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Water resources management relies on the use of hydrometric data collected mainly from in situ stations. Despite the efforts made in setting up and maintaining a network of hydrometric and meteorological stations, water resource managers face many problems, such as equipment degradation during floods, incidents of vandalism and issues related to inaccessibility. Satellite data can improve water resources monitoring, regardless of its objectives (strategic management of water resources, management of structures, forecasting of floods and low flows, etc.). These data have the advantage of covering the entire world at regular intervals, including difficult-to-access areas. Through several projects, various scientific and industrial partners (IRD, CNES, CLS, CNRS, CENEAU, etc.) have contributed to assess and enhance the use of satellite data for the management of water resources at the scale of a catchment (e.g. the Amazon) or a territory (Uganda). The objective is to deliver a method based on the combination of hydrological models, in-situ data and satellite data. This article presents the current possibilities and limitations of using satellite data to optimize the monitoring of water resources.

In agricultural areas, the downstream flow can be highly influenced by human activities during low-flow periods, especially during dam releases and irrigation withdrawals. Irrigation is indeed the major use of freshwater in the world. This study aims at precisely taking these factors into account in a watershed model. The Soil and Water Assessment Tool (SWAT+) agro-hydrological model was chosen for its capacity to model crop dynamics and management. Two different crop models were compared in terms of their ability to estimate water needs and actual irrigation. The first crop model is based on air temperature as the main determining factor for growth, whereas the second relies on high-resolution data from the Sentinel-2 satellite to monitor plant growth. Both are applied at the plot scale in a watershed of 800 km2 that is characterized by irrigation withdrawals. Results show that including remote sensing data leads to more realistic modeled emergence dates for summer crops. However, both approaches have proven to be able to reproduce the evolution of daily irrigation withdrawals throughout the year. As a result, both approaches allowed us to simulate the downstream flow with a good daily accuracy, especially during low-flow periods.

The geographical origin and source apportionment of submicron carbonaceous aerosols (organic aerosols, OAs, and black carbon, BC) have been investigated here for the first time, deploying high time-resolution measurements at an urban background site of Nicosia, the capital city of Cyprus, in the eastern Mediterranean. This study covers a half-year period, encompassing both the cold and warm periods with continuous observations of the physical and chemical properties of PM1 performed with an Aerosol Chemical Speciation Monitor (ACSM), an aethalometer, accompanied by a suite of various ancillary offline and online measurements. Carbonaceous aerosols were dominant during both seasons (cold and warm periods), with a contribution of 57 % and 48 % to PM1, respectively, and exhibited recurrent intense nighttime peaks (> 20–30 µg m−3) during the cold period, associated with local domestic heating. The findings of this study show that high concentrations of sulfate (close to 3 µg m−3) were continuously recorded, standing among the highest ever reported for Europe and originating from the Middle East region. Source apportionment of the OA and BC fractions was performed using the positive matrix factorization (PMF) approach and the combination of two models (aethalometer model and multilinear regression), respectively. Our study revealed elevated hydrocarbon-like organic aerosol (HOA) concentrations in Nicosia (among the highest reported for a European urban background site), originating from a mixture of local and regional fossil fuel combustion sources. Although air masses from the Middle East had a low occurrence and were observed mostly during the cold period, they were shown to strongly affect the mean concentrations levels of BC and OA in Nicosia during both seasons. Overall, the present study brings to our attention the need to further characterize primary and secondary carbonaceous aerosols in the Middle East, an undersampled region characterized by continuously increasing fossil fuel (oil and gas) emissions and extreme environmental conditions, which can contribute to photochemical ageing.

