Volatile organic compounds (VOCs) and ozone (O3) are key constituents of tropospheric chemistry, affecting both air quality and climate. Forests are major emitters of biogenic VOCs (BVOCs), yet large uncertainties remain regarding the diversity of exchanged compounds, the drivers of their bidirectional fluxes, and their in-canopy chemistry. Long-term and comprehensive in situ datasets remain scarce, limiting our understanding of these complex processes. We conducted a 3-year field campaign (2022-2024) at the Integrated Carbon Observation System mixed temperate forest station of Vielsalm (BE-Vie), combining vertical concentration profile and eddy covariance flux measurements above and below the canopy (concentration dataset: 10.18758/NVFBA74V, ; flux dataset: 10.18758/KHV8ZXU2, ; concentration-turbulence profile dataset: 10.18758/BED4Q2VY, ). Using a PTR-ToF-MS and an open-source data-processing workflow, we identified 48 significantly exchanged VOCs. The vertical and diurnal gradients of the mixing ratios reflected the interplay between emission, deposition, chemistry, and transport. Combined with a profile of turbulence statistics, these observations offer an opportunity to investigate their behaviour within the canopy. The forest acted as a net VOC source in summer (similar to 1.25 mu g m-2 s-1), while deposition dominated in autumn. Many oxygenated VOCs displayed bidirectional exchange. Monoterpenes, isoprene, and methanol were the most abundant flux contributors, but 15-30 (30-43) compounds were needed to account for 90 % of total emissions (depositions), depending on the season. Below-canopy BVOC and O3 fluxes reached similar to 10 % of above-canopy ones, with proportionally enhanced below-canopy ozone uptake at night. This study provides one of the most detailed long-term datasets of VOC and O3 exchange in a temperate forest and serves as a key reference for improving process-based models of biogenic, physical, and chemical exchange in forest ecosystems.

We employ an updated retrieval of space-based methanol (CH3OH) column measurements from the Infrared Atmospheric Sounding Interferometer (IASI) and an emission optimisation framework built on the MAGRITTE chemical transport model to assess terrestrial emissions of methanol to the atmosphere between 2008-2019. We first carry out a IASI CH3OH validation study based on concentration measurements from three airborne campaigns, using the model and the IASI averaging kernels to compute aircraft-based columns directly comparable to IASI data. IASI is found to underestimate high columns in the considered region. A linear regression gives Omega IASI=0.46 Omega airc+10.6 & times;1015molec.cm-2, with Omega IASI and Omega airc the IASI and aircraft-derived columns, respectively. Inverse modelling of terrestrial methanol emissions using MAGRITTE and bias-corrected IASI columns leads to much-improved overall agreement against in situ measurement campaigns and column data at eight FTIR stations. The optimised global biogenic methanol emissions (similar to 160Tgyr-1) are 22 %-60 % higher than previous top-down estimates, due to (1) column enhancements caused by the IASI bias-correction and (2) higher dry deposition velocities in the model over land, compared to previous model studies, based on a parametrisation constrained by extensive campaign data. The inversion results are less reliable over boreal forests due to shortcomings of both the bias-correction and the dry deposition scheme over these regions. The optimisation suggests large changes in the distribution and seasonality of emissions. Over tropical ecosystems, radiation and temperature appear to exert a stronger control on biogenic emissions than is currently accounted for in the MEGAN model.

This study presents results from an Intensive Measurement Period (IMP2022) conducted during the European heatwave of July 2022, focusing on ozone, volatile organic compounds (VOCs), and carbonaceous aerosols at 31 sites across Europe. The episode featured persistent high-pressure systems, record-breaking temperatures, widespread ozone exceedances and concurrent atmospheric new particle formation and growth events. Coordinated measurements and chemistry transport modelling were used to examine the spatial variability of ozone, VOC composition, and secondary organic aerosol (SOA) formation under extreme meteorological conditions. Oxygenated VOCs (O-VOCs) constituted the largest fraction of total measured VOC mixing ratios, followed by non-methane hydrocarbons (NMHCs) and aromatics, with contributions from both anthropogenic and biogenic sources. Sensitivity simulations indicate that ozone formation was predominantly NOx-limited across most regions during IMP2022. However, the highest ozone peaks occurred under conditions of elevated NOx in combination with enhanced BVOC emissions. In contrast, SOA formation was slightly enhanced under low-NOx conditions and reduced in elevated NOx. Isoprene, aliphatic NMHCs, and O-VOCs dominated the ozone formation potential, while aromatics and monoterpenes were major contributors to SOA potential. Model simulations indicated that higher NOx concentrations can reduce SOA formation by about 10 %. The campaign also highlighted observational gaps underscoring the need for broader and higher-resolution VOC monitoring across Europe. Overall, further reductions in NOx emissions, alongside targeted control of key anthropogenic VOCs, would benefit air quality under future climate extremes.

