Concentrations and fluxes of isoprene and oxygenated VOCs at a French Mediterranean oak forest

The CANOPEE project aims to better understand the biosphere–atmosphere exchanges of biogenic volatile organic compounds (BVOCs) in the case of Mediterranean ecosystems and the impact of in-canopy processes on the atmospheric chemical composition above the canopy. Based on an intensive field campaign, the objective of our work was to determine the chemical composition of the air inside a canopy as well as the net fluxes of reactive species between the canopy and the boundary layer. Measurements were carried out during spring 2012 at the field site of the Oak Observatory of the Observatoire de Haute Provence (O3HP) located in the southeast of France. The site is a forest ecosystem dominated by downy oak, Quercus pubescens Willd., a typical Mediterranean species which features large isoprene emission rates. Mixing ratios of isoprene, its degradation products methylvinylketone (MVK) and methacrolein (MACR) and several other oxygenated VOC (OxVOC) were measured above the canopy using an online proton transfer reaction mass spectrometer (PTR-MS), and fluxes were calculated by the disjunct eddy covariance approach. The O3HP site was found to be a very significant source of isoprene emissions, with daily maximum ambient concentrations ranging between 2–16 ppbv inside and 2–5 ppbv just above the top of the forest canopy. Significant isoprene fluxes were observed only during daytime, following diurnal cycles with midday net emission fluxes from the canopy ranging between 2.0 and 9.7 mg m−2 h1. Net isoprene normalized flux (at 30 °C, 1000 μmol quanta m−2 s−1) was estimated at 7.4 mg m−2 h−1. Evidence of direct emission of methanol was also found exhibiting maximum daytime fluxes ranging between 0.2 and 0.6 mg m−2 h−1, whereas flux values for monoterpenes and others OxVOC such as acetone and acetaldehyde were below the detection limit. The MVK+MACR-to-isoprene ratio provided useful information on the oxidation of isoprene, and is in agreement with recent findings proposing weak production yields of MVK and MACR, in remote forest regions where the NOx concentrations are low. In-canopy chemical oxidation of isoprene was found to be weak and did not seem to have a significant impact on isoprene concentrations and fluxes above the canopy

ACTRIS ACSM intercomparison – Part 1: Reproducibility of concentration and fragment results from 13 individual Quadrupole Aerosol Chemical Speciation Monitors (Q-ACSM) and consistency with co-located instruments

As part of the European ACTRIS project, the first large Quadrupole Aerosol Chemical Speciation Monitor (Q-ACSM) intercomparison study was conducted in the region of Paris for 3 weeks during the late-fall – early-winter period (November–December 2013). The first week was dedicated to the tuning and calibration of each instrument, whereas the second and third were dedicated to side-by-side comparison in ambient conditions with co-located instruments providing independent information on submicron aerosol optical, physical, and chemical properties. Near real-time measurements of the major chemical species (organic matter, sulfate, nitrate, ammonium, and chloride) in the non-refractory submicron aerosols (NR-PM1) were obtained here from 13 Q-ACSM. The results show that these instruments can produce highly comparable and robust measurements of the NR-PM1 total mass and its major components. Taking the median of the 13 Q-ACSM as a reference for this study, strong correlations (r2 > 0.9) were observed systematically for each individual Q-ACSM across all chemical families except for chloride for which three Q-ACSMs showing weak correlations partly due to the very low concentrations during the study. Reproducibility expanded uncertainties of Q-ACSM concentration measurements were determined using appropriate methodologies defined by the International Standard Organization (ISO 17025, 1999) and were found to be 9, 15, 19, 28, and 36 % for NR-PM1, nitrate, organic matter, sulfate, and ammonium, respectively. However, discrepancies were observed in the relative concentrations of the constituent mass fragments for each chemical component. In particular, significant differences were observed for the organic fragment at mass-to-charge ratio 44, which is a key parameter describing the oxidation state of organic aerosol. Following this first major intercomparison exercise of a large number of Q-ACSMs, detailed intercomparison results are presented, along with a discussion of some recommendations about best calibration practices, standardized data processing, and data treatment.JRC.H.2-Air and Climat

Spatial and temporal variations in the distribution of birch trees and airborne Betula pollen in Ireland

