Biogenic Volatile Organic Compounds Fluxes Research Articles

Decline of soil volatile organic compounds from a Mediterranean deciduous forest under a future drier climate

Biogenic volatile organic compounds (BVOCs) are crucial for ecosystem functioning, atmospheric chemistry and climate. While modulation of BVOC emissions from living vegetation with biotic and abiotic factors is well documented, how these factors drive soil BVOC emissions remain less understood, particularly in Mediterranean forests. To fill this gap, this pioneer study investigates whether BVOC fluxes from natural soil covered by litter (referred to as forest soil) vary under natural and amplified long-term water stress (35% annual rain exclusion over the past 10 years) in a deciduous oak Mediterranean forest (Quercus pubescens Willd.) compared to natural climate conditions. This aim has only been tackled in a single evergreen Mediterranean forest so far. Using proton transfer reaction time of flight mass spectrometer (PTR-ToF-MS) we also provide, for the first time, a detailed diurnal cycle of soil BVOCs in relation to air temperature, air humidity, and biotic factors including soil respiration and litter content in lignin, cellulose and hemicellulose. The main results revealed that forest soil represents a source of most BVOCs (e.g., acetaldehyde, acetone, acrolein, hexanol, monoterpenes) with maximum values at mid-day (45 μgC.m-2.h-1) in response to higher temperatures while it acts as a clear sink of isoprene. Total soil BVOC emission rates, together with soil respiration, decreased by 43% after a decade of partial rain restriction. These results will contribute to enhance further modeling of soil BVOC emissions under various climate scenarios both at regional and global scales.

Impact of three decades of warming, increased nutrient availability, and increased cloudiness on the fluxes of greenhouse gases and biogenic volatile organic compounds in a subarctic tundra heath.

Climate change is exposing subarctic ecosystems to higher temperatures, increased nutrient availability, and increasing cloud cover. In this study, we assessed how these factors affect the fluxes of greenhouse gases (GHGs) (i.e., methane (CH4), nitrous oxide (N2O), and carbon dioxide (CO2)), and biogenic volatile organic compounds (BVOCs) in a subarctic mesic heath subjected to 34 years of climate change related manipulations of temperature, nutrient availability, and light. GHGs were sampled from static chambers and gases analyzed with gas chromatograph. BVOCs were measured using the push-pull method and gases analyzed with chromatography-mass spectrometry. The soil temperature and moisture content in the warmed and shaded plots did not differ significantly from that in the controls during GHG and BVOC measurements. Also, the enclosure temperatures during BVOC measurements in the warmed and shaded plots did not differ significantly from temperatures in the controls. Hence, this allowed for assessment of long-term effects of the climate treatment manipulations without interference of temperature and moisture differences at the time of measurements. Warming enhanced CH4 uptake and the emissions of CO2, N2O, and isoprene. Increased nutrient availability increased the emissions of CO2 and N2O but caused no significant changes in the fluxes of CH4 and BVOCs. Shading (simulating increased cloudiness) enhanced CH4 uptake but caused no significant changes in the fluxes of other gases compared to the controls. The results show that climate warming and increased cloudiness will enhance CH4 sink strength of subarctic mesic heath ecosystems, providing negative climate feedback, while climate warming and enhanced nutrient availability will provide positive climate feedback through increased emissions of CO2 and N2O. Climate warming will also indirectly, through vegetation changes, increase the amount of carbon lost as isoprene from subarctic ecosystems.

Changes in biogenic volatile organic compound emissions in response to the El Niño–Southern Oscillation