Abstract. Volatile organic compounds (VOCs) act as precursors to ozone and secondary organic aerosols, which have significant health and environmental impacts, and they can reduce the atmospheric oxidative capacity. However, their budget remains poorly quantified, especially over remote areas such as the Tropical oceans. Here, we present high-resolution simulations of atmospheric composition over Réunion Island, in the Indian Ocean, using the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem). The coexistence and spatial heterogeneity of anthropogenic and biogenic emission sources in this region present a valuable but challenging test of the model performance. The WRF-Chem model is evaluated against several observational datasets, including Proton Transfer Reaction Mass Spectrometry (PTR-MS) measurements of VOCs and oxygenated VOCs (OVOCs) at the Maïdo Observatory (2160 m a.s.l.) in January and July 2019. While the primary goal of our study is a better understanding of (O)VOC budget at remote Tropical latitudes, important model refinements are made to improve the model performance, including the implementation of high-resolution anthropogenic and biogenic isoprene emissions, updates to the chemical mechanism, and adjustments to the boundary conditions. These refinements are supported by comparisons with PTR-MS data as well as with meteorological measurements at Maïdo, in situ NOx and O3 measurements from the air quality Atmo-Réunion network, Fourier Transform Infrared Spectroscopy (FTIR) measurements of O3, CO, ethane and several OVOCs, also at Maïdo, and satellite retrievals from the TROPOspheric Monitoring Instrument (TROPOMI). TROPOMI NO2 data suggests that anthropogenic emissions, particularly from power plants near Le Port, dominate NOx levels over the island. Both TROPOMI and in situ surface NO2 comparisons are used to adjust the power plant emissions at Le Port. Surface ozone concentrations are overestimated by ~6 ppbv on average, likely due to the neglect of halogen chemistry in the model. Whereas modelled NO2 over oceans is too low in summer when the lightning source is turned off, the inclusion of this source results in model overestimations corroborated by comparisons with upper tropospheric NO2 mixing ratios derived from TROPOMI using the cloud-slicing technique (Marais et al., 2021). The model generally succeeds in reproducing the PTR-MS isoprene and its oxidation products (Iox), except for a moderate underestimation (~30 %) of noontime isoprene concentration and for modelled concentration peaks near dawn and dusk, that are not seen in the observations. The ratio of Iox to isoprene (0.8 at noon in January) is fairly well reproduced by the model. The methanol and monoterpenes observations both suggest overestimations of their biogenic emissions, by factors of about 2 and 5, respectively. Acetaldehyde anthropogenic emissions are likely strongly overestimated, due to the lumping of higher aldehydes into this compound. Without this lumping, the modelled acetaldehyde would be underestimated by almost one order of magnitude, suggesting the existence of a large missing source, likely photochemical. The comparisons suggest the existence of a biogenic source of MEK equivalent to about 3 % of isoprene emissions, likely associated with the dry deposition and conversion to MEK of key isoprene oxidation products. A strong model underestimation of the PTR-MS signal at mass 61 is also found, by a factor of 3–5 during daytime, consistent with previously reported missing sources of acetic and peracetic acid.