Reaction of stabilized Criegee intermediates (SCIs) with SO2 was proposed as an additional pathway of gaseous sulfuric acid (H2SO4) formation in the atmosphere, supplementary to the conventional mechanism of H2SO4 production by oxidation of SO2 in reaction with OH radicals. However, because of a large uncertainty in mechanism and rate coefficients for the atmospheric formation and loss reactions of different SCIs, the importance of this additional source is not well established. In this work, we present an estimation of the role of SCIs in H2SO4 formation at a western Mediterranean (Cape Corsica) remote site, where comprehensive field observations including gas-phase H2SO4, OH radicals, SO2, volatile organic compounds (VOCs) and aerosol size distribution measurements were performed in July–August 2013 as a part of the project ChArMEx (Chemistry-Aerosols Mediterranean Experiment). The measurement site was under strong influence of local emissions of biogenic volatile organic compounds, including monoterpenes and isoprene generating SCIs in reactions with ozone, and, hence, presenting an additional source of H2SO4 via SO2 oxidation by the SCIs. Assuming the validity of a steady state between H2SO4 production and its loss by condensation on existing aerosol particles with a unity accommodation coefficient, about 90 % of the H2SO4 formation during the day could be explained by the reaction of SO2 with OH. During the night the oxidation of SO2 by OH radicals was found to contribute only about 10 % to the H2SO4 formation. The accuracy of the derived values for the contribution of OH + SO2 reaction to the H2SO4 formation is limited mostly by a large, at present factor of 2, uncertainty in the OH + SO2 reaction rate coefficient. The contribution of the SO2 oxidation by SCIs to the H2SO4 formation was evaluated using available measurements of unsaturated VOCs and steady-state SCI concentrations estimated by adopting rate coefficients for SCI reactions based on structure–activity relationships (SARs). The estimated concentration of the sum of SCIs was in the range of (1–3) × 103 molec. cm−3. During the day the reaction of SCIs with SO2 was found to account for about 10 % and during the night for about 40 % of the H2SO4 production, closing the H2SO4 budget during the day but leaving unexplained about 50 % of the H2SO4 formation during the night. Despite large uncertainties in used kinetic parameters, these results indicate that the SO2 oxidation by SCIs may represent an important H2SO4 source in VOC-rich environments, especially during nighttime.

Study region: Congo River Basin Study Focus: Precipitation is the major driving force of hydrological processes and is one of the main input datasets for hydrological models. The Congo River Basin is one of the least studied major river basins in the world and suffers from the scarcity and difficulty in accessing rain gauge data, necessitating the use of satellite precipitation estimates for hydrological studies. In this study, we have made a comprehensive comparison of different satellite-based precipitation products’ inputs for a hydrological model in the Congo River Basin. New hydrological insight for this region: Our findings showed that the products based on satellite-only source tend to overestimate the rainy season peaks in comparison with the 3B42_V7 product. On the other hand, the satellite products that consider gauge calibration presented better agreements between each other. The hydrological model was able to reproduce the general precipitation products characteristics, while the gauge-adjusted satellite products performed better than those without gauge adjustments. Overall precipitation patterns have a crucial effect on the model’s performance and leads to different streamflow and water balance components’ values. The choice of rainfall product has a significant importance in the interpretation of the simulated hydrological cycle.

