Monoterpene Emissions Research Articles

Airborne measurements of isoprene and monoterpene emissions from southeastern U.S. forests

Isoprene and monoterpene emission rates are essential inputs for atmospheric chemistry models that simulate atmospheric oxidant and particle distributions. Process studies of the biochemical and physiological mechanisms controlling these emissions are advancing our understanding and the accuracy of model predictions but efforts to quantify regional emissions have been limited by a lack of constraints on regional distributions of ecosystem emission capacities. We used an airborne wavelet-based eddy covariance measurement technique to characterize isoprene and monoterpene fluxes with high spatial resolution during the 2013 SAS (Southeast Atmosphere Study) in the southeastern United States. The fluxes measured by direct eddy covariance were comparable to emissions independently estimated using an indirect inverse modeling approach. Isoprene emission factors based on the aircraft wavelet flux estimates for high isoprene chemotypes (e.g., oaks) were similar to the MEGAN2.1 biogenic emission model estimates for landscapes dominated by oaks. Aircraft flux measurement estimates for landscapes with fewer isoprene emitting trees (e.g., pine plantations), were about a factor of two lower than MEGAN2.1 model estimates. The tendency for high isoprene emitters in these landscapes to occur in the shaded understory, where light dependent isoprene emissions are diminished, may explain the lower than expected emissions. This result demonstrates the importance of accurately representing the vertical profile of isoprene emitting biomass in biogenic emission models. Airborne measurement-based emission factors for high monoterpene chemotypes agreed with MEGAN2.1 in landscapes dominated by pine (high monoterpene chemotype) trees but were more than a factor of three higher than model estimates for landscapes dominated by oak (relatively low monoterpene emitting) trees. This results suggests that unaccounted processes, such as floral emissions or light dependent monoterpene emissions, or vegetation other than high monoterpene emitting trees may be an important source of monoterpene emissions in those landscapes and should be identified and included in biogenic emission models.

Terpenoid and carbonyl emissions from Norway spruce in Finland during the growing season

Abstract. We present spring and summer volatile organic compound (VOC) emission rate measurements from Norway spruce (Picea abies L. Karst) growing in a boreal forest in southern Finland. The measurements were conducted using in situ gas chromatograph with 1 to 2 h time resolution to reveal quantitative and qualitative short-term and seasonal variability of the emissions. The measurements cover altogether 14 weeks in years 2011, 2014 and 2015. Monoterpene (MT) and sesquiterpene (SQT) emission rates were measured all the time, but isoprene only in 2014 and 2015 and acetone and C4–C10 aldehydes only in 2015. The emission rates of all the compounds were low in spring, but MT, acetone, and C4–C10 aldehyde emission rates increased as summer proceeded, reaching maximum emission rates in July. Late summer mean values (late July and August) were 29, 17, and 33 ng g(dw)−1 h−1 for MTs, acetone, and aldehydes respectively. SQT emission rates increased during the summer and highest emissions were measured in late summer (late summer mean value 84 ng g(dw)−1 h−1) concomitant with highest linalool emissions most likely due to stress effects. The between-tree variability of emission pattern was studied by measuring seven different trees during the same afternoon using adsorbent tubes. Especially the contributions of limonene, terpinolene, and camphene were found to vary between trees, whereas proportions of α-pinene (25 ± 5 %) and β-pinene (7 ± 3 %) were more stable. Our results show that it is important to measure emissions at canopy level due to irregular emission pattern, but reliable SQT emission data can be measured only from enclosures. SQT emissions contributed more than 90 % of the ozone reactivity most of the time, and about 70 % of the OH reactivity during late summer. The contribution of aldehydes to OH reactivity was comparable to that of MT during late summer, 10–30 % most of the time.