Abstract. Emissions of biogenic volatile organic compounds (BVOCs) from the terrestrial biosphere play a significant role in major atmospheric processes. BVOCs are highly reactive compounds that influence the atmosphere's oxidation capacity and also serve as precursors for the formation of aerosols that influence global radiation budgets. Emissions depend on the response of vegetation to atmospheric conditions (primarily temperature and light), as well as other stresses, e.g. from droughts and herbivory. The El Niño–Southern Oscillation (ENSO) is a naturally occurring cycle arising from anomalies in the sea surface temperature (SST) in the tropical Pacific. ENSO perturbs the natural seasonality of weather systems on both global and regional scales and is considered the most significant driver of climate variability. Several studies have evaluated the sensitivity of BVOC fluxes during ENSO events using historical transient simulations. While this approach employs realistic scenarios, it is difficult to assess the impact of ENSO alone given the multiple types of climate forcing, e.g. from anthropogenic emissions of CO2 and aerosol. In this study, a global atmospheric chemistry–climate model with enabled interactive vegetation was used to conduct two sets of simulations: (1) isolated ENSO event simulations, in which a single ENSO event is used to perturb otherwise baseline conditions, and (2) sustained ENSO simulations, in which the same ENSO conditions are reproduced for an extended period of time. From the isolated ENSO events, we present global and regional BVOC emission changes resulting from the immediate response of vegetation to atmospheric states. More focus is given to the sustained ENSO simulations, which have the benefit of reducing the internal variability for more robust statistics when linking atmospheric and vegetation variables with BVOC flux anomalies. Additionally, these simulations explore long-term changes in the biosphere with potential shifts in vegetation in this possible climate mode, accounting for the prospect of increased intensity and frequency of ENSO with climate change. Our results show that strong El Niño events increase global isoprene emission fluxes by 2.9 % and that one single ENSO event perturbs the Earth system so markedly that BVOC emission fluxes do not return to baseline emissions within several years after the event. We show that persistent ENSO conditions shift the vegetation to a new quasi-equilibrium state, leading to an amplification of BVOC emission changes with up to a 19 % increase in isoprene fluxes over the Amazon. We provide evidence that BVOC-induced changes in plant phenology, such as the leaf area index (LAI), have a significant influence on BVOC emissions in the sustained ENSO climate mode.

Impacts of seasonality, drought, nitrogen fertilization, and litter on soil fluxes of biogenic volatile organic compounds in a Mediterranean forest

Biogenic volatile organic compounds (BVOCs) play critical roles in ecosystems at various scales, influencing above- and below-ground interactions and contributing to the atmospheric environment. Nonetheless, there is a lack of research on soil BVOC fluxes and their response to environmental changes. This study aimed to investigate the impact of drought, nitrogen (N) fertilization, and litter manipulation on soil BVOC fluxes in a Mediterranean forest. We assessed the effects of drought and N fertilization on soil BVOC exchanges and soil CO2 fluxes over two consecutive years using a dynamic chamber method, and solid-phase microextraction was utilized to quantify soil BVOCs in one year. Our findings revealed that the soil acted as an annual net sink for isoprenoids (1.30–10.33 μg m−2 h−1), with the highest uptake rates observed during summers (25.90 ± 9.36 μg m−2 h−1). The increased summer uptake can be attributed to the significant concentration gradient of BVOCs between atmosphere and soil. However, strong seasonal dynamics were observed, as the soil acted as a source of BVOCs in spring and autumn. The uptake rate of isoprenoids exhibited a significant positive correlation with soil temperature and atmospheric isoprenoid concentrations, while displaying a negative correlation with soil moisture and soil CO2 flux. The effects of drought and N fertilization on soil BVOCs were influenced by the type of VOCs, litter layer, and season. Specifically, drought significantly affected the exchange rate and quantities of sesquiterpenes. N fertilization led to increased emissions of specific BVOCs (α-pinene and camphene) due to the stimulation of litter emissions. These findings underscore the importance of the soil as a sink for atmospheric BVOCs in this dry Mediterranean ecosystem. Future drought conditions may significantly impact soil water content, resulting in drier soils throughout the year, which will profoundly affect the exchange of soil BVOCs between the soil and atmosphere.

Isoprene and monoterpene simulations using the chemistry–climate model EMAC (v2.55) with interactive vegetation from LPJ-GUESS (v4.0)