The characterization of the molecular composition of organic carbon in both gaseous and aerosol is key to understanding the processes involved in the formation and aging of secondary organic aerosol. Therefore a technique using active sampling on cartridges and filters and derivatization followed by analysis using a thermal desorption–gas chromatography–mass spectrometer (TD–GC–MS) has been used. It is aimed at studying the molecular composition of organic carbon in both gaseous and aerosol phases (PM2.5) during an intensive field campaign which took place in Corsica (France) during the summer of 2013: the ChArMEx (Chemistry and Aerosol Mediterranean Experiment) SOP1b (Special Observation Period 1B) campaign. These measurements led to the identification of 51 oxygenated (carbonyl and or hydroxyl) compounds in the gaseous phase with concentrations between 21 and 3900 ng m−3 and of 85 compounds in the particulate phase with concentrations between 0.3 and 277 ng m−3. Comparisons of these measurements with collocated data using other techniques have been conducted, showing fair agreement in general for most species except for glyoxal in the gas phase and malonic, tartaric, malic and succinic acids in the particle phase, with disagreements that can reach up to a factor of 8 and 20 on average, respectively, for the latter two acids. Comparison between the sum of all compounds identified by TD–GC–MS in the particle phase and the total organic matter (OM) mass reveals that on average 18 % of the total OM mass can be explained by the compounds measured by TD–GC–MS. This number increases to 24 % of the total water-soluble OM (WSOM) measured by coupling the Particle Into Liquid Sampler (PILS)-TOC (total organic carbon) if we consider only the sum of the soluble compounds measured by TD–GC–MS. This highlights the important fraction of the OM mass identified by these measurements but also the relative important fraction of OM mass remaining unidentified during the campaign and therefore the complexity of characterizing exhaustively the organic aerosol (OA) molecular chemical composition. The fraction of OM measured by TD–GC–MS is largely dominated by di-carboxylic acids, which represent 49 % of the PM2.5 content detected and quantified by this technique. Other contributions to PM2.5 composition measured by TD–GC–MS are then represented by tri-carboxylic acids (15 %), alcohols (13 %), aldehydes (10 %), di-hydroxy-carboxylic acids (5 %), monocarboxylic acids and ketones (3 % each), and hydroxyl-carboxylic acids (2 %). These results highlight the importance of polyfunctionalized carboxylic acids for OM, while the chemical processes responsible for their formation in both phases remain uncertain. While not measured by the TD–GC–MS technique, humic-like substances (HULISs) represent the most abundant identified species in the aerosol, contributing for 59 % of the total OM mass on average during the campaign. A total of 14 compounds were detected and quantified in both phases, allowing the calculation of experimental partitioning coefficients for these species. The comparison of these experimental partitioning coefficients with theoretical ones, estimated by three different models, reveals large discrepancies varying from 2 to 7 orders of magnitude. These results suggest that the supposed instantaneous equilibrium being established between gaseous and particulate phases assuming a homogeneous non-viscous particle phase is questionable.

An original time series of about 300 atmospheric measurements of a wide range of volatile organic compounds (VOCs) was obtained at a remote Mediterranean station on the northern tip of Corsica (Ersa, France) over 25 months from June 2012 to June 2014. This study presents the seasonal variabilities of 35 selected VOCs and their various associated sources. The VOC abundance was largely dominated by oxygenated VOCs (OVOCs) along with primary anthropogenic VOCs with a long lifetime in the atmosphere. VOC temporal variations were then examined. Primarily of local origin, biogenic VOCs exhibited notable seasonal and interannual variations, related to temperature and solar radiation. Anthropogenic compounds showed increased concentrations in winter (JFM months) followed by a decrease in spring/summer (AMJ/JAS months) and higher winter concentration levels in 2013 than in 2014 by up to 0.3 µg m−3 in the cases of propane, acetylene and benzene. OVOC concentrations were generally high in summertime, mainly due to secondary anthropogenic/biogenic and primary biogenic sources, whereas their lower concentrations during autumn and winter were potentially more influenced by primary/secondary anthropogenic sources. Moreover, an apportionment factorial analysis was applied to a database comprising a selection of 14 individual or grouped VOCs by means of the positive matrix factorization (PMF) technique. A PMF five-factor solution was taken on. It includes an anthropogenic factor (which contributed 39 % to the total concentration of the VOCs selected in the PMF analysis) connected to the regional background pollution, three other anthropogenic factors (namely short-lived anthropogenic sources, evaporative sources, and long-lived combustion sources, which together accounted for 57 %) originating from either nearby or more distant emission areas (such as Italy and south of France), and a local biogenic source (4 %). Variations in these main sources impacting VOC concentrations observed at the Ersa station were also investigated at seasonal and interannual scales. In spring and summer, VOC concentrations observed at Ersa were the lowest in the 2-year period, despite higher biogenic source contributions. During these seasons, anthropogenic sources advected to Ersa were largely influenced by chemical transformations and vertical dispersion phenomena and were mainly of regional origins. During autumn and winter, anthropogenic sources showed higher contributions when European air masses were advected to Ersa and could be associated with potential emission areas located in Italy and possibly more distant ones in central Europe. Higher VOC winter concentrations in 2013 than in 2014 could be related to contribution variations in anthropogenic sources probably governed by their emission strength with external parameters, i.e. weaker dispersion phenomena and the pollutant depletion. High-frequency observations collected during several intensive field campaigns conducted at Ersa during the three summers 2012–2014 confirmed findings drawn from bi-weekly samples of the 2-year period in terms of summer concentration levels and source apportionment. However, they also suggested that higher sampling frequency and temporal resolution, in particular to observe VOC concentration variations during the daily cycle, would have been necessary to confirm the deconvolution of the different anthropogenic sources identified following the PMF approach. Finally, comparisons of the 25 months of Ersa observations with VOC measurements conducted at 17 other European monitoring stations highlighted the representativeness of the Ersa station for monitoring seasonal variations in VOC regional pollution impacting continental Europe. Nevertheless, VOC winter concentration levels can significantly vary between sites, pointing out spatial variations in anthropogenic source contributions. As a result, Ersa concentration variations in winter were more representative of VOC regional pollution impacting central Europe. Moreover, interannual and spatial variations in VOC winter concentration levels were significantly impacted by synoptic phenomena influencing meteorological conditions observed in continental Europe, suggesting that short observation periods may reflect the variability of the identified parameters under the specific meteorological conditions of the study period.