Springtime ecosystem-scale monoterpene fluxes from Mediterranean pine forests across a precipitation gradient

We quantified springtime ecosystem-scale monoterpene fluxes from two similar Aleppo pine (Pinus halepensis Mill.) forests, located in Israel, that differed in the amount of received precipitation: Yatir in the arid south and Birya in the northern part of Israel (291 and 755mm annual average rainfall, respectively). In addition to the lower water availability, during our measurement campaign the Yatir site suffered from a heat wave with temperatures up to 35°C, which made the campaign-average net CO2 assimilation to occur in the morning (1μmolm−2s−1), with the rest of the daytime hours mainly dominated by net release of CO2. The milder conditions at Birya favored a higher net CO2 assimilation during all daytime hours (with average peaks higher than 10μmolm−2s−1). Despite these large differences in ambient conditions and CO2 net assimilation, daytime monoterpene emission capacities at both sites were comparable. While observed monoterpene fluxes were lower at Yatir than at Birya (hourly averages up to 0.4 and 1mgm−2h−1, respectively), the standardized hourly fluxes, after accounting for the differences in light, temperature and stand density between both sites, were comparable (0–1.3mgm−2h−1). The approach typically used by biogenic emission models overestimated monoterpene fluxes at Yatir when temperatures rose during the heat wave. This result, together with complementary leaf-level measurements showing that summertime monoterpene fluxes almost completely ceased at Yatir while being enhanced at Birya, highlight the interaction of water scarcity and high temperatures that drive monoterpene emissions from vegetation in such extreme climate zones and the need to further improve model performance.

Global isoprene and monoterpene emissions under changing climate, vegetation, CO2 and land use

Plants emit large quantities of isoprene and monoterpenes, the main components of global biogenic volatile organic compound (BVOC) emissions. BVOCs have an important impact on the atmospheric composition of methane, and of short-lived radiative forcing agents (e.g. ozone, aerosols etc.). It is therefore necessary to know how isoprene and monoterpene emissions have changed over the past and how future changes in climate, land-use and other factors will impact them. Here we present emission estimates of isoprene and monoterpenes over the period 1901–2 100 based on the dynamic global vegetation model LPJ-GUESS, including the effects of all known important drivers. We find that both isoprene and monoterpene emissions at the beginning of the 20th century were higher than at present. While anthropogenic land-use change largely drives the global decreasing trend for isoprene over the 20th century, changes in natural vegetation composition caused a decreasing trend for monoterpene emissions. Future global isoprene and monoterpene emissions depend strongly on the climate and land-use scenarios considered. Over the 21st century, global isoprene emissions are simulated to either remain stable (RCP 4.5), or decrease further (RCP 8.5), with important differences depending on the underlying land-use scenario. Future monoterpene emissions are expected to continue their present decreasing trend for all scenarios, possibly stabilizing from 2050 onwards (RCP 4.5). These results demonstrate the importance to take both natural vegetation dynamics and anthropogenic changes in land-use into account when estimating past and future BVOC emissions. They also indicate that a future global increase in BVOC emissions is improbable.

Monoterpene 'thermometer' of tropical forest-atmosphere response to climate warming.

Tropical forests absorb large amounts of atmospheric CO2 through photosynthesis but elevated temperatures suppress this absorption and promote monoterpene emissions. Using 13 CO2 labeling, here we show that monoterpene emissions from tropical leaves derive from recent photosynthesis and demonstrate distinct temperature optima for five groups (Groups 1-5), potentially corresponding to different enzymatic temperature-dependent reaction mechanisms within β-ocimene synthases. As diurnal and seasonal leaf temperatures increased during the Amazonian 2015 El Niño event, leaf and landscape monoterpene emissions showed strong linear enrichments of β-ocimenes (+4.4% °C-1 ) at the expense of other monoterpene isomers. The observed inverse temperature response of α-pinene (-0.8% °C-1 ), typically assumed to be the dominant monoterpene with moderate reactivity, was not accurately simulated by current global emission models. Given that β-ocimenes are highly reactive with respect to both atmospheric and biological oxidants, the results suggest that highly reactive β-ocimenes may play important roles in the thermotolerance of photosynthesis by functioning as effective antioxidants within plants and as efficient atmospheric precursors of secondary organic aerosols. Thus, monoterpene composition may represent a new sensitive 'thermometer' of leaf oxidative stress and atmospheric reactivity, and therefore a new tool in future studies of warming impacts on tropical biosphere-atmosphere carbon-cycle feedbacks.