Volatile organic compounds (VOCs) act as precursors to ozone and secondary organic aerosols, which have significant health and environmental impacts. They can also reduce the atmospheric oxidative capacity. However, their budget remains poorly quantified, especially over remote areas such as the tropical oceans. Here, we present high-resolution simulations of atmospheric composition over Réunion Island, located in the Indian Ocean, using the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem). The coexistence and spatial heterogeneity of anthropogenic and biogenic emission sources in this region present a valuable but challenging test of the model performance. The WRF-Chem model is evaluated against several observational datasets, including proton transfer reaction mass spectrometry (PTR-MS) measurements of VOCs and oxygenated VOCs (OVOCs) at the Maïdo Observatory, Réunion Island (2160 m above sea level), in January and July 2019, representing austral summer and winter, respectively, and capturing the seasonal extremes for the region. While the primary goal of our study is to gain a better understanding of the (O)VOC budget at remote tropical latitudes, important model refinements have been made to improve the model performance, including the implementation of high-resolution anthropogenic and biogenic isoprene emissions, updates to the chemical mechanism, and adjustments to the boundary conditions. These refinements are supported by comparisons with PTR-MS data as well as with meteorological measurements at Maïdo; in situ NOx and O3 measurements from the air quality Atmo-Réunion network; Fourier transform infrared spectroscopy (FTIR) measurements of O3, CO, ethane, and several OVOCs, also at Maïdo; and satellite retrievals from the TROPOspheric Monitoring Instrument (TROPOMI). TROPOMI NO2 data suggest that anthropogenic emissions, particularly from power plants near Le Port, dominate NOx levels over the island. Both TROPOMI and in situ surface NO2 comparisons are used to adjust the power plant emissions at Le Port. Surface ozone concentrations are overestimated by ∼6 ppbv on average, likely due to the neglect of halogen chemistry in the model, though other factors may also contribute. While modelled NO2 over oceans is too low in summer when the lightning source is excluded, including this source results in model overestimations, as corroborated by comparisons with upper tropospheric NO2 mixing ratios derived from TROPOMI using the cloud-slicing technique (Marais et al., 2021). The model generally succeeds in reproducing the PTR-MS isoprene and its oxidation products (Iox), except for a moderate underestimation (∼30 %) of noontime isoprene concentrations, and modelled concentration peaks near dawn and dusk, which are not seen in the observations. The ratio of Iox to isoprene (0.8 at noon in January) is fairly well reproduced by the model. The methanol and monoterpenes observations both suggest overestimations of their biogenic emissions, by factors of about 2 and 5, respectively. Acetaldehyde anthropogenic emissions are likely strongly overestimated, due to the lumping of higher aldehydes into this compound. Without this lumping, the modelled acetaldehyde would be underestimated by almost one order of magnitude, suggesting the existence of a large missing source, likely photochemical. The comparisons suggest the existence of a biogenic source of methyl ethyl ketone (MEK), equivalent to about 3 % of isoprene emissions, likely associated with the dry deposition and conversion of key isoprene oxidation products to MEK. A strong model underestimation of the PTR-MS signal at mass 61 is also found, by a factor of 3–5 during daytime, consistent with previously reported missing sources of acetic and peracetic acid.

The BIO-MAÏDO (Bio-physicochemistry of tropical clouds at Maïdo: processes and impacts on secondary organic aerosols formation) campaign was conducted from 13 March to 4 April 2019 on the tropical island of Réunion. The main objective of the project was to improve understanding of cloud impacts on the formation of secondary organic aerosols (SOA) from biogenic volatile organic compound (BVOC) precursors in a tropical environment. Instruments were deployed at five sites: a receptor site, Maïdo Observatory (MO) at 2165 m a.s.l. and four sites along the slope of the Maïdo mountain. Observations include measurements of volatile organic compounds (VOCs) and characterization of the physical, chemical and biological (bacterial diversity and culture-based approaches) properties of aerosols and cloud water. Turbulent parameters of the boundary layer, radiative fluxes and emissions fluxes of BVOCs from the surrounding vegetation were measured to help interpret observed chemical concentrations in the different phases. Dynamical analyses showed two preferred trajectory routes for air masses arriving at MO during the daytime. Both trajectories correspond to return branches of the trade winds associated with upslope thermal breezes, where air masses likely encountered cloud processing. The highest mixing ratios of oxygenated VOCs (OVOCs) were measured above the site located in the endemic forest and the highest contribution of OVOCs to total VOCs at MO. Chemical compositions of particles during daytime showed higher concentrations of oxalic acid, a tracer of cloud processing and photochemical aging, and a more oxidized organic aerosol at MO than at other sites. Approximately 20 % of the dissolved organic compounds were analyzed. Additional analyses by ultra-high-resolution mass spectrometry will explore the complexity of the missing cloud organic matter.