Abstract. Earth system models (ESMs) integrate previously separate models of the ocean, atmosphere and vegetation into one comprehensive modelling system enabling the investigation of interactions between different components of the Earth system. Global isoprene and monoterpene emissions from terrestrial vegetation, which represent the most important source of volatile organic compounds (VOCs) in the Earth system, need to be included in global and regional chemical transport models given their major chemical impacts on the atmosphere. Due to the feedback of vegetation activity involving interactions with weather and climate, a coupled modelling system between vegetation and atmospheric chemistry is recommended to address the fate of biogenic volatile organic compounds (BVOCs). In this work, further development in linking LPJ-GUESS, a global dynamic vegetation model, to the atmospheric-chemistry-enabled atmosphere–ocean general circulation model EMAC is presented. New parameterisations are included to calculate the foliar density and leaf area density (LAD) distribution from LPJ-GUESS information. The new vegetation parameters are combined with existing LPJ-GUESS output (i.e. leaf area index and cover fractions) and used in empirically based BVOC modules in EMAC. Estimates of terrestrial BVOC emissions from EMAC's submodels ONEMIS and MEGAN are evaluated using (1) prescribed climatological vegetation boundary conditions at the land–atmosphere interface and (2) dynamic vegetation states calculated in LPJ-GUESS (replacing the “offline” vegetation inputs). LPJ-GUESS-driven global emission estimates for isoprene and monoterpenes from the submodel ONEMIS were 546 and 102 Tg yr−1, respectively. MEGAN determines 657 and 55 Tg of isoprene and monoterpene emissions annually. The new vegetation-sensitive BVOC fluxes in EMAC are in good agreement with emissions from the semi-process-based module in LPJ-GUESS. The new coupled system is used to evaluate the temperature and vegetation sensitivity of BVOC fluxes in doubling CO2 scenarios. This work provides evidence that the new coupled model yields suitable estimates for global BVOC emissions that are responsive to vegetation dynamics. It is concluded that the proposed model set-up is useful for studying land–biosphere–atmosphere interactions in the Earth system.

Seasonal and diel patterns of biogenic volatile organic compound fluxes in a subarctic tundra

In arctic and subarctic regions, rapid climate changes enhance biogenic volatile organic compound (BVOC) emissions from vegetation, with potentially significant influence on atmospheric processes. However, the seasonal and diel patterns of bidirectional exchange (flux) of BVOCs remain poorly studied in these regions. Here, we deployed a proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF-MS) to investigate ecosystem-level BVOC fluxes over a growing season in a subarctic tundra heath in Abisko, Northern Sweden, and to quantify BVOC emissions from two widespread dwarf shrubs in the high latitudes, Salix myrsinites and Betula nana. As expected, ecosystem fluxes of short-chained oxygenated compounds (e.g., methanol, acetaldehyde and acetone) and terpenoids (e.g., isoprene, monoterpenes and sesquiterpenes) followed different seasonal and diel patterns. For the short-chained oxygenated compounds, net emissions dominated and peaked in the early growing season, while net deposition occurred sporadically, particularly at night. In contrast, terpenoids were almost exclusively emitted from the ecosystem, with maxima occurring in the peak growing season. At the branch level, these compound groups were emitted from both S. myrsinites and B. nana in clear diel patterns with high emissions during the day. S. myrsinites was dominated by isoprene emissions whilst B. nana was dominated by terpene emissions. Methanol, acetaldehyde and acetone were emitted at comparable levels and similar patterns from both species. Both ecosystem fluxes and branch emissions responded exponentially to enclosure temperature and depended on light levels. Compared to the BVOC emission models, however, the temperature responses were steeper for isoprene, monoterpenes, methanol and acetone, but weaker for sesquiterpenes. Apart from the well-known compounds, many other BVOCs, such as some carbonyls and nitrogen-containing compounds, were emitted from both the ecosystem and plants with significant contributions to the season variation in ecosystem fluxes. Overall, our study highlights the complexity of subarctic ecosystem BVOC fluxes, which vary both seasonally and diurnally. Vegetation composition changes triggered by climate change will shift BVOC composition, with important implications for atmospheric processes and local climate.

Bidirectional Exchange of Biogenic Volatile Organic Compounds in Subarctic Heath Mesocosms During Autumn Climate Scenarios.