Variation in short-term and long-term responses of photosynthesis and isoprenoid-mediated photoprotection to soil water availability in four Douglas-fir provenances

For long-lived forest tree species, the understanding of intraspecific variation among populations and their response to water availability can reveal their ability to cope with and adapt to climate change. Dissipation of excess excitation energy, mediated by photoprotective isoprenoids, is an important defense mechanism against drought and high light when photosynthesis is hampered. We used 50-year-old Douglas-fir trees of four provenances at two common garden experiments to characterize provenance-specific variation in photosynthesis and photoprotective mechanisms mediated by essential and non-essential isoprenoids in response to soil water availability and solar radiation. All provenances revealed uniform photoprotective responses to high solar radiation, including increased de-epoxidation of photoprotective xanthophyll cycle pigments and enhanced emission of volatile monoterpenes. In contrast, we observed differences between provenances in response to drought, where provenances sustaining higher CO2 assimilation rates also revealed increased water-use efficiency, carotenoid-chlorophyll ratios, pools of xanthophyll cycle pigments, β-carotene and stored monoterpenes. Our results demonstrate that local adaptation to contrasting habitats affected chlorophyll-carotenoid ratios, pool sizes of photoprotective xanthophylls, β-carotene, and stored volatile isoprenoids. We conclude that intraspecific variation in isoprenoid-mediated photoprotective mechanisms contributes to the adaptive potential of Douglas-fir provenances to climate change.

亚热带竹林地区的臭氧及其影响因子

2012年7月至2013年1月，在我国浙江省亚热带竹林开展了挥发性有机物(BVOCs)排放、O3、太阳辐射、气象参数等的综合测量。基于PAR能量平衡原理和冠层尺度异戊二烯和单萜烯排放经验模式，建立了考虑O3与异戊二烯和O3与单萜烯关系的O3经验模式，该模式对于O3日变化和平均值有较好的模拟。对经验模式进行了检验，结果表明它可以较好地捕捉O3的变化特征。利用经验模式计算了O3对各个因子(异戊二烯或单萜烯、PAR、水汽、S/Q-散射因子，散射辐射/总辐射)变化的敏感性：对于O3与异戊二烯关系的O3经验模式，O3对PAR的变化最敏感，其次是水汽因子，再次是异戊二烯；最后是S/Q；对于O3与单萜烯关系的O3经验模式，O3对PAR的变化最敏感，其次是水汽和S/Q因子，最后是单萜烯；O3对各因子变化的响应均是非线性的。敏感性研究给出了与实测数据较为一致的结果，增加了我们对于O3、BVOCs化学和光化学机制的理解和认识。基于测量和敏感性研究，提出未来控制高浓度O3污染的一些建议：控制人为原因引起的BVOCs排放、人为源挥发性有机物排放、以及NOx和SO2排放等。 During July 2012-January 2013, integrated measurements of biogenic volatile organic compounds (BVOCs), O3 and solar radiation at a subtropical bamboo forest, Zhejiang province, were carried out. Based on PAR energy balance and empirical models of isoprene and monoterpene emissions at canopy scale, O3 empirical models considering the relationships between O3 and isoprene and O3 and monoterpenes, respectively, were developed. O3 diurnal variation and mean value were better simulated by O3 empirical models. The validation of O3 empirical models was made, which showed that it can capture O3 variation characteristics. A sensitivity study of the response of O3 to changes in its controlling factors (i.e., isoprene or monoterpenes, PAR, water vapor and S/Q-scat- tering factor, ratio of solar scattering radiation to solar global radiation) showed that O3 was most sensitive to PAR, and more sensitive to water vapor, isoprene emission and S/Q, for O3 empirical model considering the relationship of O3 with isoprene emission; O3 was also most sensitive to PAR, and more sensitive to water vapor, S/Q and monoterpene emissions, for O3 empirical model considering the relationship of O3 with monoterpene emissions. The responses of O3 to changes of all controlling factors were nonlinear. The sensitivity studies exhibited good agreements with the observations, and improved our understanding of chemical and photochemical mechanisms associated with O3 and BVOCs. Some suggestions in controlling future high O3 pollution were put forwarded, e.g., controlling emissions of Human-induced BVOC emissions, anthropogenic volatile organic compound emissions, and NOx and SO2 emissions.