Volatile organic compounds (VOCs) play a key role in atmospheric chemistry. These gases impact air quality by participating in the formation of ozone and secondary organic aerosols and extend the lifetime of methane in the atmosphere. Approximately 90% of global VOC emissions are biogenic (BVOCs), and since forests are the main emitters of BVOCs, these ecosystems deserve special attention in order to better characterize BVOCs exchanges with the atmosphere. Traditionally, flux measurements were mainly limited to a few dominant BVOC species, such as isoprene, terpenes and methanol, due to technical measurement limitations. Most of the measured species were found to be emitted by vegetation, but some studies detected significant net depositions of compounds such as methanol, driven by environmental factors favouring the formation of surface wetness. This observation supports the need for a more detailed and complete picture of BVOC bidirectional exchanges at forest sites as well as the mechanisms controlling these fluxes, which are essential to better characterize the in-canopy atmospheric chemistry.To address this gap, BVOC fluxes were measured in spring-summer 2022 using a PTR-TOF-MS instrument (PTR-TOF-4000, Ionicon Analytik GmbH) over a mixed temperate forest in the Belgian Ardenne (Vielsalm), which is part of the ICOS network. The use of a PTR-TOF-MS instrument, deployed at Vielsalm in the framework of ACTRIS, allows for the simultaneous detection of a very wide range of VOC-related ion masses with increased sensitivity (especially for ions at high m/z ratios) and higher mass resolving power compared to conventional PTR-Quad-MS instruments. O3 fluxes were also simultaneously acquired using fast and slow ozone analysers in order to complete the BVOC fluxes dataset and BVOC+O3 concentration profiles were frequently measured at seven levels along the flux tower from ground level up to 51 m.(Un)calibrated BVOC mixing ratios were first derived from results of the Ionicon Data Analyzer software (IDA, Ionicon Analytik GmbH) obtained on a near-daily basis, and these concentrations were then used in a computational tool based on InnFLUX (Atmospheric Physics and Chemistry Group, University of Innsbruck) to compute fluxes by eddy covariance. Along with these fluxes, uncertainties and limits of detection (LODs) were estimated, and quality control statistical tests were performed. During the whole measurement campaign, about 570 m/z peaks were detected by the IDA software.Based on this extensive dataset, our goals are to: (1) perform spectral analysis (which often turns out to be trickier for low signal-to-noise ratios), (2) determine the significant fluxes based on LODs, (3) analyse their response to meteorological variables, phenology and O3 concentrations/fluxes, (4) attempt compound attribution based on scientific literature and site-related information, and (5) establish the budget of BVOC emissions and depositions for the forest site. The obtained results will be compared to BVOC studies previously conducted at the Vielsalm ICOS forest site with a PTR-Quad-MS instrument and should improve our previous BVOC budget estimates at the site.

