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Aerosolized black carbon is monitored worldwide to quantify its impact on air quality and climate. Given its importance, measurements of black carbon mass concentrations must be conducted with instruments operating in quality-checked and ensured conditions to generate data which are reliable and comparable temporally and geographically. In this study, we report the results from the largest characterization and intercomparison of filter-based absorption photometers, the Aethalometer model AE33, belonging to several European monitoring networks. Under controlled laboratory conditions, a total of 23 instruments measured mass concentrations of black carbon from three well-characterized aerosol sources: synthetic soot, nigrosin particles, and ambient air from the urban background of Leipzig, Germany. The objective was to investigate the individual performance of the instruments and their comparability; we analyzed the response of the instruments to the different aerosol sources and the impact caused by the use of obsolete filter materials and the application of maintenance activities. Differences in the instrument-to-instrument variabilities from equivalent black carbon (eBC) concentrations reported at 880 nm were determined before maintenance activities (for soot measurements, average deviation from total least square regression was −2.0 % and the range −16 % to 7 %; for nigrosin measurements, average deviation was 0.4 % and the range −15 % to 17 %), and after they were carried out (for soot measurements, average deviation was −1.0 % and the range −14 % to 8 %; for nigrosin measurements, the average deviation was 0.5 % and the range −12 % to 15 %). The deviations are in most of the cases explained by the type of filter material employed by the instruments, the total particle load on the filter, and the flow calibration. The results of this intercomparison activity show that relatively small unit-to-unit variability of AE33-based particle light absorbing measurements is possible with well-maintained instruments. It is crucial to follow the guidelines for maintenance activities and the use of the proper filter tape in the AE33 to ensure high quality and comparable black carbon (BC) measurements among international observational networks.

The role of polar regions is increasing in terms of megatrends such as globalization, new transport routes, demography, and the use of natural resources with consequent effects on regional and transported pollutant concentrations. We set up the ERA-PLANET Strand 4 project “iCUPE – integrative and Comprehensive Understanding on Polar Environments” to provide novel insights and observational data on global grand challenges with an Arctic focus. We utilize an integrated approach combining in situ observations, satellite remote sensing Earth observations (EOs), and multi-scale modeling to synthesize data from comprehensive long-term measurements, intensive campaigns, and satellites to deliver data products, metrics, and indicators to stakeholders concerning the environmental status, availability, and extraction of natural resources in the polar areas. The iCUPE work consists of thematic state-of-the-art research and the provision of novel data in atmospheric pollution, local sources and transboundary transport, the characterization of arctic surfaces and their changes, an assessment of the concentrations and impacts of heavy metals and persistent organic pollutants and their cycling, the quantification of emissions from natural resource extraction, and the validation and optimization of satellite Earth observation (EO) data streams. In this paper we introduce the iCUPE project and summarize initial results arising out of the integration of comprehensive in situ observations, satellite remote sensing, and multi-scale modeling in the Arctic context.

The scope of this study was to estimate the contribution of fossil fuel and wood burning combustion to black carbon (BC) and carbon monoxide (CO) during wintertime, in Athens. For that purpose, in situ measurements of equivalent black carbon (eBC) and CO were simultaneously conducted in a suburban and an urban background monitoring site in Athens during the 3 months of winter 2014–2015. For the deconvolution of eBC into eBC emitted from fossil fuel (BCff) and wood burning (BCwb), a method based on the spectral dependency of the absorption of pure black carbon and brown carbon was used. Thereafter, BCwb and BCff estimated fractions were used along with measured CO concentrations in a multiple regression analysis, in order to quantify the contribution of each one of the combustion sources to the ambient CO levels. For a comparative analysis of the results, we additionally estimated the wood burning and fossil fuel contribution to CO, calculated on the basis of their CO ∕ NOx emission ratios. The results indicate that during wintertime BC and CO are mainly emitted by local sources within the Athens Metropolitan Area (AMA). Fossil fuel combustion, mainly from road traffic, is found to be the major contributor to both eBC in PM2.5 and CO ambient concentrations in AMA. However, wintertime wood burning makes a significant contribution to the observed eBC (of about 30 %) and CO concentrations (on average, 11 and 16 % of total CO in the suburban and urban background sites respectively). Both BC and CO from biomass burning (BCwb and COwb, respectively) present a clear diurnal pattern, with the highest concentrations during night-time, supporting the theory of local domestic heating being their main source.