New insights into the parametrization of temperature and light responses of mono - and sesquiterpene emissions from Aleppo pine and rosemary

Phytogenic emission of large volatile organic compounds (VOCs) such as monoterpenes (MTs) and sesquiterpenes (SQTs) are key precursors to the formation and growth of atmospheric particles. However, controlled environment studies to elucidate emission responses to temperature and light are still sparse. In this study, the volatile contents and emission responses of Aleppo pine and Rosemary have been investigated. These two common Mediterranean species store semivolatiles inside (resin ducts) and outside (trichomes) their foliage tissues respectively. Both species emitted mainly MTs with basal emission rates of around 5 (Rosemary) and 10 (pine) μg g−1 h−1 and SQTs about one order of magnitude lower. In Aleppo pine, two volatile sources could be clearly distinguished: 1) de-novo synthesized emission of (E)-β-ocimene and linalool, which accounted for about 70% of the total VOC release, were not found in foliar VOC extracts and expressed light dependency (LD) and temperature responses typical for enzyme driven emissions; and 2) storage-derived emissions of various MTs and SQTs whose emissions increased exponentially with temperature, showed no light dependency and were all present in leaf extracts. In Rosemary, all emitted MTs and SQTs including many oxygenated compounds, showed responses typical for stored volatiles and were all found in leaf extracts. The emissions of individual volatiles or volatile classes could be well described with the commonly applied empirical algorithms developed for LD or non LD emissions. However, the shapes of the temperature responses, and hence the deduced coefficient values, were significantly different between oxygenated and non-oxygenated compounds. They also differed between the storage-derived emissions of the two plant species, for individual VOCs or VOC classes. We address the possible reasons for this variation in temperature responses and argue that they are mostly due to molecular interactions along the species specific leaf-internal diffusion paths including the build-up of transient VOC pools and degradation.

Challenges in modelling isoprene and monoterpene emission dynamics of Arctic plants: a case study from a subarctic tundra heath

Abstract. The Arctic is warming at twice the global average speed, and the warming-induced increases in biogenic volatile organic compounds (BVOCs) emissions from Arctic plants are expected to be drastic. The current global models' estimations of minimal BVOC emissions from the Arctic are based on very few observations and have been challenged increasingly by field data. This study applied a dynamic ecosystem model, LPJ-GUESS, as a platform to investigate short-term and long-term BVOC emission responses to Arctic climate warming. Field observations in a subarctic tundra heath with long-term (13-year) warming treatments were extensively used for parameterizing and evaluating BVOC-related processes (photosynthesis, emission responses to temperature and vegetation composition). We propose an adjusted temperature (T) response curve for Arctic plants with much stronger T sensitivity than the commonly used algorithms for large-scale modelling. The simulated emission responses to 2 °C warming between the adjusted and original T response curves were evaluated against the observed warming responses (WRs) at short-term scales. Moreover, the model responses to warming by 4 and 8 °C were also investigated as a sensitivity test. The model showed reasonable agreement to the observed vegetation CO2 fluxes in the main growing season as well as day-to-day variability of isoprene and monoterpene emissions. The observed relatively high WRs were better captured by the adjusted T response curve than by the common one. During 1999–2012, the modelled annual mean isoprene and monoterpene emissions were 20 and 8 mg C m−2 yr−1, with an increase by 55 and 57 % for 2 °C summertime warming, respectively. Warming by 4 and 8 °C for the same period further elevated isoprene emission for all years, but the impacts on monoterpene emissions levelled off during the last few years. At hour-day scale, the WRs seem to be strongly impacted by canopy air T, while at the day–year scale, the WRs are a combined effect of plant functional type (PFT) dynamics and instantaneous BVOC responses to warming. The identified challenges in estimating Arctic BVOC emissions are (1) correct leaf T estimation, (2) PFT parameterization accounting for plant emission features as well as physiological responses to warming, and (3) representation of long-term vegetation changes in the past and the future.

Monoterpene emissions in response to long-term night-time warming, elevated CO2 and extended summer drought in a temperate heath ecosystem.

Monoterpenes emitted from plants have an important role in atmospheric chemistry through changing atmospheric oxidative capacity, forming new particles and secondary organic aerosols. The emission rates and patterns can be affected by changing climate. In this study, emission responses to six years of climatic manipulations (elevated CO2, extended summer drought and night-time warming) were investigated in a temperate semi-natural heath ecosystem. Samples for monoterpene analysis were collected in seven campaigns during an entire growing season (April-November, 2011). The results showed that the temperate heath ecosystem was a considerable source of monoterpenes to the atmosphere, with the emission averaged over the 8month measurement period of 21.7±6.8μgm-2groundareah-1 for the untreated heath. Altogether, 16 monoterpenes were detected, of which the most abundant were α-pinene, δ-3-carene and limonene. The emissions of these three compounds were positively correlated with light, chamber temperature and litter abundance, but negatively correlated with soil temperature. Elevated CO2 tended to decrease the average monoterpene emissions by 40% over the whole growing season, and significantly reduced emissions in August. Extended summer drought significantly decreased the emission right after the drought treatment period, but also in the late growing season. Night-time warming significantly increased the total emissions (mainly α-pinene) in April, and tended to mitigate the decrease caused by drought. The inhibition effects of elevated CO2 on emissions were diminished when the treatment was combined with drought or warming. The emission responses to different treatments were not explained by vegetation changes, and the monoterpene emission profile was only moderately related to plant species coverage. The emission responses to these long-term climate manipulations varied over the growing season (with strong correlation with litter abundance) and the observed antagonistic effects in the combined treatments underlie the importance of long-term studies with multiple factors acting in concert.