Oxygenated volatile organic compounds (OVOC) have a significant impact on atmospheric oxidation capacity and climate. OVOCs are directly emitted from biogenic sources and are produced from the oxidation of hydrocarbons in the atmosphere. However, their budget remains poorly understood, due to incomplete representation of photochemical OVOC production and uncertainties in terrestrial emissions and ocean/atmosphere exchanges. In addition, OVOC atmospheric measurements are scarce in remote areas, in particular in tropical regions. In this work, we exploit a 2-year high-temporal resolution dataset of mass spectrometry (PTR-MS) measurements of OVOC compounds at a remote high-altitude tropical site, the Maïdo Observatory (2155m asl) on Reunion Island. More precisely, the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) is used to provide an updated evaluation of the budget of OVOCs over Reunion Island, based on the PTR-MS dataset complemented with meteorological measurements and satellite (TROPOMI) retrievals of relevant compounds. The model is configured to allow three nested domains centred on Reunion Island, with spatial resolution from 12.5, 2.5 and 0.5 km. The finest resolution is needed due to the complex orography of the island and the spatially heterogeneous distribution of reactive species. For computational reasons, the focus is on two one-month simulations in January and July 2019, allowing analysis of seasonal differences and their impacts on model performance and chemical budget.The WRF-simulated meteorology is first evaluated against meteorological measurements at a remote site (Maïdo) and two urban sites (Saint Denis and Saint Pierre). The impact of physical parameterizations (i.e. planetary boundary layer parameterizations, surface scheme, etc.) is tested through sensitivity simulations. A high-resolution (1km2) anthropogenic emission inventory for Reunion is implemented, complemented with information from global inventories. Biogenic VOC emissions (primarily isoprene) are calculated on-line using the MEGAN algorithm and high-resolution distributions of standard emission factors and plant functional types (PFTs). The MOZART chemical mechanism is adopted. The chemical simulations are evaluated against (1) NO2 and HCHO vertical columns from TROPOMI, (2) the PTR-MS OVOC dataset at Maïdo, and (3) network air quality measurements at several sites. Those comparisons will provide new constraints on the emissions of NOx and VOCs, and will result in recommendations for further refinements. This work will lead to a better appraisal of OVOC sources and sinks over the island. The main unknowns and potential issues will be discussed.

Atmospheric mercury (Hg) observations in the lower free troposphere (LFT) can give important insights into Hg redox chemistry and can help constrain Hg background concentrations on a regional level. Relatively continuous sampling of LFT air, inaccessible to most ground-based stations, can be achieved at high-altitude observatories. However, such high-altitude observatories are rare, especially in the Southern Hemisphere (SH), and atmospheric Hg in the SH LFT is unconstrained. To fill this gap, we continuously measured gaseous elemental mercury (GEM; hourly) and reactive mercury (RM; integrated over ∼ 6–14 d) for 9 months at Maïdo mountain observatory (2160 m a.s.l.) on remote Réunion Island (21.1∘ S, 55.5∘ E) in the tropical Indian Ocean. GEM exhibits a marked diurnal variation characterized by a midday peak (mean: 0.95 ng m−3; SD: 0.08 ng m−3) and a nighttime low (mean: 0.78 ng m−3; SD: 0.11 ng m−3). We find that this diurnal variation is likely driven by the interplay of important GEM photo-reemission from the islands' vegetated surfaces (i.e. vegetation + soil) during daylight hours (8–22 ng m−2 h−1), boundary layer influences during the day, and predominant LFT influences at night. We estimate GEM in the LFT based on nighttime observations in particularly dry air masses and find a notable seasonal variation, with LFT GEM being lowest from December to March (mean 0.66 ng m−3; SD: 0.07 ng m−3) and highest from September to November (mean: 0.79 ng m−3; SD: 0.09 ng m−3). Such a clear GEM seasonality contrasts with the weak seasonal variation reported for the SH marine boundary layer but is in line with modeling results, highlighting the added value of continuous Hg observations in the LFT. Maïdo RM is 10.6 pg m−3 (SD: 5.9 pg m−3) on average, but RM in the cloud-free LFT might be about twice as high, as weekly–biweekly sampled RM observations are likely diluted by low-RM contributions from the boundary layer and clouds.

This study presents a high‐resolution dynamical analysis of Volatile Organic Compound (VOC) concentrations measured from March 11 to April 4 2019 at Réunion Island during the BIO‐MAÏDO (Bio‐physicochemistry of tropical clouds at Maïdo: processes and impacts on secondary organic aerosols formation) campaign. We detail the dynamical and chemical processes that govern atmospheric VOC concentrations at two targeted sites of the western slope of Réunion Island: Petite France (PF), 950 m above sea level (a.s.l.) and Maïdo Observatory (MO), 2150 m a.s.l. A dynamical connection between PF and MO is found during four selected days: March 28 and 31, April 1 and 3. Trajectory calculations using the coupling of Meso‐Computing Advection‐interpolation of atmospheric parameters and Trajectory tool (CAT) (100 m horizontal resolution of Meso‐NH high‐resolution non‐hydrostatic model and the CAT trajectory model) Lagrangian transport model showed that air masses were dynamically linked between the two measurements sites for 19% of the time during the complete campaign. Trajectories from the Meso‐CAT model combined with the Corine Land Cover‐2018 register shows that backward‐trajectories are frequently located above biogenic area (mixed forest, 3%–46% of total number trajectory point) and cultures area (e.g., sugar cane plantation, 1%–17%). Regarding VOCs concentrations, air masses coming from downhill MO are associated with significant measured concentrations of isoprene, isoprene oxidation products and benzene. Averaged concentration daytime ratios of isoprene and isoprene oxidation products from PF to MO are 0.73 ± 1.01 and 0.26 ± 0.26 respectively illustrating a loss of these VOCs due to deposition, oxidation, or possibility dilution on clouds.