Biogenic volatile organic compound (BVOC) flux dynamics during the subarctic autumn are largely unexplored and have been considered insignificant due to the relatively low biological activity expected during autumn. Here, we exposed subarctic heath ecosystems to predicted future autumn climate scenarios (ambient, warming, and colder, dark conditions), changes in light availability, and flooding, to mimic the more extreme rainfall or snowmelt events expected in the future. We used climate chambers to measure the net ecosystem fluxes and bidirectional exchange of BVOCs from intact heath mesocosms using a dynamic enclosure technique coupled to a proton‐transfer‐reaction time‐of‐flight mass spectrometer (PTR–ToF–MS). We focused on six BVOCs (methanol, acetic acid, acetaldehyde, acetone, isoprene, and monoterpenes) that were among the most dominant and that were previously identified in arctic tundra ecosystems. Warming increased ecosystem respiration and resulted in either net BVOC release or increased uptake compared to the ambient scenario. None of the targeted BVOCs showed net release in the cold and dark scenario. Acetic acid exhibited significantly lower net uptake in the cold and dark scenario than in the ambient scenario, which suggests reduced microbial activity. Flooding was characterized by net uptake of the targeted BVOCs and overruled any temperature effects conferred by the climate scenarios. Monoterpenes were mainly taken up by the mesocosms and their fluxes were not affected by the climate scenarios or flooding. This study shows that although autumn BVOC fluxes on a subarctic heath are generally low, changes in future climate may strongly modify them.

Modeling Intra‐ and Interannual Variability of BVOC Emissions From Maize, Oil‐Seed Rape, and Ryegrass

AbstractAir chemistry is affected by the emission of biogenic volatile organic compounds (BVOCs), which originate from almost all plants in varying qualities and quantities. They also vary widely among different crops, an aspect that has been largely neglected in emission inventories. In particular, bioenergy‐related species can emit mixtures of highly reactive compounds that have received little attention so far. For such species, long‐term field observations of BVOC exchange from relevant crops covering different phenological phases are scarcely available. Therefore, we measured and modeled the emission of three prominent European bioenergy crops (maize, ryegrass, and oil‐seed rape) for full rotations in north‐eastern Germany. Using a proton transfer reaction–mass spectrometer combined with automatically moving large canopy chambers, we were able to quantify the characteristic seasonal BVOC flux dynamics of each crop species. The measured BVOC fluxes were used to parameterize and evaluate the BVOC emission module (JJv) of the physiology‐oriented LandscapeDNDC model, which was enhanced to cover de novo emissions as well as those from plant storage pools. Parameters are defined for each compound individually. The model is used for simulating total compound‐specific reactivity over several years and also to evaluate the importance of these emissions for air chemistry. We can demonstrate substantial differences between the investigated crops with oil‐seed rape having 37‐fold higher total annual emissions than maize. However, due to a higher chemical reactivity of the emitted blend in maize, potential impacts on atmospheric OH‐chemistry are only 6‐fold higher.

Effect of senescence on biogenic volatile organic compound fluxes in wheat plants

Exchanges of biogenic volatile organic compounds (BVOC) between plants and the atmosphere are likely to vary, in amount and composition, between different plant species but also for a single plant during its development. However, the effect of plant development stages, including senescence, on BVOC exchanges remains poorly investigated, especially in the case of crop plants. We investigated the BVOC exchange patterns for wheat plants, the most grown crop species worldwide, during seed maturation, senescence and after harvest. Fluxes were measured online, in situ, at the plant scale by combining automated chambers and a Proton Transfer - Reaction - Quadrupole ion guide - Time of Flight - Mass Spectrometer (PTR-Qi-Tof-MS). The high resolution and sensitivity of this method enabled the measurement of a large mass spectrum of compounds emitted at very small amounts, allowing a precise characterization of BVOC exchanges. We found that the overall BVOC emissions increased twofold during the senescence stage compared to the maturation stage. Methanol was found to be the most emitted compound (49–60% of the overall flux on a molar basis) followed by acetone (7.5–8.2% of the overall flux on a molar basis) during each developmental stage investigated. Acetaldehyde was another major emitted compound contributing mainly during late senescence to the overall flux (9.7%). When normalized for temperature and light conditions, most BVOC emissions increased during senescence, showing a clear effect of senescence on BVOC exchanges. Chamber emissions were comparable to whole ecosystem fluxes measured at the same site by eddy covariance the previous year. The OH reactivity of the emitted compounds was evaluated based on known reaction rate constants and was the largest during the first senescence stage, peaking at 12 s−1 in the chambers. The results of this study show the need for considering plant phenology when computing BVOC emissions from crops.