Biogenic emission algorithms predict that oak forests account for ∼ 70 % of the total European isoprene budget. Yet the isoprene emission potentials (IEPs) that underpin these model estimates are calculated from a very limited number of leaf-level observations and hence are highly uncertain. Increasingly, micrometeorological techniques such as eddy covariance are used to measure whole-canopy fluxes directly, from which isoprene emission potentials can be calculated. Here, we review five observational datasets of isoprene fluxes from a range of oak forests in the UK, Italy and France. We outline procedures to correct the measured net fluxes for losses from deposition and chemical flux divergence, which were found to be on the order of 5–8 and 4–5 %, respectively. The corrected observational data were used to derive isoprene emission potentials at each site in a two-step process. Firstly, six commonly used emission algorithms were inverted to back out time series of isoprene emission potential, and then an average isoprene emission potential was calculated for each site with an associated uncertainty. We used these data to assess how the derived emission potentials change depending upon the specific emission algorithm used and, importantly, on the particular approach adopted to derive an average site-specific emission potential. Our results show that isoprene emission potentials can vary by up to a factor of 4 depending on the specific algorithm used and whether or not it is used in a big-leaf or canopy environment (CE) model format. When using the same algorithm, the calculated average isoprene emission potential was found to vary by as much as 34 % depending on how the average was derived. Using a consistent approach with version 2.1 of the Model for Emissions of Gases and Aerosols from Nature (MEGAN), we derive new ecosystem-scale isoprene emission potentials for the five measurement sites: Alice Holt, UK (10 500 ± 2500 µg m−2 h−1); Bosco Fontana, Italy (1610 ± 420 µg m−2 h−1); Castelporziano, Italy (121 ± 15 µg m−2 h−1); Ispra, Italy (7590 ± 1070 µg m−2 h−1); and the Observatoire de Haute Provence, France (7990 ± 1010 µg m−2 h−1). Ecosystem-scale isoprene emission potentials were then extrapolated to the leaf-level and compared to previous leaf-level measurements for Quercus robur and Quercus pubescens, two species thought to account for 50 % of the total European isoprene budget. The literature values agreed closely with emission potentials calculated using the G93 algorithm, which were 85 ± 75 and 78 ± 25 µg g−1 h−1 for Q. robur and Q. pubescens, respectively. By contrast, emission potentials calculated using the G06 algorithm, the same algorithm used in a previous study to derive the European budget, were significantly lower, which we attribute to the influence of past light and temperature conditions. Adopting these new G06 specific emission potentials for Q. robur (55 ± 24 µg g−1 h−1) and Q. pubescens (47 ± 16 µg g−1 h−1) reduced the projected European budget by ∼ 17 %. Our findings demonstrate that calculated isoprene emission potentials vary considerably depending upon the specific approach used in their calculation. Therefore, it is our recommendation that the community now adopt a standardised approach to the way in which micrometeorological flux measurements are corrected and used to derive isoprene, and other biogenic volatile organic compounds, emission potentials.

Total hydroxyl radical (OH) reactivity, the total loss frequency of the hydroxyl radical in ambient air, provides the total loading of OH reactants in air. We measured the total OH reactivity for the first time during summertime at a coastal receptor site located in the western Mediterranean Basin. Measurements were performed at a temporary field site located in the northern cape of Corsica (France), during summer 2013 for the project CARBOSOR (CARBOn within continental pollution plumes: SOurces and Reactivity)–ChArMEx (Chemistry and Aerosols Mediterranean Experiment). Here, we compare the measured total OH reactivity with the OH reactivity calculated from the measured reactive gases. The difference between these two parameters is termed missing OH reactivity, i.e., the fraction of OH reactivity not explained by the measured compounds. The total OH reactivity at the site varied between the instrumental LoD (limit of detection = 3 s−1) to a maximum of 17 ± 6 s−1 (35 % uncertainty) and was 5 ± 4 s−1 (1σ SD – standard deviation) on average. It varied with air temperature exhibiting a diurnal profile comparable to the reactivity calculated from the concentration of the biogenic volatile organic compounds measured at the site. For part of the campaign, 56 % of OH reactivity was unexplained by the measured OH reactants (missing reactivity). We suggest that oxidation products of biogenic gas precursors were among the contributors to missing OH reactivity.