Volatile organic compounds (VOCs) are key precursors for the formation of surface level ozone (O3) and secondary organic aerosols, and therefore, they have a significant impact on air quality and climate. In addition, through their interaction with the hydroxyl radical (OH), they impact the atmospheric lifetime of methane, further affecting climate. Among non-methane VOCs, the oxygenated species (OVOCs) are especially relevant in remote regions where they constitute the largest OH sink. Due to the paucity of data at these locations, OVOCs sources and sinks are poorly constrained in models. This work addresses the critical need for OVOC observations at remote locations. A high-sensitivity quadrupole-based proton-transfer-reaction mass-spectrometry VOC analyzer (hs-PTR-MS) was deployed at La Réunion --- a remote tropical island located in the south west Indian Ocean, home to the Maïdo observatory --- between October 2017 and November 2019. As the observatory is located near the top of the planetary boundary layer (PBL), pristine marine boundary layer air masses, enriched with compounds emitted by mesoscale sources, reach the observatory during the day. At night, the observatory is located in the free troposphere. The variability in PBL development drives the diel concentration profiles of a variety of biogenic and anthropogenic tracers recorded with the hs-PTR-MS instrument. The seasonal variability of biogenic tracers is driven by the hot and wet versus the cold and dry seasons. Every year, biomass burning plumes originating from African and Madagascan fires reach the observatory between August and November, significantly impacting local air quality at La Réunion. We will present both the diel and seasonal variability using the 2-year near-continuous (O)VOC dataset recorded with the hs-PTR-MS instrument. The analysis of the complete dataset is performed using the positive matrix factorization approach, complemented by back-trajectory calculations using the Lagrangian transport model FLEXPART-AROME to identify mesoscale sources.

We present a source apportionment study of a near-continuous 2-year dataset of volatile organic compounds (VOCs), recorded between October 2017 and November 2019 with a quadrupole-based high-sensitivity proton-transfer-reaction mass-spectrometry (hs-PTR-MS) instrument deployed at the Maïdo observatory (21.1∘ S, 55.4∘ E, 2160 m altitude). The observatory is located on La Réunion island in the southwest Indian Ocean. We discuss seasonal and diel profiles of six key VOC species unequivocally linked to specific sources – acetonitrile (CH3CN), isoprene (C5H8), isoprene oxidation products (Iox), benzene (C6H6), C8-aromatic compounds (C8H10), and dimethyl sulfide (DMS). The data are analyzed using the positive matrix factorization (PMF) method and back-trajectory calculations based on the Lagrangian mesoscale transport model FLEXPART-AROME to identify the impact of different sources on air masses sampled at the observatory. As opposed to the biomass burning tracer CH3CN, which does not exhibit a typical diel pattern consistently throughout the dataset, we identify pronounced diel profiles with a daytime maximum for the biogenic (C5H8 and Iox) and anthropogenic (C6H6, C8H10) tracers. The marine tracer DMS generally displays a daytime maximum except for the austral winter when the difference between daytime and nighttime mixing ratios vanishes. Four factors were identified by the PMF: background/biomass burning, anthropogenic, primary biogenic, and secondary biogenic. Despite human activity being concentrated in a few coastal areas, the PMF results indicate that the anthropogenic source factor is the dominant contributor to the VOC load (38 %), followed by the background/biomass burning source factor originating in the free troposphere (33 %), and by the primary (15 %) and secondary biogenic (14 %) source factors. FLEXPART-AROME simulations showed that the observatory was most sensitive to anthropogenic emissions west of Maïdo while the strongest biogenic contributions coincided with air masses passing over the northeastern part of La Réunion. At night, the observatory is often located in the free troposphere, while during the day, the measurements are influenced by mesoscale sources. Interquartile ranges of nighttime 30 min average mixing ratios of methanol (CH3OH), CH3CN, acetaldehyde (CH3CHO), formic acid (HCOOH), acetone (CH3COCH3), acetic acid (CH3COOH), and methyl ethyl ketone (MEK), representative for the atmospheric composition of the free troposphere, were found to be 525–887, 79–110, 61–101, 172–335, 259–379, 64–164, and 11–21 pptv, respectively.