Global biogenic volatile organic compound emissions in the ORCHIDEE and MEGAN models and sensitivity to key parameters

Abstract. A new version of the biogenic volatile organic compounds (BVOCs) emission scheme has been developed in the global vegetation model ORCHIDEE (Organizing Carbon and Hydrology in Dynamic EcosystEm), which includes an extended list of biogenic emitted compounds, updated emission factors (EFs), a dependency on light for almost all compounds and a multi-layer radiation scheme. Over the 2000–2009 period, using this model, we estimate mean global emissions of 465 Tg C yr−1 for isoprene, 107.5 Tg C yr−1 for monoterpenes, 38 Tg C yr−1 for methanol, 25 Tg C yr−1 for acetone and 24 Tg C yr−1 for sesquiterpenes. The model results are compared to state-of-the-art emission budgets, showing that the ORCHIDEE emissions are within the range of published estimates. ORCHIDEE BVOC emissions are compared to the estimates of the Model of Emissions of Gases and Aerosols from Nature (MEGAN), which is largely used throughout the biogenic emissions and atmospheric chemistry community. Our results show that global emission budgets of the two models are, in general, in good agreement. ORCHIDEE emissions are 8 % higher for isoprene, 8 % lower for methanol, 17 % higher for acetone, 18 % higher for monoterpenes and 39 % higher for sesquiterpenes, compared to the MEGAN estimates. At the regional scale, the largest differences between ORCHIDEE and MEGAN are highlighted for isoprene in northern temperate regions, where ORCHIDEE emissions are higher by 21 Tg C yr−1, and for monoterpenes, where they are higher by 4.4 and 10.2 Tg C yr−1 in northern and southern tropical regions compared to MEGAN. The geographical differences between the two models are mainly associated with different EF and plant functional type (PFT) distributions, while differences in the seasonal cycle are mostly driven by differences in the leaf area index (LAI). Sensitivity tests are carried out for both models to explore the response to key variables or parameters such as LAI and light-dependent fraction (LDF). The ORCHIDEE and MEGAN emissions are differently affected by LAI changes, with a response highly depending on the compound considered. Scaling the LAI by a factor of 0.5 and 1.5 changes the isoprene global emission by −21 and +8 % for ORCHIDEE and −15 and +7 % for MEGAN, and affects the global emissions of monoterpenes by −43 and +40 % for ORCHIDEE and −11 and +3 % for MEGAN. Performing a further sensitivity test, forcing ORCHIDEE with the MODIS LAI, confirms the high sensitivity of the ORCHIDEE emission module to LAI variation. We find that MEGAN is more sensitive to variation in the LDF parameter than ORCHIDEE. Our results highlight the importance and the need to further explore the BVOC emission estimate variability and the potential for using models to investigate the estimated uncertainties.

Monoterpene emissions from needles of hybrid larch F1 (Larix gmelinii var. japonica × Larix kaempferi) grown under elevated carbon dioxide and ozone

We measured monoterpene emissions from needles of hybrid larch F1 (Larix gmelinii var. japonica × Larix kaempferi) to evaluate the response of monoterpene emission rates and their composition to elevated CO2 (600 μmol mol−1) and O3 (60 nmol mol−1) conditions. The dominant monoterpenes were α-pinene and β-pinene. The emission rate of total monoterpenes significantly decreased under elevated CO2 conditions (P < 0.05). The ratio of carbon emission in the form of monoterpenes to photosynthetically fixed carbon also significantly decreased under elevated CO2 conditions. By contrast, elevated O3 did not significantly affect the emission rate of total monoterpenes. The ratios of α-pinene/β-pinene, limonene/β-pinene, and myrcene/β-pinene were all significantly decreased by O3 exposure (P < 0.05). High reactivity of α-pinene, limonene, and myrcene when combining with O3 may be able to mitigate oxidative damage inside the larch needles. No significant combined effects of elevated CO2 and O3 on individual or total monoterpene emissions were detected.