The role that soil, foliage, and atmospheric dynamics have on surface carbonyl sulfide (OCS) exchange in a Mediterranean forest ecosystem in southern France (the Oak Observatory at the Observatoire de Haute Provence, O3HP) was investigated in June of 2012 and 2013 with essentially a top-down approach. Atmospheric data suggest that the site is appropriate for estimating gross primary production (GPP) directly from eddy covariance measurements of OCS fluxes, but it is less adequate for scaling net ecosystem exchange (NEE) to GPP from observations of vertical gradients of OCS relative to CO2 during the daytime. Firstly, OCS and carbon dioxide (CO2) diurnal variations and vertical gradients show no net exchange of OCS at night when the carbon fluxes are dominated by ecosystem respiration. This contrasts with other oak woodland ecosystems of a Mediterranean climate, where nocturnal uptake of OCS by soil and/or vegetation has been observed. Since temperature, water, and organic carbon content of soil at the O3HP should favor the uptake of OCS, the lack of nocturnal net uptake would indicate that its gross consumption in soil is compensated for by emission processes that remain to be characterized. Secondly, the uptake of OCS during the photosynthetic period was characterized in two different ways. We measured ozone (O3) deposition velocities and estimated the partitioning of O3 deposition between stomatal and non-stomatal pathways before the start of a joint survey of OCS and O3 surface concentrations. We observed an increasing trend in the relative importance of the stomatal pathway during the morning hours and synchronous steep drops of mixing ratios of OCS (amplitude in the range of 60–100 ppt) and O3 (amplitude in the range of 15–30 ppb) after sunrise and before the break up of the nocturnal boundary layer. The uptake of OCS by plants was also characterized from vertical profiles. However, the time window for calculation of the ecosystem relative uptake (ERU) of OCS, which is a useful tool for partitioning measured NEE, was limited in June 2012 to a few hours after midday. This was due to the disruption of the vertical distribution of OCS by entrainment of OCS rich tropospheric air in the morning and because the vertical gradient of CO2 reverses when it is still light. Moreover, polluted air masses (up to 700 ppt of OCS) produced dramatic variation in atmospheric OCS ∕ CO2 ratios during the daytime in June 2013, further reducing the time window for ERU calculation.

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).

We aimed at quantifying biogenic volatile organic compound (BVOC) emissions in June from three Mediterranean species located at the O3HP site (southern France): Quercus pubescens, Acer monspessulanum and C. coggygria (for isoprene only). As Q. pubescens was shown to be the main BVOC emitter with isoprene representing ≈ 99% of the carbon emitted as BVOC, we mainly focused on this species. C. coggygria was found to be a non-isoprene emitter (no other BVOCs were investigated). To fully understand both the canopy effect on Q. pubescens isoprene emissions and the inter-individual variability (tree to tree and within canopy), diurnal variations of isoprene were investigated from nine branches (seven branches located to the top of canopy at ≈ 4 m above ground level (a.g.l.), and two inside the canopy at ≈ 2 m a.g.l.). The Q. pubescens daily mean isoprene emission rate (ERd) fluctuated between 23 and 98 μgC gDM−1 h−1. Q. pubescens daily mean net assimilation (Pn) ranged between 5.4 and 13.8, and 2.8 and 6.4 μmol CO2 m−2 s−1 for sunlit and shaded branches respectively. Both ERd and isoprene emission factors (Is), assessed according to Guenther et al. (1993) algorithm, varied by a factor of 4.3 among the sunlit branches. While sunlit branches ERd was clearly higher than for shaded branches, there was a non-significant variability of Is (59 to 77 μgC gDM−1 h−1). Diurnal variations of isoprene emission rates (ERs) for sunlit branches were also investigated. ERs were detected at dawn 2 h after Pn became positive and were mostly exponentially dependent on Pn. Diurnal variations of ERs were not equally well described throughout the day by temperature (CT) and light (CL) parameters according to G93 algorithm. Temperature had more impact than photosynthetically active radiation (PAR) on the morning emissions increase, and ER was no longer correlated to CL × CT between solar noon (maximum ER) and mid-afternoon, possibly due to thermal stress of the plant. A comparison between measured and calculated emissions using two isoprene algorithms (G93 and MEGAN – Model of Emissions of Gases and Aerosols from Nature) highlighted the importance of isoprene emission factor Is value used, and some weakness in assessing isoprene emissions under Mediterranean climate conditions (drought) with current isoprene models.

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.