Age-related response of forest floor biogenic volatile organic compound fluxes to boreal forest succession after wildfires

The amplification of global warming in the Northern regions results in a higher probability of wildfires in boreal forests. On the forest floor, wildfires have long-term effects on vegetation composition as well as soil and its microbial communities. A large variety of biogenic volatile organic compounds (BVOCs) such as isoprene, monoterpenes, sesquiterpenes have been observed to be emitted from soil and understory vegetation of boreal forest floor. Ultimately, the fire-induced changes in the forest floor affect its BVOC fluxes, and the recovery of the forest floor determines the quantity and quality of BVOC fluxes. However, the effects of wildfires on forest floor BVOC fluxes are rarely studied. Here we conducted a study of the impacts of post-fire succession on forest floor BVOC fluxes along a 158-year fire chronosequence in boreal Scots pine stands near the northern timberline in north-eastern Finland throughout a growing season. We determined the forest floor BVOC fluxes and investigated how the environmental and ground vegetation characteristics, soil respiration rates, and soil microbial and fungal biomass are associated with the BVOC fluxes during the post-fire succession. The forest floor was a source of diverse BVOCs. Monoterpenes (MTs) were the largest group of emitted BVOCs. We observed forest age-related differences in the forest floor BVOC fluxes along the fire chronosequence. The forest floor BVOC fluxes decreased with the reduction in ground vegetation coverage resulted from wildfire, and the decreased fluxes were also connected to a decrease in microbial activity as a result of the loss of plant roots and soil organic matter. The increase in BVOC fluxes was associated with the recovery of aboveground plant coverage and soils. Our results suggested taking into consideration the implications of BVOC flux variations on the atmospheric chemistry and climate feedbacks.

Phenological stage of tundra vegetation controls bidirectional exchange of BVOCs in a climate change experiment on a subarctic heath.

Traditionally, biogenic volatile organic compound (BVOC) emissions are often considered a unidirectional flux, from the ecosystem to the atmosphere, but recent studies clearly show the potential for bidirectional exchange. Here we aimed to investigate how warming and leaf litter addition affect the bidirectional exchange (flux) of BVOCs in a long‐term field experiment in the Subarctic. We also assessed changes in net BVOC fluxes in relation to the time of day and the influence of different plant phenological stages. The study was conducted in a full factorial experiment with open top chamber warming and annual litter addition treatments in a tundra heath in Abisko, Northern Sweden. After 18 years of treatments, ecosystem‐level net BVOC fluxes were measured in the experimental plots using proton‐transfer‐reaction time‐of‐flight mass spectrometry (PTR–ToF–MS). The warming treatment increased monoterpene and isoprene emissions by ≈50%. Increasing temperature, due to diurnal variations, can both increase BVOC emission and simultaneously, increase ecosystem uptake. For any given treatment, monoterpene, isoprene, and acetone emissions also increased with increasing ambient air temperatures caused by diurnal variability. Acetaldehyde, methanol, and sesquiterpenes decreased likely due to a deposition flux. For litter addition, only a significant indirect effect on isoprene and monoterpene fluxes (decrease by ~50%–75%) was observed. Litter addition may change soil moisture conditions, leading to changes in plant species composition and biomass, which could subsequently result in changes to BVOC emission compositions. Phenological stages significantly affected fluxes of methanol, isoprene and monoterpenes. We suggest that plant phenological stages differ in impacts on BVOC net emissions, but ambient air temperature and photosynthetically active radiation (PAR) also interact and influence BVOC net emissions differently. Our results may also suggest that BVOC fluxes are not only a response to changes in temperature and light intensity, as the circadian clock also affects emission rates.