The presence of cows on a pasture considerably modifies exchanges of biogenic volatile organic compounds (BVOCs). By regulating the biomass present, they can have an impact on the constitutive flux (exchanges from soil and grass that are not induced by leaf wounding or trampling by cows) but they can also cause direct emissions from exhalation and indirect emissions by leaf injury (grazing), trampling and wastes. In this study conducted on the ICOS pasture site of Dorinne (Belgium), we disentangled these different sources/sinks for three oxygenated BVOCs commonly exchanged on grasslands (methanol, acetaldehyde and acetone), using a combination of turbulent flux measurements, enclosure flux measurements, tools to detect the presence and activity of cows in the footprint of the turbulent flux measurements and a flux footprint model. Direct exhalation emissions were low, representing only 2.3% and 10% of the spring total flux of methanol and acetone respectively. Comparison of grazed and non-grazed enclosures pointed out that emissions following leaf wounding were significant for all studied BVOCs, decreased exponentially with time to become negligible after maximum five days. Cow indirect emissions at the pasture scale (turbulent flux measurements) where likely dominated by grazing and were shown to be a major component of the total diurnal flux for each of the three studied BVOCs. Comparison with a hay meadow also showed that the temporal dynamics of those BVOC emissions were very different according to the grass management type, calling for specific parametrization in up-scaling emission models.

We present an investigation of biomass burning (BB) plumes originating from Africa and Madagascar based on measurements of a suite of volatile organic compounds (VOCs), carbon monoxide (CO), ozone (O3) and nitrogen dioxide (NO2) obtained during the dry season of 2018 and 2019 at the high-altitude Maïdo observatory (21.1∘ S, 55.4∘ E, 2160 ma.s.l.), located on the remote island of La Réunion in the south-west Indian Ocean (SWIO). Biomass burning plume episodes were identified from increased acetonitrile (CH3CN) mixing ratios. Enhancement ratios (EnRs) – relative to CO – were calculated from in situ measurements for CH3CN, acetone (CH3COCH3), formic acid (HCOOH), acetic acid (CH3COOH), benzene (C6H6), methanol (CH3OH) and O3. We compared the EnRs to emission ratios (ERs) – relative to CO – reported in the literature in order to estimate loss or production of these compounds during transport. For CH3CN and CH3COOH, the calculated EnRs are similar to the ERs. For C6H6 and CH3OH, the EnR is lower than the ER, indicating a net sink of these compounds which was found to be in line with the expected atmospheric lifetime. For CH3COCH3 and HCOOH, the calculated EnRs are larger than the ERs. The discrepancy reaches an order of magnitude for HCOOH (18–34 pptv ppbv−1 compared to 1.8–4.5 pptv ppbv−1). This points to significant secondary production of HCOOH during transport. The Copernicus Atmospheric Monitoring Service (CAMS) global model simulations reproduce the temporal variation of CO mixing ratios well at the observatory but underestimate O3 and NO2 mixing ratios in the plumes by on average 16 ppbv and 60 pptv respectively. This discrepancy between modelled and measured O3 mixing ratios was attributed to (i) large uncertainties in VOC and NOx (NO+NO2) emissions due to BB in CAMS and (ii) misrepresentation of NOx recycling in the model during transport. Finally, transport of pyrogenically emitted CO is calculated with FLEXPART in order to (i) determine the mean plume age during the intrusions at the observatory and (ii) estimate the impact of BB on the pristine marine boundary layer (MBL). By multiplying the excess CO in the MBL with inferred EnRs at the observatory, we calculated the expected impact of BB on CH3CN, CH3COCH3, CH3OH and C6H6 concentrations in the MBL. These excesses constitute increases of ∼20 %–150 % compared to background measurements in the SWIO MBL reported in the literature.