In an Irish context, and indeed in Northern Europe, one of the most important allergenic pollen types is birch (Betula spp.). Thus, forecasts of such atmospheric pollen are important tools for helping patients suffering from allergenic rhinitis and/or atopic asthma to avoid high ambient concentrations and manage their symptoms. This work aims to improve knowledge about the spatial and temporal variations in the distribution of birch trees and airborne Betula pollen in Ireland, which is an important step towards producing such forecasts. The footprint of airborne Betula pollen recorded in Ireland was determined by using HYSPLIT backward Lagrangian dispersion modelling methodology and mapped using Geographic Information System (GIS) software during the Main Pollen Season (MPS) and for days with airborne concentrations > 80 pollen grains/m3 in Dublin and Carlow (72 km apart) for 2018 and 2019. An inventory of birch trees within broadleaved forests was constructed using statistical data from different vegetation inventories for Ireland with a resolution of 100 m x 100 m. Historical datasets of airborne Betula pollen recorded in Dublin during 1978-1980 and 2010-2011 were also related to changes in land cover and climatic conditions over the same period. Dispersion modelling showed that air masses arriving in Ireland on days with Betula pollen concentrations >80 pollen grains/m3 resided for a longer time over Great Britain. The birch tree inventory for Ireland will enhance the performance of forecast models. Airborne Betula pollen concentrations in Ireland have increased over the last 40 years, which is related to concomitant increases in the fraction of birch trees in forest areas as well as the ornamental use of birch trees in urban areas and their reaching maturity. Climate change did not seem to influence birch pollination

Global modelling of direct and indirect effects of sea spray aerosol using a source function encapsulating wave state

International audienceRecently developed parameterizations for the sea spray aerosol source flux, encapsulating wave state, and its organic fraction were incorporated into the aerosol–climate model ECHAM-HAMMOZ to investigate the direct and indirect radiative effects of sea spray aerosol particles. Our simulated global sea salt emission of 805 Tg yr−1 (uncertainty range 378–1233 Tg yr−1) was much lower than typically found in previous studies. Modelled sea salt and sodium ion concentrations agreed relatively well with measurements in the smaller size ranges at Mace Head (annual normalized mean model bias −13% for particles with vacuum aerodynamic diameter Dva < 1 μm), Point Reyes (−29% for particles with aerodynamic diameter Da < 2.5 μm) and Amsterdam Island (−52% for particles with Da < 1 μm) but the larger sizes were overestimated (899% for particles with 2.5 μm < Da < 10 μm) at Amsterdam Island. This suggests that at least the high end of the previous estimates of sea spray mass emissions is unrealistic. On the other hand, the model clearly underestimated the observed concentrations of organic or total carbonaceous aerosol at Mace Head (−82%) and Amsterdam Island (−68%). The large overestimation (212%) of organic matter at Point Reyes was due to the contribution of continental sources. At the remote Amsterdam Island site, the organic concentration was underestimated especially in the biologically active months, suggesting a need to improve the parameterization of the organic sea spray fraction. Globally, the satellite-retrieved AOD over the oceans, using PARASOL data, was underestimated by the model (means over ocean 0.16 and 0.10, respectively); however, in the pristine region around Amsterdam Island the measured AOD fell well within the simulated uncertainty range. The simulated sea spray aerosol contribution to the indirect radiative effect was positive (0.3 W m−2), in contrast to previous studies. This positive effect was ascribed to the tendency of sea salt aerosol to suppress both the in-cloud supersaturation and the formation of cloud condensation nuclei from sulfate. These effects can be accounted for only in models with sufficiently detailed aerosol microphysics and physics-based parameterizations of cloud activation. However, due to a strong negative direct effect, the simulated effective radiative forcing (total radiative) effect was −0.2 W m−2. The simulated radiative effects of the primary marine organic emissions were small, with a direct effect of 0.03 W m−2 and an indirect effect of −0.07 W m−2

Effect of agricultural practices on volatile organic compound (VOC) emissions from winter wheat

