Dimethyl sulfide (DMS) plays an important role in the atmosphere by influencing the formation of aerosols and cloud condensation nuclei. In contrast, the role of methanethiol (MeSH) for the budget and flux of reduced sulfur remains poorly understood. In the present study, we quantified DMS and MeSH together with the trace gases carbon monoxide (CO), isoprene, acetone, acetaldehyde and acetonitrile in North Atlantic and Arctic Ocean surface waters, covering a transect from 57.2 to 80.9∘ N in high spatial resolution in May–June 2015. Whereas isoprene, acetone, acetaldehyde and acetonitrile concentrations decreased northwards, CO, DMS and MeSH retained substantial concentrations at high latitudes, indicating specific sources in polar waters. DMS was the only compound with a higher average concentration in polar (31.2 ± 9.3 nM) than in Atlantic waters (13.5 ± 2 nM), presumably due to DMS originating from sea ice. At eight sea-ice stations north of 80∘ N, in the diatom-dominated marginal ice zone, DMS and chlorophyll a markedly correlated (R2 = 0.93) between 0–50 m depth. In contrast to previous studies, MeSH and DMS did not co-vary, indicating decoupled processes of production and conversion. The contribution of MeSH to the sulfur budget (represented by DMS + MeSH) was on average 20 % (and up to 50 %) higher than previously observed in the Atlantic and Pacific oceans, suggesting MeSH as an important source of sulfur possibly emitted to the atmosphere. The potential importance of MeSH was underlined by several correlations with bacterial taxa, including typical phytoplankton associates from the Rhodobacteraceae and Flavobacteriaceae families. Furthermore, the correlation of isoprene and chlorophyll a with Alcanivorax indicated a specific relationship with isoprene-producing phytoplankton. Overall, the demonstrated latitudinal and vertical patterns contribute to understanding how concentrations of central marine trace gases are linked with chemical and biological dynamics across oceanic waters.

Levels and sources of non-Methane Hydrocarbons (NMHCs) were investigated at the urban background Thissio station, close to the historical center of Athens (Greece) from March 2016 to February 2017 (12 months), by means of an automated GC-FID. Alkanes dominated over aromatics and alkenes, with hourly mean levels ranging from detection limit up to 60 μg m-3 for i-pentane and 90 μg m-3 for toluene. Higher levels were recorded in the cold period relative to the warmer one. In addition, NMHCs seasonal diurnal cycles were characterized by a bimodal pattern, following the trend of tracers of anthropogenic sources. The Positive Matrix Factorization (PMF) was used for the allocation of NMHC to their sources. Five factors were identified and quantified, with traffic-related sources being the main one contributing up to 60% to total NMHCs, while biomass burning contributes up to 19%. A supplementary PMF assimilation was applied on a seasonal basis further including α-pinene, C6-C16 alkanes and aromatics. This PMF resulted to a seven-factor solution that allowed the examination of two additional sources, in addition to five already identified, highlighting the main contribution of anthropogenic sources (70%) to α-pinene.