Fluxes of biogenic volatile organic compounds above temperate Norway spruce forest of the Czech Republic

Norway spruce (Picea abies), the most representative forest species in central and northern Europe, has previously been described as a monoterpene emitter. However, past studies have shown variable emission rates. In order to understand emissions at the ecosystem scale, a technique utilizing proton-transfer-reaction-time-of-flight (PTR-TOF) mass spectrometry coupled with eddy covariance was applied to determine fluxes of volatile organic compounds and CO2 above a mountainous Norway spruce forest in the Czech Republic during an intensive field campaign in summer. In addition, an Inverse Lagrangian Transport Model was applied to derive fluxes of various monoterpenes using concentrations measured along a vertical canopy profile by wet effluent diffusion denuder. The Model of Emissions of Gases and Aerosols from Nature (MEGAN) was applied using basal emission factors for sun and shade shoots to predict diurnal fluxes and annual monoterpene emission sums for 5 years. The forest showed itself to be a monoterpene emitter up to 2.03nmolm−2s−1. Isoprene and 2-methyl-3-buten-2-ol (MBO) reached maximum levels during central hours of the day of 1.6nmolm−2s−1, whereas daily average maximum fluxes were 1.29nmolm−2s−1 and 0.77nmolm−2s−1 for monoterpenes and sum of isoprene and MBO, respectively. The relationship between monoterpene and CO2 fluxes revealed that as much as 47% of variance in MT emission is predictable from the actual gross primary production of a spruce ecosystem. Modelled MT fluxes agreed with the measured fluxes in terms of diurnal pattern, particularly when basal emission factors 2.72nmolm−2s−1 and 0.55nmolm−2s−1 for sun and shade shoots, respectively, were used. Nevertheless, strong seasonal variability in MT emission was observed. Our results contribute to better understanding emissions of biogenic volatile organic compounds in central Europe.

Mono- and sesquiterpene release from tomato (Solanum lycopersicum) leaves upon mild and severe heat stress and through recovery: From gene expression to emission responses

Plants frequently experience heat ramps of various severities, but how and to what degree plant metabolic activity recovers from mild and severe heat stress is poorly understood. In this study, we exposed the constitutive terpene emitter, Solanum. lycopersicum leaves to mild (37 and 41°C), moderate (46°C) and severe (49°C) heat ramps of 5min and monitored foliage photosynthetic activity, lipoxygenase pathway volatile (LOX), and mono- and sesquiterpene emissions and expression of two terpene synthase genes, β-phellandrene synthase and (E)-β-caryophyllene/α-humulene synthase, through a 24h recovery period upon return to pre-stress conditions. Leaf monoterpene emissions were dominated by β-phellandrene and sesquiterpene emissions by (E)-β-caryophyllene, and thus, these two terpene synthase genes were representative for the two volatile terpene classes. Photosynthetic characteristics partly recovered under moderate heat stress, and very limited recovery was observed under severe stress. All stress treatments resulted in elicitation of LOX emissions that declined during recovery. Enhanced mono- and sesquiterpene emissions were observed immediately after the heat treatment, but the emissions decreased even to below the control treatment during recovery between 2 and 10h, and raised again by 24h. The expression of β-phellandrene and (E)-β-caryophyllene synthase genes decreased between 2 and 10h after heat stress, and recovered to pre-stress level in mild heat stress treatment by 24h. Overall, this study demonstrates a highly sensitive heat response of terpenoid synthesis that is mainly controlled by gene level responses under mild stress, while severe stress leads to non-recoverable declines in foliage physiological and gene expression activities.

Airborne Monoterpenes Emitted from a Cupressus lusitanica Cell Culture Induce a Signaling Cascade that Produces β-Thujaplicin.