International audienceDespite the important land cover of crops, biogenic volatile organic compounds (BVOCs) emissions from agricultural areas remain poorly characterized, especially from field experiments. There is even less knowledge about the effect of agricultural practices (fertilization, pesticide spreading, etc.) on these emissions. The global aim of the present study is to reinforce our knowledge on BVOC emissions from agricultural crops. A field campaign was carried out at a measurement station located at Grignon ICOS site(France), 40 km southwest from Paris. The goal of the study was i) to quantify BVOC fluxes over a wheat stand and ii) to evaluate the effect of agricultural practices (manure and pesticide spreading) on these emissions. The experimental set-up consisted in measuring eddy covariance fluxes of momentum, latent and sensible heat, CO2 and BVOCs (with a PTR-Qi-TOF-MS - national instrument within the ANAEE-France framework). Results show that methanol was the most emitted BVOC, in agreement with few reported studies about wheat. Immediately after manure spreading, an increase of emissions of several compounds was observed. Especially, m/z 109.06 (C7H8O), which was previously characterized as strongly emitted by liquid manure, was observed in the field. We also report the first online measurement of pesticide with a PTR-Qi-TOF-MS. The spread fungicide Chlorothalonil was surprisingly still detected in the gas phase 21 days after spreading. Our results provide new insights in BVOC emissions from crops and the effect of pesticide and manure spreading on these emissions

ACTRIS ACSM intercomparison - Part 1: Reproducibility of concentration and fragment results from 13 individual Quadrupole Aerosol Chemical Speciation Monitors (Q-ACSM) and consistency with co-located instruments

As part of the European ACTRIS project, the first large Quadrupole Aerosol Chemical Speciation Monitor (Q-ACSM) intercomparison study was conducted in the region of Paris for 3 weeks during the late-fall - early-winter period (November-December 2013). The first week was dedicated to the tuning and calibration of each instrument, whereas the second and third were dedicated to side-by-side comparison in ambient conditions with co-located instruments providing independent information on submicron aerosol optical, physical, and chemical properties. Near real-time measurements of the major chemical species (organic matter, sulfate, nitrate, ammonium, and chloride) in the non-refractory submicron aerosols (NR-PM) were obtained here from 13 Q-ACSM. The results show that these instruments can produce highly comparable and robust measurements of the NR-PM total mass and its major components. Taking the median of the 13 Q-ACSM as a reference for this study, strong correlations (r > 0.9) were observed systematically for each individual Q-ACSM across all chemical families except for chloride for which three Q-ACSMs showing weak correlations partly due to the very low concentrations during the study. Reproducibility expanded uncertainties of Q-ACSM concentration measurements were determined using appropriate methodologies defined by the International Standard Organization (ISO 17025, 1999) and were found to be 9, 15, 19, 28, and 36 % for NR-PM, nitrate, organic matter, sulfate, and ammonium, respectively. However, discrepancies were observed in the relative concentrations of the constituent mass fragments for each chemical component. In particular, significant differences were observed for the organic fragment at mass-to-charge ratio 44, which is a key parameter describing the oxidation state of organic aerosol. Following this first major intercomparison exercise of a large number of Q-ACSMs, detailed intercomparison results are presented, along with a discussion of some recommendations about best calibration practices, standardized data processing, and data treatment

Seasonal variability and source apportionment of volatile organic compounds (VOCs) in the Paris megacity (France)

Within the framework of air quality studies at the megacity scale, highly time-resolved volatile organic compound (C₂–C₈) measurements were performed in downtown Paris (urban background sites) from January to November 2010. This unique dataset included non-methane hydrocarbons (NMHCs) and aromatic/oxygenated species (OVOCs) measured by a GC-FID (gas chromatograph with a flame ionization detector) and a PTR-MS (proton transfer reaction – mass spectrometer), respectively. This study presents the seasonal variability of atmospheric VOCs being monitored in the French megacity and their various associated emission sources. Clear seasonal and diurnal patterns differed from one VOC to another as the result of their different origins and the influence of environmental parameters (solar radiation, temperature). Source apportionment (SA) was comprehensively conducted using a multivariate mathematical receptor modeling. The United States Environmental Protection Agency's positive matrix factorization tool (US EPA, PMF) was used to apportion and quantify ambient VOC concentrations into six different sources. The modeled source profiles were identified from near-field observations (measurements from three distinct emission sources: inside a highway tunnel, at a fireplace and from a domestic gas flue, hence with a specific focus on road traffic, wood-burning activities and natural gas emissions) and hydrocarbon profiles reported in the literature. The reconstructed VOC sources were cross validated using independent tracers such as inorganic gases (NO, NO₂, CO), black carbon (BC) and meteorological data (temperature). The largest contributors to the predicted VOC concentrations were traffic-related activities (including motor vehicle exhaust, 15 % of the total mass on the annual average, and evaporative sources, 10 %), with the remaining emissions from natural gas and background (23 %), solvent use (20 %), wood-burning (18 %) and a biogenic source (15 %). An important finding of this work is the significant contribution from wood-burning, especially in winter, where it could represent up to  ∼  50 % of the total mass of VOCs. Biogenic emissions also surprisingly contributed up to  ∼  30 % in summer (due to the dominating weight of OVOCs in this source). Finally, the mixed natural gas and background source exhibited a high contribution in spring (35 %, when continental air influences were observed) and in autumn (23 %, for home heating consumption)

