Abstract. 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.

Abstract. The FLEXible PARTicle dispersion model FLEXPART, first released in 1998, is a Lagrangian particle dispersion model developed to simulate atmospheric transport over large and mesoscale distances. Due to FLEXPART's success and its open source nature, different limited area model versions of FLEXPART were released making it possible to run FLEXPART simulations by ingesting WRF (Weather Research Forecasting model), COSMO (Consortium for Small-scale Modeling) or MM5 (mesoscale community model maintained by Penn State university) meteorological fields on top of the ECMWF (European Centre for Medium-Range Weather Forecasts) and GFS (Global Forecast System) meteorological fields. Here, we present a new FLEXPART limited area model that is compatible with the AROME mesoscale meteorological forecast model (the Applications of Research to Operations at Mesoscale model).1 FLEXPART-AROME was originally developed to study mesoscale transport around La Réunion, a small volcanic island in the southwest Indian Ocean with a complex orographic structure, which is not well represented in current global operational models. We present new turbulent modes in FLEXPART-AROME. They differ from each other by dimensionality, mixing length parameterization, turbulent transport constraint interpretation and time step configuration. A novel time step was introduced in FLEXPART-AROME. Performances of new turbulent modes are compared to the ones in FLEXPART-WRF by testing the conservation of well-mixedness by turbulence, the dispersion of a point release at the surface and the marine boundary layer evolution around Réunion. The novel time step configuration proved necessary to conserve the well-mixedness in the new turbulent modes. An adaptive vertical turbulence time step was implemented, allowing the model to adapt on a finer timescale when significant changes in the local turbulent state of the atmosphere occur.

Abstract. 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, 2,160 m altitude). The observatory is located on La Réunion island in the south-west 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-aromatics (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 recorded at the observatory. As opposed to the biomass burning tracer CH3CN, which does not exhibit a consistent diel variability, 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 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 sources (14 %). FLEXPART-AROME simulations showed that the observatory was most sensitive to anthropogenic emissions west of Maïdo while the strongest biogenic contributions coincided with airmasses passing over the north-eastern 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-minute average concentrations 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 pptv, 79–110 pptv, 61–101 pptv, 172–335 pptv, 259–379 pptv, 64–164 and 11–21 pptv, respectively.

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.

Abstract. 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.

Trends of formaldehyde (HCHO) linked to anthropogenic activity over large cities located in the Asian continent are calculated for the period 2005–2019 using the Quality Assurance for Essential Climate Variables (QA4ECV) dataset from the Ozone Monitoring Instrument (OMI) aboard the Aura satellite. Contributions due to anthropogenic emissions are isolated by applying a correction based on near-surface temperature in order to account for interference from local biogenic emissions. Strong positive trends are derived over the Middle East and the Indian subcontinent (up to 3.6% yr-1 and 2.4% yr-1 respectively) where regulations of anthropogenic non-methane volatile organic compound (NMVOC) emissions are currently limited. Weaker trends are observed over cities located in China, where the air pollution action plan (2013) may have mitigated NMVOC trends early on, but targeted legislature concerning VOC emissions was only recently introduced. HCHO trends for cities located in South and Equatorial Asia are mostly not significant or very uncertain. Cities located in Taiwan and Japan (regions in Asia where legislation has been in place since the early 2000s) display mostly negative trends.

Abstract. The FLEXible PARTicle dispersion model FLEXPART, first released in 1998, is a Lagrangian particle dispersion model developed to simulate atmospheric transport over large and meso-scale distances. Due to FLEXPART's success and its open source nature, different limited area model versions of FLEXPART were released making it possible to run FLEXPART simulations by ingesting WRF (Weather Research Forecasting model) or MM5 (meso-scale community model maintained by Penn State university) meteorological fields on top of the ECMWF (European Centre for Medium-Range Weather Forecasts) and GFS (Global Forecast System) meteorological fields. Here, we present a new FLEXPART limited area model that is compatible with the AROME mesoscale meteorological forecast model (the Applications of Research to Operations at Meso-scale model). FLEXPART-AROME was originally developed to study meso-scale transport around La Réunion, a small volcanic island in the South West Indian Ocean with a complex orographic structure which is not well represented in current global operational models. The AROME vertical hybrid sigma grid is projected on the Cartesian terrain following FLEXPART grid. We present new turbulent modes in FLEXPART-AROME. They differ from each other by: dimensionality, mixing length parameterisation, turbulent transport constraint interpretation and a novel time-step configuration. Performances of new turbulent modes are compared to the ones in FLEXPART-WRF by testing the conservation of well-mixedness by turbulence, the dispersion of a point release at the surface and the marine boundary layer evolution around Reunion island. An adaptive time step for the vertical turbulent motions has been implemented to improve conservation of well-mixedness in the model.

Abstract. The tropical and subtropical Indian Ocean (IO) is expected to be a significant source of water-soluble organic aerosols (WSOAs), which are important factors relevant to cloud formation of aerosol particles. Current atmospheric numerical models significantly underestimate the budget of organic aerosols and their precursors, especially over tropical oceans. This is primarily due to poor knowledge of sources and the paucity of observations of these parameters considering spatial and temporal variation over the tropical open ocean. To evaluate the contribution of sources to WSOA as well as their formation processes, submicrometer aerosol sampling was conducted at the high-altitude Maïdo observatory (21.1∘ S, 55.4∘ E; 2160 m a.s.l.), located on the remote island of La Réunion in the southwest IO. The aerosol samples were continuously collected during local daytime and nighttime, which corresponded to the ambient conditions of the marine boundary layer (MBL) and free troposphere (FT), respectively, from 15 March to 24 May 2018. Chemical analysis showed that organic matter was the dominant component of submicrometer water-soluble aerosol (∼ 45 ± 17 %) during the wet season (15 March–23 April). On the other hand, sulfate dominated (∼ 77 ± 17 %) during the dry season (24 April–24 May), most of which was attributable to the effect of volcanic eruption. Measurements of the stable carbon isotope ratio of water-soluble organic carbon (WSOC) suggested that marine sources contributed significantly to the observed WSOC mass in both the MBL and the FT in the wet season, whereas a mixture of marine and terrestrial sources contributed to WSOC in the dry season. The distinct seasonal changes in the dominant source of WSOC were also supported by Lagrangian trajectory analysis. Positive matrix factorization analysis suggested that marine secondary organic aerosol (OA) dominantly contributed to the observed WSOC mass (∼ 70 %) during the wet season, whereas mixtures of marine and terrestrial sources contributed during the dry season in both MBL and FT. Overall, this study demonstrates that the effect of marine secondary sources is likely important up to the FT in the wet season, which may affect cloud formation as well as direct radiative forcing over oceanic regions.