A cell culture of Cupressus lusitanica was used to investigate the reaction of a plant to certain airborne chemicals. Compared with laboratory and field methods using intact plants or tissues, a cell culture is advantageous because it is not affected by environmental factors, and the experiments are easier to reproduce. When exposed to an elicitor, our cell line produces 10 monoterpenes and β-thujaplicin, which is a strong phytoalexin. These monoterpenes are emitted into the vapor phase and are expected to play a role in airborne signaling. In the present study, the cells were exposed to monoterpene vapors, and the volatiles present in the culture flasks were monitored. When the culture cells were exposed to low doses of sabinene, we detected γ-terpinene and p-cymene. After exposure to γ-terpinene, we found p-cymene and terpinolene, whereas p-cymene exposure resulted in terpinolene emission. By contrast, the other seven monoterpenes we investigated did not induce any emissions of other monoterpenes. These results strongly suggest that in C. lusitanica a signaling cascade exists that starts with the emission of sabinene and moves to γ-terpinene, p-cymene, and finally to terpinolene, which accelerates the production of the phytoalexin β-thujaplicin.

How specialized volatiles respond to chronic and short-term physiological and shock heat stress in Brassica nigra.

Brassicales release volatile glucosinolate breakdown products upon tissue mechanical damage, but it is unclear how the release of glucosinolate volatiles responds to abiotic stresses such as heat stress. We used three different heat treatments, simulating different dynamic temperature conditions in the field to gain insight into stress-dependent changes in volatile blends and photosynthetic characteristics in the annual herb Brassica nigra (L.) Koch. Heat stress was applied by either heating leaves through temperature response curve measurements from 20 to 40 °C (mild stress), exposing plants for 4 h to temperatures 25-44 °C (long-term stress) or shock-heating leaves to 45-50 °C. Photosynthetic reduction through temperature response curves was associated with decreased stomatal conductance, while the reduction due to long-term stress and collapse of photosynthetic activity after heat shock stress were associated with non-stomatal processes. Mild stress decreased constitutive monoterpene emissions, while long-term stress and shock stress resulted in emissions of the lipoxygenase pathway and glucosinolate volatiles. Glucosinolate volatile release was more strongly elicited by long-term stress and lipoxygenase product released by heat shock. These results demonstrate that glucosinolate volatiles constitute a major part of emission blend in heat-stressed B. nigra plants, especially upon chronic stress that leads to induction responses.

Canopy-scale flux measurements and bottom-up emission estimates of volatile organic compounds from a mixed oak and hornbeam forest in northern Italy

Abstract. This paper reports the fluxes and mixing ratios of biogenically emitted volatile organic compounds (BVOCs) 4 m above a mixed oak and hornbeam forest in northern Italy. Fluxes of methanol, acetaldehyde, isoprene, methyl vinyl ketone + methacrolein, methyl ethyl ketone and monoterpenes were obtained using both a proton-transfer-reaction mass spectrometer (PTR-MS) and a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) together with the methods of virtual disjunct eddy covariance (using PTR-MS) and eddy covariance (using PTR-ToF-MS). Isoprene was the dominant emitted compound with a mean daytime flux of 1.9 mg m−2 h−1. Mixing ratios, recorded 4 m above the canopy, were dominated by methanol with a mean value of 6.2 ppbv over the 28-day measurement period. Comparison of isoprene fluxes calculated using the PTR-MS and PTR-ToF-MS showed very good agreement while comparison of the monoterpene fluxes suggested a slight over estimation of the flux by the PTR-MS. A basal isoprene emission rate for the forest of 1.7 mg m−2 h−1 was calculated using the Model of Emissions of Gases and Aerosols from Nature (MEGAN) isoprene emission algorithms (Guenther et al., 2006). A detailed tree-species distribution map for the site enabled the leaf-level emission of isoprene and monoterpenes recorded using gas-chromatography mass spectrometry (GC–MS) to be scaled up to produce a bottom-up canopy-scale flux. This was compared with the top-down canopy-scale flux obtained by measurements. For monoterpenes, the two estimates were closely correlated and this correlation improved when the plant-species composition in the individual flux footprint was taken into account. However, the bottom-up approach significantly underestimated the isoprene flux, compared with the top-down measurements, suggesting that the leaf-level measurements were not representative of actual emission rates.