Cross-correlations of Biogenic Volatile Organic Compounds (BVOC) emissions typify different phenological stages and stressful events in a Mediterranean Sorghum plantation

Climate change will affect the growing season and increase the occurrence of extreme stressful events, thus altering crop phenological phases and the associated emission of biogenic volatile organic compounds (BVOC). BVOC exchange has been poorly investigated in field crops, especially in the Mediterranean area. In this study we report continuous measurements of BVOC fluxes and CO2 net ecosystem exchange (NEE), together with environmental variables, green area index (GAI) and aboveground biomass (AGB) during a whole growing season in a grain sorghum (Sorghum bicolor x Sorghum sudangrass., cv. Nicol, Pioneer) plantation located in Southern Europe. Results of this intensive field campaign showed that, while the bare soil of our site was a sink of BVOC, the sorghum plantation became a source of oxygenated BVOC, mainly methanol and acetaldehyde, which were emitted over the season at an average rate of 0.137 ± 0.013 and 0.070 ± 0.004 nmol m−2 s−1, respectively. In addition, the application of the advanced data mining method of Self-Organizing Maps (SOM) revealed distinctive patterns of BVOC fluxes correlating with sorghum growth stages (GS): in the first stage (GS1), developing plantlets emitted a mixture of BVOC uniquely characterized by monoterpenes; in GS2, adult plants forming an homogeneous dense canopy emitted the most abundant fluxes of a mixture of oxygenated BVOC comprising methanol, acetaldehyde, formic acid, acetone, acetic acid and n-pentenol; once plants entered the flowering stage (in GS3), only a few BVOC continued to be emitted at the highest rates (i.e. formic acid, acetone, acetic acid, n-pentenol). Moreover, the application of SOM to a sub-set of BVOC fluxes highlighted the possibility to qualitatively differentiate stressful events of plant lodging and harvest cutting. In fact, enhanced emission of acetaldehyde distinguished the BVOC mixture emitted from lodged rather than from cut and harvested sorghum plants in the field.

Vapor pressure deficit helps explain biogenic volatile organic compound fluxes from the forest floor and canopy of a temperate deciduous forest.

Biogenic volatile organic compounds (BVOCs) play critical roles in ecological and earth-system processes. Ecosystem BVOC models rarely include soil and litter fluxes and their accuracy is often challenged by BVOC dynamics during periods of rapid ecosystem change like spring leaf out. We measured BVOC concentrations within the air space of a mixed deciduous forest and used a hybrid Lagrangian/Eulerian canopy transport model to estimate BVOC flux from the forest floor, canopy, and whole ecosystem during spring. Canopy flux measurements were dominated by a large methanol source and small isoprene source during the leaf-out period, consistent with past measurements of leaf ontogeny and theory, and indicative of a BVOC flux situation rarely used in emissions model testing. The contribution of the forest floor to whole-ecosystem BVOC flux is conditional on the compound of interest and is often non-trivial. We created linear models of forest floor, canopy, and whole-ecosystem flux for each study compound and used information criteria-based model selection to find the simplest model with the best fit. Most published BVOC flux models do not include vapor pressure deficit (VPD), but it entered the best canopy, forest floor, and whole-ecosystem BVOC flux model more than any other study variable in the present study. Since VPD is predicted to increase in the future, future studies should investigate how it contributes to BVOC flux through biophysical mechanisms like evaporative demand, leaf temperature and stomatal function.

PTR-TOF-MS eddy covariance measurements of isoprene and monoterpene fluxes from an eastern Amazonian rainforest

Abstract. Biogenic volatile organic compounds (BVOCs) are important components of the atmosphere due to their contribution to atmospheric chemistry and biogeochemical cycles. Tropical forests are the largest source of the dominant BVOC emissions (e.g. isoprene and monoterpenes). In this study, we report isoprene and total monoterpene flux measurements with a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) using the eddy covariance (EC) method at the Tapajós National Forest (2.857∘ S, 54.959∘ W), a primary rainforest in eastern Amazonia. Measurements were carried out from 1 to 16 June 2014, during the wet-to-dry transition season. During the measurement period, the measured daytime (06:00–18:00 LT) average isoprene mixing ratios and fluxes were 1.15±0.60 ppb and 0.55±0.71 mg C m−2 h−1, respectively, whereas the measured daytime average total monoterpene mixing ratios and fluxes were 0.14±0.10 ppb and 0.20±0.25 mg C m−2 h−1, respectively. Midday (10:00–14:00 LT) average isoprene and total monoterpene mixing ratios were 1.70±0.49 and 0.24±0.05 ppb, respectively, whereas midday average isoprene and monoterpene fluxes were 1.24±0.68 and 0.46±0.22 mg C m−2 h−1, respectively. Isoprene and total monoterpene emissions in Tapajós were correlated with ambient temperature and solar radiation. Significant correlation with sensible heat flux, SHF (r2=0.77), was also observed. Measured isoprene and monoterpene fluxes were strongly correlated with each other (r2=0.93). The MEGAN2.1 (Model of Emissions of Gases and Aerosols from Nature version 2.1) model could simulate most of the observed diurnal variations (r2=0.7 to 0.8) but declined a little later in the evening for both isoprene and total monoterpene fluxes. The results also demonstrate the importance of site-specific vegetation emission factors (EFs) for accurately simulating BVOC fluxes in regional and global BVOC emission models.