Driving parameters of biogenic volatile organic compounds and consequences on new particle formation observed at an eastern Mediterranean background site

International audienceAs a part of the Chemistry-Aerosol Mediterranean Experiment (ChArMEx) and Cyprus Aerosols and Gas Precursors (ENVI-Med CyAr) programs, this study aims primarily to provide an improved understanding of the sources and the fate of volatile organic compounds (VOCs) in the eastern Mediterranean. More than 60 VOCs, including bio-genic species (isoprene and eight monoterpenes) and oxy-genated VOCs, were measured during a 1-month intensive field campaign performed in March 2015 at the Cyprus Atmospheric Observatory (CAO), a regional background site in Cyprus. VOC measurements were conducted using complementary online and offline techniques. Biogenic VOCs (BVOCs) were principally imputed to local sources and characterized by compound-specific daily cycles such as diur-nal maximum for isoprene and nocturnal maximum for α-and β-pinenes, in connection with the variability of emission sources. The simultaneous study of pinene and iso-prene temporal evolution and meteorological parameters has shown that BVOC emissions were mainly controlled by ambient temperature, precipitation and relative humidity. It was found that isoprene daytime emissions at CAO depended on temperature and solar radiation changes, whereas nocturnal BVOC concentrations (e.g., from oak and pine forests) were more prone to the relative humidity and temperature changes. Significant changes in monoterpene mixing ratios occurred during and after rainfall. The second part of the study focused on new particle formation (NPF) events at CAO. BVOCs are known to potentially play a role in the growth as well as in the early stages of formation of new atmospheric particles. Based on observations of the particle size distribution performed with a differential mobility particle sizer (DMPS) and the total number concentrations of particles larger than 1 nm diameter measured by particle size magnifier (PSM), NPF events were found on 14 out of 20 days of the field campaign. For all possible proxy parameters (meteorological parameters, calculated H 2 SO 4 and measured gaseous compounds) having a role in NPF, we present daily variations of different classes during nucleation event and non-event days. NPF can occur at various condensational sink (CS) values and both under polluted and clean atmospheric conditions. High H 2 SO 4 concentrations coupled with high BVOC concentrations seemed to be one of the most favorable conditions Published by Copernicus Publications on behalf of the European Geosciences Union. 14298 C. Debevec et al.: Biogenic VOCs at an eastern Mediterranean background site to observe NPF at CAO in March 2015. NPF event days were characterized by either (1) a predominant anthropogenic influence (high concentrations of anthropogenic source trac-ers observed), (2) a predominant biogenic influence (high BVOC concentrations coupled with low anthropogenic tracer concentrations), (3) a mixed influence (high BVOC concentrations coupled with high anthropogenic tracer concentrations) and (4) a marine influence (both low BVOC and an-thropogenic tracer concentrations). More pronounced NPF events were identified during mixed anthropogenic-biogenic conditions compared to the pure anthropogenic or biogenic ones, for the same levels of precursors. Analysis of a specific NPF period of the mixed influence type highlighted that BVOC interactions with anthropogenic compounds enhanced nucleation formation and growth of newly formed particles. During this period, the nucleation-mode particles may be formed by the combination of high H 2 SO 4 and iso-prene amounts, under favorable meteorological conditions (high temperature and solar radiation and low relative humidity) along with low CS. During the daytime, growth of the newly formed particles, not only sulfate but also oxygen-like organic aerosol (OOA) mass contributions, increased in the particle phase. High BVOC concentrations were observed during the night following NPF events, accompanied by an increase in CS and in semi-volatile OOA contributions, suggesting further BVOC contribution to aerosol nighttime growth by condensing onto pre-existing aerosols

Origin and variability in volatile organic compounds observed at an Eastern Mediterranean background site (Cyprus)

International audienc