In complex atmospheric emission environments such as urban agglomerates, multiple sources control the ambient chemical composition driving air quality and regional climate. In contrast to pristine sites, where reliance on single or a few chemical tracers is often adequate for resolving pollution plumes and source influences, the comprehensive chemical fingerprinting of sources using non-methane hydrocarbons (NMHCs) and the identification of suitable tracer molecules and emission ratios becomes necessary. Here, we characterise and present chemical fingerprints of some major urban and agricultural emission sources active in South Asia, such as paddy stubble burning, garbage burning, idling vehicular exhaust and evaporative fuel emissions. A total of 121 whole air samples were actively collected from the different emission sources in passivated air sampling steel canisters and then analysed for 49 NMHCs (22 alkanes, 16 aromatics, 10 alkenes and one alkyne) using thermal desorption gas chromatography flame ionisation detection. Several new insights were obtained. Propane was found to be present in paddy stubble fire emissions (8 %), and therefore, for an environment impacted by crop residue fires, the use of propane as a fugitive liquefied petroleum gas (LPG) emission tracer must be done with caution. Propene was found to be ∼ 1.6 times greater (by weight) than ethene in smouldering paddy fires. Compositional differences were observed between evaporative emissions of domestic LPG and commercial LPG, which are used in South Asia. While the domestic LPG vapours had more propane (40 ± 6 %) than n-butane (19 ± 2 %), the converse was true for commercial LPG vapours (7 ± 6 % and 37 ± 4 %, respectively). Isoprene was identified as a new tracer for distinguishing paddy stubble and garbage burning in the absence of isoprene emissions at night from biogenic sources. Analyses of source-specific inter-NMHC molar ratios revealed that toluene/benzene ratios can be used to distinguish among paddy stubble fire emissions in the flaming (0.38 ± 0.11) and smouldering stages (1.40 ± 0.10), garbage burning flaming (0.26 ± 0.07) and smouldering emissions (0.59 ± 0.16), and traffic emissions (3.54 ± 0.21), whereas i-pentane ∕ n-pentane can be used to distinguish biomass burning emissions (0.06–1.46) from the petrol-dominated traffic and fossil fuel emissions (2.83–4.13). i-butane ∕ n-butane ratios were similar (0.20–0.30) for many sources and could be used as a tracer for photochemical ageing. In agreement with previous studies, i-pentane, propane and acetylene were identified as suitable chemical tracers for petrol vehicular and evaporative emissions, LPG evaporative and vehicular emissions and flaming-stage biomass fires, respectively. The secondary pollutant formation potential and human health impact of the sources was also assessed in terms of their hydroxyl radical (OH) reactivity (s−1), ozone formation potential (OFP; gO3/gNMHC) and fractional benzene, toluene, ethylbenzene and xylenes (BTEX) content. Petrol vehicular emissions, paddy stubble fires and garbage fires were found to have a higher pollution potential (at ≥95 % confidence interval) relative to the other sources studied in this work. Thus, many results of this study provide a new foundational framework for quantitative source apportionment studies in complex emission environments.

Monoterpenes and isoprene are important constituents of the volatile organic compounds (VOCs) due to their high reactivity and participation in ozone and secondary aerosol formation. The current work focuses on the results of a 13-month intensive campaign of high resolution time-resolved measurements of these compounds, at an urban background site in Athens, Greece. On an annual basis, monoterpenes (alpha-pinene and limonene) surpass the isoprene levels presenting mean values of 0.70 +/- 0.83 mu g m(-3), 0.33 +/- 0.78 mu g m(-3) and 0.19 +/- 0.36 mu g m(-3), respectively. The large standard deviation highlights the significant diurnal and day-to-day variability. Isoprene presents a typical seasonal cycle, with a photochemically induced summer-time maximum. Enhanced noon levels are observed during summer, whereas a morning peak in the autumn and winter profiles occurs, depite the generally low levels encountered during these seasons. The monoterpenes deviate from the expected biogenic pattern, presenting higher mean levels during the cold period and a night-to-early morning enhancement strongly related to local anthropogenic tracers such as BC, CO, NO or toluene, as well as increased levels under wind speeds lower than 3 m s(-1). Estimations of the anthropogenic and biogenic fractions based on the enhancement ratios of a-pinene versus a variety of anthropogenic tracers, demonstrate a clear dominance of the anthropogenic sources in all studied seasons. Simultaneously, the biogenic fraction increased during summer relative to winter by more than 10 times. Both a-pinene and limonene significantly contribute to locally formed secondary organic aerosol (SOA), determined by means of an ACSM, accounting for at least 22% and 13% of their levels in summer and winter respectively. Additionally, monoterpenes and isoprene contribute 6% to the observed oxidants levels (O-3 + NOx) during summer.

As 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 biogenic species (isoprene and eight monoterpenes) and oxygenated 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 diurnal 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 isoprene 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 H2SO4 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 H2SO4 concentrations coupled with high BVOC concentrations seemed to be one of the most favorable conditions 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 tracers 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 anthropogenic 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 H2SO4 and isoprene 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.

