase at higher altitude led to an increase of OA by up to 30% over the tropics and northern midlatitude to higher altitude. The model evaluation showed an underestimation of model OA mostly for the campaigns dominated by regional anthropogenic pollution. The increase of SOA production from sesquiterpenes reduced the discrepancies between modeled and observed OA concentrations over the remote and rural areas. The increase of SOA concentrations by up to 200% from preindustrial to present scenarios was found over the tropical oceans.