In this paper, we quantify the CO2 and N2O emissions from denitrification over the Amazonian wetlands. The study concerns the entire Amazonian wetland ecosystem with a specific focus on three floodplain (FP) locations: the Branco FP, the Madeira FP and the FP alongside the Amazon River. We adapted a simple denitrification model to the case of tropical wetlands and forced it by open water surface extent products from the Soil Moisture and Ocean Salinity (SMOS) satellite. A priori model parameters were provided by in situ observations and gauging stations from the HYBAM Observatory. Our results show that the denitrification and the trace gas emissions present a strong cyclic pattern linked to the inundation processes that can be divided into three distinct phases: activation, stabilization and deactivation. We quantify the average yearly denitrification and associated emissions of CO2 and N2O over the entire watershed at 17.8 kgN ha−1 yr−1, 0.37 gC-CO2 m−2 yr−1 and 0.18 gN-N2O m−2 yr−1 respectively for the period 2011–2015. When compared to local observations, it was found that the CO2 emissions accounted for 0.01 % of the integrated ecosystem, which emphasizes the fact that minor changes to the land cover may induce strong impacts on the Amazonian carbon budget. Our results are consistent with the state of the art of global nitrogen models with a positive bias of 28 %. When compared to other wetlands in different pedoclimatic environments we found that the Amazonian wetlands have similar emissions of N2O with the Congo tropical wetlands and lower emissions than the temperate and tropical anthropogenic wetlands of the Garonne (France), the Rhine (Europe) and south-eastern Asia rice paddies. In summary our paper shows that a data-model-based approach can be successfully applied to quantify N2O and CO2 fluxes associated with denitrification over the Amazon basin. In the future, the use of higher-resolution remote sensing products from sensor fusion or new sensors like the Surface Water and Ocean Topography (SWOT) mission will permit the transposition of the approach to other large-scale watersheds in tropical environments.