Non-methane hydrocarbons (NMHCs) play an important role in atmospheric chemistry, contributing to ozone and secondary organic aerosol formation. They can also serve as tracers for various emission sources such as traffic, solvents, heating and vegetation. The current work presents, for the first time to our knowledge, time-resolved data of NMHCs, from two to six carbon atoms, for a period of 5 months (mid-October 2015 to mid-February 2016) in the greater Athens area (GAA), Greece. The measured NMHC levels are among the highest reported in the literature for the Mediterranean area during winter months, and the majority of the compounds demonstrate a remarkable day-to-day variability. Their levels increase by up to factor of 4 from autumn (October–November) to winter (December–February). Microscale meteorological conditions, especially wind speed in combination with the planetary boundary layer (PBL) height, seem to contribute significantly to the variability of NMHC levels, with an increase of up to a factor of 10 under low wind speed ( < 3 m s−1) conditions; this reflects the impact of local sources rather than long-range transport. All NMHCs demonstrated a pronounced bimodal, diurnal pattern with a morning peak followed by a second peak before midnight. The amplitude of both peaks gradually increased towards winter, in comparison to autumn, by a factor of 3 to 6 and closely followed that of carbon monoxide (CO), which indicates a contribution from sources other than traffic, e.g., domestic heating (fuel or wood burning). By comparing the NMHC diurnal variability with that of black carbon (BC), its fractions associated with wood burning (BCwb) and fossil fuel combustion (BCff), and with source profiles we conclude that the morning peak is attributed to traffic while the night peak is mainly attributed to heating. With respect to the night peak, the selected tracers and source profiles clearly indicate a contribution from both traffic and domestic heating (fossil fuel and wood burning). NMHCs slopes versus BCwb are similar when compared with those versus BCff (slight difference for ethylene), which indicates that NMHCs are most likely equally produced by wood and oil fossil fuel burning.

More than 7000 atmospheric measurements of over 60 C2 − C16 volatile organic compounds (VOCs) were conducted at a background site in Cyprus during a 1-month intensive field campaign held in March 2015. This exhaustive dataset consisted of primary anthropogenic and biogenic VOCs, including a wide range of source-specific tracers, and oxygenated VOCs (with various origins) that were measured online by flame ionization detection–gas chromatography and proton transfer mass spectrometry. Online submicron aerosol chemical composition was performed in parallel using an aerosol mass spectrometer. This study presents the high temporal variability in VOCs and their associated sources. A preliminary analysis of their time series was performed on the basis of independent tracers (NO, CO, black carbon), meteorological data and the clustering of air mass trajectories. Biogenic compounds were mainly attributed to a local origin and showed compound-specific diurnal cycles such as a daily maximum for isoprene and a nighttime maximum for monoterpenes. Anthropogenic VOCs as well as oxygenated VOCs displayed higher mixing ratios under the influence of continental air masses (i.e., western Asia), indicating that long-range transport significantly contributed to the VOC levels in the area. Source apportionment was then conducted on a database of 20 VOCs (or grouped VOCs) using a source receptor model. The positive matrix factorization and concentration field analyses were hence conducted to identify and characterize covariation factors of VOCs that were representative of primary emissions as well as chemical transformation processes. A six-factor PMF solution was selected, namely two primary biogenic factors (relative contribution of 43 % to the total mass of VOCs) for different types of emitting vegetation; three anthropogenic factors (short-lived combustion source, evaporative sources, industrial and evaporative sources; 21 % all together), identified as being either of local origin or from more distant emission zones (i.e., the south coast of Turkey); and a last factor (36 %) associated with regional background pollution (air masses transported both from the Western and Eastern Mediterranean regions). One of the two biogenic and the regional background factors were found to be the largest contributors to the VOC concentrations observed at our sampling site. Finally, a combined analysis of VOC PMF factors with source-apportioned organic aerosols (OAs) helped to better distinguish between anthropogenic and biogenic influences on the aerosol and gas phase compositions. The highest OA concentrations were observed when the site was influenced by air masses rich in semi-volatile OA (less oxidized aerosols) originating from the southwest of Asia, in contrast with OA factor contributions associated with the remaining source regions. A reinforcement of secondary OA formation also occurred due to the intense oxidation of biogenic precursors.