Current estimates of biogenic emissions from eucalypts uncertain for southeast Australia

Abstract. The biogenic emissions of isoprene and monoterpenes are one of the main drivers of atmospheric photochemistry, including oxidant and secondary organic aerosol production. In this paper, the emission rates of isoprene and monoterpenes from Australian vegetation are investigated for the first time using the Model of Emissions of Gases and Aerosols from Nature version 2.1 (MEGANv2.1); the CSIRO chemical transport model; and atmospheric observations of isoprene, monoterpenes and isoprene oxidation products (methacrolein and methyl vinyl ketone). Observations from four field campaigns during three different seasons are used, covering urban, coastal suburban and inland forest areas. The observed concentrations of isoprene and monoterpenes were of a broadly similar magnitude, which may indicate that southeast Australia holds an unusual position where neither chemical species dominates. The model results overestimate the observed atmospheric concentrations of isoprene (up to a factor of 6) and underestimate the monoterpene concentrations (up to a factor of 4). This may occur because the emission rates currently used in MEGANv2.1 for Australia are drawn mainly from young eucalypt trees (&lt; 7 years), which may emit more isoprene than adult trees. There is no single increase/decrease factor for the emissions which suits all seasons and conditions studied. There is a need for further field measurements of in situ isoprene and monoterpene emission fluxes in Australia.

Canopy level emissions of 2-methyl-3-buten-2-ol, monoterpenes, and sesquiterpenes from an experimental Pinus taeda plantation

Emissions of Biogenic Volatile Organic Compounds (BVOCs) observed during 2007 from an experimental Pinus taeda plantation in Central North Carolina are compared with model estimates from the Model of Emissions of Gases and Aerosols from Nature (MEGAN) version 2.1. Relaxed eddy accumulation (REA) estimates of 2-methyl-3-buten-2-ol (MBO) fluxes are a factor of 3–4 higher than MEGAN estimates. MEGAN monoterpene emission estimates were a factor of approximately two higher than REA flux measurements. MEGAN β-caryophyllene emission estimates were within 60% of growing season REA flux estimates but were several times higher than REA fluxes during cooler, dormant season periods. The sum of other sesquiterpene emissions estimated by MEGAN was several times higher than REA estimates throughout the year. Model components are examined to understand these discrepancies. Measured summertime leaf area index (LAI) (and therefore foliar biomass) is a factor of two higher than assumed in MEGAN for the P. taeda default. Increasing the canopy mean MBO emission factor from 0.35 to 1.0mgm−2h−1 also reduces MEGAN vs. REA flux differences. This increase is within current MBO emission factor uncertainties. The algorithm within MEGAN which adjusts isoprene emission estimates as a function of the temperature and light of the previous 24h seems also to improve the seasonal MEGAN MBO correlation with REA fluxes. Including the effects of the previous 240h, however, seems to degrade temporal model correlation with fluxes. Monoterpene and sesquiterpene composition data from the REA are compared with MEGAN2.1 estimates and also branch enclosure and needle extract data collected at this site. To our knowledge, the flux data presented here are the first reported for MBO and sesquiterpenes from a P. taeda ecosystem.

Remote sensing estimation of isoprene and monoterpene emissions generated by natural vegetation in Monterrey, Mexico.

In addition to oxygen, hydrocarbons are the most reactive chemical compounds produced by plants into the atmosphere. These compounds are part of the family of volatile organic compounds (VOCs) and are discharged in a great variety of forms. Among the VOCs produced by natural sources such as vegetation, the most studied until today are the isoprene and monoterpene. These substances can play an important role in the chemical balance of the atmosphere of a region. In this project, we develop a methodology to estimate the natural (vegetation) emission of isoprene and monoterpenes and applied it to the Monterrey Metropolitan Area, Mexico and its surrounding areas. Landsat-TM data was used to identify the dominant vegetation communities and field work to determine the foliage biomass density of key species. The studied communities were submontane scrub, oak, and pine forests and a combination of both. We carried out the estimation of emissions for isoprene and monoterpenes compounds in the different plant communities, with two different criteria: (1) taking into account the average foliage biomass density obtained from the various sample point in each vegetation community, and (2) using the foliage biomass density obtained for each transect, associated to an individual spectral class within a particular vegetation type. With this information, we obtained emission maps for each case. The results show that the main producers of isoprene are the communities that include species of the genus Quercus, located mainly on the Sierra Madre Oriental and Sierra de Picachos, with average isoprene emissions of 314.6 ton/day and 207.3 ton/day for the two methods utilized. The higher estimates of monoterpenes were found in the submontane scrub areas distributed along the valley of the metropolitan zone, with an estimated average emissions of 47.1 ton/day and 181.4 tons for the two methods respectively.