Comparative study of biogenic volatile organic compounds fluxes by wheat, maize and rapeseed with dynamic chambers over a short period in northern France

Biogenic volatile organic compounds (BVOC) are mainly emitted from vegetation. However there is still little information on BVOC exchanges with crops. In this study we measured fluxes of BVOC from wheat, maize and rapeseed crops near Paris at the plant level during a full-week period for each species. We used dynamic automated chambers coupled to a Proton Transfer Reaction, Quadrupole ion guide, Time of Flight mass spectrometer (PTR-Qi-Tof-MS) instrument for online measurements of BVOC. Our results confirm the hypothesis that many unexplored compounds contribute to BVOC exchanges between crops and the atmosphere, although for all plant species methanol was dominating the emissions (55–85% of the sum of the BVOC exchanges fluxes on a mass basis) followed by acetone and acetaldehyde. The 10 most exchanged compounds, excluding methanol, contributed more than 50% of the summed fluxes and the 100 most exchanged contributed to more than 90%. The summed BVOC emission and deposition presented large interspecies variations, but limited intra-species variability, with a summed net flux of 0.11 ± 0.02 μgBVOC gDW−1 h−1 for maize, 1.5 ± 0.7 μgBVOC gDW−1 h−1 for wheat, and 9.1 ± 2.4 μgBVOC gDW−1 h−1 for rapeseed. The 10 most emitted compounds were mostly emitted during the day and were correlated with both photosynthetically active radiation and temperature and anti-correlated with relative humidity. This study provides the first evaluation so far of the biosphere-atmosphere fluxes for several BVOC. In particular we provide a first evaluation of standard emission factor for isoprene and monoterpene for wheat and rapeseed at their respective growth stages. This study is however limited to a week period at a given stage for each species and at the plant level.

Global climate forcing driven by altered BVOC fluxes from 1990 to 2010 land cover change in maritime Southeast Asia

Abstract. Over the period of 1990–2010, maritime Southeast Asia experienced large-scale land cover changes, including expansion of high-isoprene-emitting oil palm plantations and contraction of low-isoprene-emitting natural forests. The ModelE2-Yale Interactive terrestrial Biosphere global chemistry–climate model is used to quantify the atmospheric composition changes, and for the first time, the associated radiative forcing induced by the land-cover-change-driven biogenic volatile organic compound (BVOC) emission changes (+6.5 TgC y−1 isoprene, −0.5 TgC y−1 monoterpenes). Regionally, surface-level ozone concentrations largely decreased (−3.8 to +0.8 ppbv). The tropical land cover changes occurred in a region of strong convective transport, providing a mechanism for the BVOC perturbations to affect the composition of the upper troposphere. Enhanced concentrations of isoprene and its degradation products are simulated in the upper troposphere, and, on a global-mean basis, land cover change had a stronger impact on ozone in the upper troposphere (+0.5 ppbv) than in the lower troposphere (<0.1 ppbv increase). The positive climate forcing from ozone changes (+9.2 mW m−2) was partially offset by a negative forcing (−0.8 mW m−2) associated with an enhancement in secondary organic aerosol (SOA). The sign of the net forcing is sensitive to uncertainty in the SOA yield from BVOCs. The global-mean ozone forcing per unit of regional oil palm expansion is +1 mW m−2 Mha−1. In light of expected continued expansion of oil palm plantations, regional land cover changes may play an increasingly important role in driving future global ozone radiative forcing.