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 presented manuscript presents data on NMHCs and OVOCs from two sampling sites in Paris covering about 10 months of quasi-continuous measurements as well as on-site measurements at three potential major source categories. Since long-term datasets covering more than several weeks (usually obtained from short campaigns) are quite rare, in particular for combined NMHCs and OVOCs, this dataset is very valuable. However, the presented paper needs some major improvement before it can be considered for publication in ACP.

Les composés organiques volatils (COV) sont des composants clés en chimie atmosphérique. À l'échelle globale, on estime que 10 % ont une origine anthropique et 90 % une origine biogénique. L'impact des COV biogéniques (COVB), notamment sur la formation d'ozone (polluant et gaz à effet de serre) et d'aérosols organiques secondaires (à impact sanitaire et radiatif) en font un objet d'étude d'actualité. Toutefois, l'importance de l'impact des COVB sur la qualité de l'air est encore marquée par de larges incertitudes, en partie parce que les émissions demeurent mal quantifiées. Dans le cadre du projet Canopee, une campagne de mesure a eu lieu à l'O3HP, Observatoire du chêne pubescent à l'OHP (Observatoire de Haute-Provence), avec pour objectif de quantifier les émissions de COVB issues d'une forêt représentative de la région méditerranéenne. Des mesures de concentrations et de flux d'émission ont été réalisées à plusieurs échelles : de la branche à la canopée. L'étude des émissions à l'échelle du de la plante a permis une meilleure compréhension des paramètres environnementaux et physiologiques qui régissent les émissions. Les flux de COVB sortant de la canopée et exportés vers la troposphère ont pu être quantifiés. Les résultats montrent que le chêne blanc est un fort émetteur d'isoprène, mais un faible émetteur de méthanol et de monoterpènes. À l'échelle de la forêt, les flux d'émissions d'isoprène ont été estimés à 7,2 mg m-2 h-1 en conditions standard, ce qui fait de l'O3HP un des écosystèmes les plus fortement émetteurs d'isoprène à travers le monde.

Total OH reactivity, defined as the total loss frequency of the hydroxyl radical in the atmosphere, has proved to be an excellent tool to identify the total loading of reactive species in ambient air. High levels of unknown reactivity were found in several forests worldwide and were often higher than at urban sites.Our study presents atmospheric mixing ratios of biogenic compounds and total OH reactivity measured during late spring 2014 at the forest of downy oak trees of the Observatoire de Haute Provence (OHP), France. Air masses were sampled at two heights: 2 m, i.e., inside the canopy, and 10 m, i.e., above the canopy, where the mean canopy height is 5 m.We found that the OH reactivity at the site mainly depended on the main primary biogenic species emitted by the forest, which was isoprene and to a lesser extent by its degradation products and long-lived atmospheric compounds (up to 26 % during daytime). During daytime, no significant missing OH reactivity was reported at the site, either inside or above the canopy. However, during two nights we determined a missing fraction of OH reactivity up to 50 %, possibly due to unmeasured oxidation products. We confirmed that no significant oxidation of the primary species occurred within the canopy; primary compounds emitted by the forest were fast transported to the atmosphere. Finally, the OH reactivity at this site was maximum 69 s−1, which is a high value for a forest characterized by a temperate climate. Observations in various and diverse forests in the Mediterranean region are therefore needed to better constrain the impact of reactive gases over this area.

We propose an approach to estimate urban emission ratios that takes advantage of the enhanced local urban signal in the atmosphere at low wind speed. We apply it to estimate monthly ratios between CO2, CO and some VOCs from several atmospheric concentration measurement datasets acquired in the centre of Paris between 2010 and 2014. We find that this approach is not very sensitive to the regional background level definition and that, in the case of Paris, it samples all days (weekdays and weekends) and all hours of the day evenly. A large seasonal variability of the ΔCO ∕ ΔCO2 ratio in Paris is shown, with a difference of around 60 % between the extreme values and a strong anti-correlation (r2 = 0.75) with atmospheric temperature. The comparison of the ratios obtained for two short measurement campaigns conducted in two different districts and two different periods (autumn and winter) shows differences ranging from −120 to +63 %. A comparison with a highly resolved regional emission inventory suggests some spatial variations of the ratio within the city.

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).