The Oxygenated Compounds in the Tropical Atmosphere: Variability and Exchanges (OCTAVE) campaign aimed to improve the assessment of the budget and role of oxygenated volatile organic compounds (OVOCs) in tropical regions, and especially over oceans, relying on an integrated approach combining in situ measurements, satellite retrievals, and modeling. As part of OCTAVE, volatile organic compounds (VOCs) were measured using a comprehensive suite of instruments on Reunion Island (21.07° S, 55.38° E) from 7 March to 2 May 2018. VOCs were measured at a receptor site at the Maïdo observatory during the entire campaign and at two source sites: Le Port from 19 to 24 April 2018 (source of anthropogenic emissions) and Bélouve from 25 April to 2 May 2018 (source of biogenic emissions) within a mobile lab. The Maïdo observatory is a remote background site located at an altitude of 2200 m, whereas Bélouve is located in a tropical forest to the east of Maïdo and Le Port is an urban area located northwest of Maïdo. The major objective of this study was to understand the sources and distributions of atmospheric formaldehyde (HCHO) in the Maïdo observatory on Reunion Island. To address this objective, two different approaches were used to quantify and determine the main drivers of HCHO at Maïdo. First, a chemical-kinetics-based (CKB) calculation method was used to determine the sources and sinks (biogenic, anthropogenic/primary, or secondary) of HCHO at the Maïdo site. The CKB method shows that 9% of the formaldehyde formed from biogenic emissions and 89% of HCHO had an unknown source; that is, the sources cannot be explicitly described by this method. Next, a positive matrix factorization (PMF) model was applied to characterize the VOC source contributions at Maïdo. The PMF analysis including VOCs measured at the Maïdo observatory shows that the most robust solution was obtained with five factors: secondary biogenic accounting for 17%, primary anthropogenic/solvents (24%), primary biogenic (14%), primary anthropogenic/combustion (22%), and background (23%). The main contributions to formaldehyde sources as described by the PMF model are secondary biogenic (oxidation of biogenic VOCs with 37%) and background (32%). Some assumptions were necessary concerning the high percentage of unknown HCHO sources of the CKB calculation method such as the biogenic emission factor resulting in large discrepancies between the two methods.

The understanding of biogenic volatile organic compound (BVOC) exchanges has become a key scientific issue because of their high reactivity and their impact in the atmosphere. However, so far, few studies have focused on BVOCs exchanged by agricultural species, and in particular by winter wheat, despite this species being the leading worldwide crop in terms of harvested area. This study for the first time investigated BVOC exchanges from winter wheat during most developmental stages of the plant. Fluxes were measured in Belgium at the ecosystem-scale using the disjunct eddy covariance by mass scanning technique, and a proton-transfer-reaction mass spectrometer for BVOC ambient mixing ratio measurements. As is usually observed for crops and grasses, the winter wheat field emitted mainly methanol, although bi-directional exchanges were observed. The second most exchanged compound was acetic acid which was captured during the entire growing season. Bi-directional exchanges of acetaldehyde and acetone were also reported. Terpene exchanges were 22 times smaller than oxygenated VOC (OVOC) exchanges. For all compounds, the exchanges were the most pronounced at the end of the growing season, i.e., under warm, dry and sunny conditions. Senescence-induced emissions were furthermore observed for methanol and acetaldehyde. For all investigated OVOCs, the exchanges very likely originated from both the soil and the plants. Despite their mixed origin, the MEGAN (Model of Emissions of Gases and Aerosols from Nature) v2.1 up-scaling model could adequately reproduce the methanol, acetaldehyde and acetone exchanges measured at this site during the mature and senescence phases of the plant, when the standard emission factor and the leaf age factor were adapted based on the measurements. In contrast, the model failed to reproduce the measured acetic acid exchanges. When the standard emission factor values currently assigned in MEGAN were applied, however, the exchanges were largely over-estimated for all compounds.