Impact of Short‐Term Climate Variability on Volatile Organic Compounds Emissions Assessed Using OMI Satellite Formaldehyde Observations

AbstractA major feedback between climate and atmospheric chemistry lies in the meteorological dependence of the emissions of biogenic volatile organic compounds (BVOCs), precursors of important climate forcers, aerosols, and ozone. Whereas the short‐term response of BVOC emissions to meteorological drivers is fairly well simulated by current emission models, it is yet unclear whether models can faithfully predict their response to climate change, given the scarcity of long observation records of BVOC fluxes. Here we take advantage of the high yield of formaldehyde (HCHO) in the oxidation of VOCs and use a long‐term spaceborne record of HCHO observations in combination with model simulations to show that (i) HCHO interannual variability is primarily driven by climate through its impacts on photochemistry, vegetation fire occurrence, and above all, biogenic emissions and (ii) the HCHO record validates the interannual variability of biogenic emissions calculated by the state‐of‐the‐art Model of Emissions of Gases and Aerosols from Nature (MEGAN) emission model in vegetated regions.

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.

VOC emission rates over London and South East England obtained by airborne eddy covariance.

Volatile organic compounds (VOCs) originate from a variety of sources, and play an intrinsic role in influencing air quality. Some VOCs, including benzene, are carcinogens and so directly affect human health, while others, such as isoprene, are very reactive in the atmosphere and play an important role in the formation of secondary pollutants such as ozone and particles. Here we report spatially-resolved measurements of the surface-to-atmosphere fluxes of VOCs across London and SE England made in 2013 and 2014. High-frequency 3-D wind velocities and VOC volume mixing ratios (made by proton transfer reaction - mass spectrometry) were obtained from a low-flying aircraft and used to calculate fluxes using the technique of eddy covariance. A footprint model was then used to quantify the flux contribution from the ground surface at spatial resolution of 100 m, averaged to 1 km. Measured fluxes of benzene over Greater London showed positive agreement with the UK's National Atmospheric Emissions Inventory, with the highest fluxes originating from central London. Comparison of MTBE and toluene fluxes suggest that petroleum evaporation is an important emission source of toluene in central London. Outside London, increased isoprene emissions were observed over wooded areas, at rates greater than those predicted by a UK regional application of the European Monitoring and Evaluation Programme model (EMEP4UK). This work demonstrates the applicability of the airborne eddy covariance method to the determination of anthropogenic and biogenic VOC fluxes and the possibility of validating emission inventories through measurements.

Are BVOC exchanges in agricultural ecosystems overestimated? Insights from fluxes measured in a maize field over a whole growing season

Abstract. Although maize is the second most important crop worldwide, and the most important C4 crop, no study on biogenic volatile organic compounds (BVOCs) has yet been conducted on this crop at ecosystem scale and over a whole growing season. This has led to large uncertainties in cropland BVOC emission estimations. This paper seeks to fill this gap by presenting, for the first time, BVOC fluxes measured in a maize field at ecosystem scale (using the disjunct eddy covariance by mass scanning technique) over a whole growing season in Belgium. The maize field emitted mainly methanol, although exchanges were bi-directional. The second most exchanged compound was acetic acid, which was taken up mainly in the growing season. Bi-directional exchanges of acetaldehyde, acetone and other oxygenated VOCs also occurred, whereas the terpenes, benzene and toluene exchanges were small, albeit significant. Surprisingly, BVOC exchanges were of the same order of magnitude on bare soil and on well developed vegetation, suggesting that soil is a major BVOC reservoir in agricultural ecosystems. Quantitatively, the maize BVOC emissions observed were lower than those reported in other maize, crops and grasses studies. The standard emission factors (SEFs) estimated in this study (231 ± 19 µg m−2 h−1 for methanol, 8 ± 5 µg m−2 h−1 for isoprene and 4 ± 6 µg m−2 h−1 for monoterpenes) were also much lower than those currently used by models for C4 crops, particularly for terpenes. These results suggest that maize fields are small BVOC exchangers in north-western Europe, with a lower BVOC emission impact than that modelled for growing C4 crops in this part of the world. They also reveal the high variability in BVOC exchanges across world regions for maize and suggest that SEFs should be estimated for each region separately.