Abstract. We propose a new approach to estimate urban emission ratios that takes advantage of the enhanced local urban signal in the atmosphere at low wind speed. We apply it to estimate monthly ratios between CO2, CO and some VOCs from several atmospheric concentration measurement datasets acquired in the centre of Paris between 2010 and 2014. We find that this approach is little sensitive to the regional background level definition and that, in the case of Paris, it samples all days (weekdays and weekends) and all hours of the day evenly. A large seasonal variability of the ΔCO/ΔCO2 ratio in Paris is shown, with a difference of around 60 % between the extreme values and a strong anti-correlation (r2 = 0.75) with atmospheric temperature. The comparison of the ratios obtained for two short measurement campaigns conducted in two different districts and two different periods (fall and winter) shows differences ranging from −120 to +63 %. A comparison with a highly resolved regional emission inventory suggests some spatial variations of the ratio within the city, although most of these differences seem to be rather driven by the seasonal variability.

Understanding the processes between the biosphere and the atmosphere is challenged by the difficulty to determine with enough accuracy the composition of the atmosphere. Total OH reactivity, which is defined as the total loss of the hydroxyl radical in the atmosphere, has proved to be an excellent tool to identify indirectly the important reactive species in ambient air. High levels of unknown reactivity were found in several forests worldwide and were often higher than at urban sites. Such results demonstrated the importance of OH reactivity for characterizing two of the major unknowns currently present associated to forests: the set of primary emissions from the canopy to the atmosphere and biogenic compounds oxidation pathways. Previous studies also highlighted the need to quantify OH reactivity and missing OH reactivity at more forested sites. Our study presents results of a field experiment conducted during late spring 2014 at the forest site at the Observatoire de Haute Provence, OHP, France. The forest is mainly composed of downy oak trees, a deciduous tree species characteristic of the Mediterranean region. We deployed the Comparative Reactivity Method and a set of state-of-the-art techniques such as Proton Transfer Reaction-Mass Spectrometry and Gas Chromatography to measure the total OH reactivity, the concentration of volatile organic compounds and main atmospheric constituents at the site. We sampled the air masses at two heights: 2 m, i.e. inside the canopy, and 10 m, i.e. above the canopy, where the mean canopy height is 5 m. We found that the OH reactivity at the site mainly depended on the main primary biogenic species emitted by the forest, which was isoprene and to a lesser extent by its degradation products and long lived atmospheric compounds (up to 26 % during daytime). We determined that the daytime total measured reactivity equaled the calculated reactivity obtained from the concentrations of the compounds measured at the site. Hence, no significant missing reactivity is reported in this specific site, neither inside, nor above the canopy. However, during two nights we reported a missing fraction of OH reactivity up to 50 %, possibly due to unmeasured oxidation products. Our results confirm the weak intra canopy oxidation, already suggested in a previous study focused on isoprene fluxes. They also demonstrate how helpful can be the OH reactivity as a tool to clearly characterize the suite of species present in the atmosphere. We show that our result of reactivity is among the highest reported in forests worldwide and stress the importance to quantify OH reactivity at more and diverse Mediterranean forests.