For the last 25 years, CO-PDD (Cézeaux-Aulnat-Opme-puy de Dôme) has evolved to become a full instrumented platform for atmospheric research. It has received credentials as a national observing platform in France and is internationally recognized as a global station in the GAW (Global Atmosphere Watch) network. It is a reference site of European and national research infrastructures ACTRIS (Aerosol Cloud and Trace gases Research Infrastructure) and ICOS (Integrated Carbon Observing System). The site located on top of the puy de Dôme mountain (1465 m a.s.l.) is completed by additional sites located at lower altitudes and adding the vertical dimension to the atmospheric observations: Opme (660 m a.s.l.), Cézeaux (410 m), and Aulnat (330 m). The integration of different sites offers a unique combination of in situ and remote sensing measurements capturing and documenting the variability of particulate and gaseous atmospheric composition, but also the optical, biochemical, and physical properties of aerosol particles, clouds, and precipitations. Given its location far away from any major emission sources, its altitude, and the mountain orography, the puy de Dôme station is ideally located to sample different air masses in the boundary layer or in the free troposphere depending on time of day and seasons. It is also an ideal place to study cloud properties with frequent presence of clouds at the top in fall and winter. As a result of the natural conditions prevailing at the site and of the very exhaustive instrumental deployment, scientific studies at the puy de Dôme strongly contribute to improving knowledge in atmospheric sciences, including the characterization of trends and variability, the understanding of complex and interconnected processes (microphysical, chemical, biological, chemical and dynamical), and the provision of reference information for climate/chemistry models. In this context, CO-PDD is a pilot site to conduct instrumental development inside its wind tunnel for testing liquid and ice cloud probes in natural conditions, or in situ systems to collect aerosol and cloud. This paper reviews 25 years (1995–2020) of atmospheric observation at the station and related scientific research contributing to atmospheric and climate science.

Total hydroxyl radical (OH) reactivity measurements were conducted during the LANDEX intensive field campaign in a coniferous temperate forest located in the Landes area, southwestern France, during July 2017. In order to investigate inter-canopy and intra-canopy variability, measurements were performed inside (6 m) and above the canopy level (12 m), as well as at two different locations within the canopy, using a comparative reactivity method (CRM) and a laser photolysis–laser-induced fluorescence (LP-LIF) instrument. The two techniques were intercompared at the end of the campaign by performing measurements at the same location. Volatile organic compounds were also monitored at both levels with a proton transfer time-of-flight mass spectrometer and online gas chromatography instruments to evaluate their contribution to total OH reactivity, with monoterpenes being the main reactive species emitted in this forest dominated by Pinus pinaster Aiton. Total OH reactivity varied diurnally, following the trend of biogenic volatile organic compounds (BVOCs), the emissions and concentrations of which were dependent on meteorological parameters. Average OH reactivity was around 19.2 and 16.5 s−1 inside and above the canopy, respectively. The highest levels of total OH reactivity were observed during nights with a low turbulence (u*≤0.2 m s−1), leading to lower mixing of emitted species within the canopy and thus an important vertical stratification characterized by a strong concentration gradient. Comparing the measured and the calculated OH reactivity highlighted an average missing OH reactivity of 22 % and 33 % inside and above the canopy, respectively. A day–night variability was observed on missing OH reactivity at both heights. Investigations showed that during daytime, missing OH sinks could be due to primary emissions and secondary products linked to a temperature-enhanced photochemistry. Regarding nighttime missing OH reactivity, higher levels were seen for the stable and warm night of 4–5 July, showing that these conditions could have been favorable for the accumulation of long-lived species (primary and secondary species) during the transport of the air mass from nearby forests.