The hydroxyl radical (OH) plays a key role in the atmosphere, as it initiates most of the oxidation processes of volatile organic compounds (VOCs), and can ultimately lead to the formation of ozone and secondary organic aerosols (SOAs). There are still uncertainties associated with the OH budget assessed using current models of atmospheric chemistry and direct measurements of OH sources and sinks have proved to be valuable tools to improve our understanding of the OH chemistry. The total first order loss rate of OH, or total OH reactivity, can be directly measured using three different methods, such as the following: total OH loss rate measurement, laser-induced pump and probe technique and comparative reactivity method. Observations of total OH reactivity are usually coupled to individual measurements of reactive compounds in the gas phase, which are used to calculate the OH reactivity. Studies using the three methods have highlighted that a significant fraction of OH reactivity is often not explained by individually measured reactive compounds and could be associated to unmeasured or unknown chemical species. Therefore accurate and reproducible measurements of OH reactivity are required. The comparative reactivity method (CRM) has demonstrated to be an advantageous technique with an extensive range of applications, and for this reason it has been adopted by several research groups since its development. However, this method also requires careful corrections to derive ambient OH reactivity. Herein we present an intercomparison exercise of two CRM instruments, CRM-LSCE (Laboratoire des Sciences du Climat et de l'Environnement) and CRM-MD (Mines Douai), conducted during July 2013 at the Mediterranean site of Ersa, Cape Corsica, France. The intercomparison exercise included tests to assess the corrections needed by the two instruments to process the raw data sets as well as OH reactivity observations. The observation was divided in three parts: 2 days of plant emissions (8–9 July), 2 days of ambient measurements (10–11 July) and 2 days (12–13 July) of plant emissions. We discuss in detail the experimental approach adopted and how the data sets were processed for both instruments. Corrections required for the two instruments lead to higher values of reactivity in ambient air; overall 20 % increase for CRM-MD and 49 % for CRM-LSCE compared to the raw data. We show that ambient OH reactivity measured by the two instruments agrees very well (correlation described by a linear least squares fit with a slope of 1 and R2 of 0.75). This study highlights that ambient measurements of OH reactivity with differently configured CRM instruments yield consistent results in a low NOx (NO + NO2), terpene rich environment, despite differential corrections relevant to each instrument. Conducting more intercomparison exercises, involving more CRM instruments operated under different ambient and instrumental settings will help in assessing the variability induced due to instrument-specific corrections further.

On average, atmospheric CO2 increases in the atmosphere at a rate of about 2 parts per million (ppm) per year, due to the accumulation of about half of the anthropogenic CO2 emissions in the atmosphere (mostly from the combustion of fossil fuels), while the other half is being re-absorbed by the ocean and the continental biosphere. today, more than 70% of global fossil-fuel CO2 emissions come from punctual sources such as megacities. paris is the third megacity in europe and it emits about 15% of the total French emissions, while it covers only less than 2% of the national territory. Currently, most of the estimates of urban CO2 emissions are given by bottom-up CO2 emissions inventories, which rely on activity proxies and benchmarked emission factors. the associated uncertainties can be as high as several tenths of percents, especially when it comes to discriminate the CO2 urban emissions by emission sectors. therefore, there is an urgent need for developing new methods to better Monitoring, reporting and Veryfying (MrV) CO2 emissions from megacities, dedicated to provide robust results to policy makers for taking efficient decisions and actions in matter of controling CO2 anthropogenic emissions and mitigating climate change. since 2009, the CO2-Megaparis project aims to quantify CO2 emissions from paris using top-down approaches based on a synergy between atmospheric observations and modeling. For the first time, a mini-network of 3 greenhouse gases (GHG) monitoring stations was developed by lsCe in paris agglomeration within the infrastructure of the regional air quality monitoring agency, airpariF, completing 2 other GHG stations from the iCOs european greenhouse monitoring network. One of our urban station was located on top of the eiffel tower above paris megacity. the analysis of one year of data showed that paris CO2 emissions lead to a mean increase of the atmospheric CO2 concentration in the mid-afternoon of 2 to 3 ppm, and is strongly season, windspeed and wind direction dependent: the CO2 urban plume is characterized by a very large spatio-temporal variability and can reach about 60 ppm at low windspeeds on top of the eiffel tower. in addition, analysis of correlations between CO2, CO and 14C02 were carried out from field measurements and allowed an independent assessment of the inventories emission sectors. Furthermore, direct modeling of CO2 at a very fine resolution (2x2 km2, 1h) was performed and matched well with the observations. last but not least, inverse modeling efforts at the same resolution allowed a significant improvment of the regional inventory from airparif. Finally, a campaign conducted during springtime and based on lidar facilities revealed that due to the effect of the urban heat island, the boundary layer height (that can be seen on the first degree as the man dilution factor of CO2 emissions in the atmosphere), is 10 to 40% time higher in Paris than in surrounding rural areas: this is an important result that supports the implementation of urban canopy models in future fine scale urban CO2 modeling framework. a synthesis of the different results will be presented, as well as an attempt of defining the strengths and weaknesses of the atmospheric approach to quantify urban CO2 emissions. Contributions from sister studies (MultiCO2 - ipsl, le CO2 parisien - Ville de paris 2030, CarboCount-City - KiC Climat...) will also be mentionned.