Here we report results of a detailed analysis of the urban and non-urban contributions to particulate matter (PM) concentrations and source contributions in five European cities, namely Schiedam (the Netherlands, NL), Lens (France, FR), Leipzig (Germany, DE), Zurich (Switzerland, CH) and Barcelona (Spain, ES). PM chemically speciated data from 12 European paired monitoring sites (one traffic, five urban, five regional and one continental background) were analysed by positive matrix factorisation (PMF) and Lenschow's approach to assign measured PM and source contributions to the different spatial levels. Five common sources were obtained at the 12 sites: sulfate-rich (SSA) and nitrate-rich (NSA) aerosols, road traffic (RT), mineral matter (MM), and aged sea salt (SS). These sources explained from 55 % to 88 % of PM mass at urban low-traffic-impact sites (UB) depending on the country. Three additional common sources were identified at a subset of sites/countries, namely biomass burning (BB) (FR, CH and DE), explaining an additional 9 %–13 % of PM mass, and residual oil combustion (V–Ni) and primary industrial (IND) (NL and ES), together explaining an additional 11 %–15 % of PM mass. In all countries, the majority of PM measured at UB sites was of a regional+continental (R+C) nature (64 %–74 %). The R+C PM increments due to anthropogenic emissions in DE, NL, CH, ES and FR represented around 66 %, 62 %, 52 %, 32 % and 23 %, respectively, of UB PM mass. Overall, the R+C PM increments due to natural and anthropogenic sources showed opposite seasonal profiles with the former increasing in summer and the latter increasing in winter, even if exceptions were observed. In ES, the anthropogenic R+C PM increment was higher in summer due to high contributions from regional SSA and V–Ni sources, both being mostly related to maritime shipping emissions at the Spanish sites. Conversely, in the other countries, higher anthropogenic R+C PM increments in winter were mostly due to high contributions from NSA and BB regional sources during the cold season. On annual average, the sources showing higher R+C increments were SSA (77 %–91 % of SSA source contribution at the urban level), NSA (51 %–94 %), MM (58 %–80 %), BB (42 %–78 %) and IND (91 % in NL). Other sources showing high R+C increments were photochemistry and coal combustion (97 %–99 %; identified only in DE). The highest regional SSA increment was observed in ES, especially in summer, and was related to ship emissions, enhanced photochemistry and peculiar meteorological patterns of the Western Mediterranean. The highest R+C and urban NSA increments were observed in NL and associated with high availability of precursors such as NOx and NH3. Conversely, on average, the sources showing higher local increments were RT (62 %–90 % at all sites) and V–Ni (65 %–80 % in ES and NL). The relationship between SSA and V–Ni indicated that the contribution of ship emissions to the local sulfate concentrations in NL has strongly decreased since 2007 thanks to the shift from high-sulfur- to low-sulfur-content fuel used by ships. An improvement of air quality in the five cities included here could be achieved by further reducing local (urban) emissions of PM, NOx and NH3 (from both traffic and non-traffic sources) but also SO2 and PM (from maritime ships and ports) and giving high relevance to non-urban contributions by further reducing emissions of SO2 (maritime shipping) and NH3 (agriculture) and those from industry, regional BB sources and coal combustion.

In the framework of the TRANSport Emissions and Mitigation in the East Mediterranean (TRANSEMED/ChArMEx) program, volatile organic compound (VOC) measurements were performed for the first time in Istanbul (Turkey) at an urban site in September 2014. One commercial gas chromatograph coupled to a flame ionization detector (GC–FID) and one proton transfer mass spectrometer (PTR-MS) were deployed. In addition, sorbent tubes and canisters were implemented within the megacity close to major emission sources. More than 70 species including non-methane hydrocarbons (NMHCs), oxygenated VOCs (OVOCs), and organic compounds of intermediate volatility (IVOCs) have been quantified. Among these compounds, 23 anthropogenic and biogenic species were continuously collected at the urban site. VOC concentrations show a great variability with maxima exceeding 10 ppb (i.e., n-butane, toluene, methanol, and acetaldehyde) and mean values between 0.1 (methacrolein + methyl vinyl ketone) and 4.9 ppb (methanol). OVOCs represent 43.9 % of the total VOC concentrations followed by alkanes (26.3 %), aromatic compounds (20.7 %), alkenes (4.8 %), terpenes (3.4 %), and acetonitrile (0.8 %). Five factors have been extracted from the Positive Matrix Factorization model (EPA PMF 5.0) and have been compared to source profiles established by near-field measurements and other external variables (meteorological parameters, NOx, CO, SO2, etc.). Surprisingly, road transport is not the dominant source, only explaining 15.8 % of measured VOC concentrations contrary to the local emission inventory. Other factors are toluene from solvent use (14.2 %), biogenic terpenes (7.8 %), natural gas evaporation (25.9 %) composed of butanes, and a last factor characterized by mixed regional emissions and composed of most of the species (36.3 %). The PMF model results point out the influence of industrial emissions while there is no clear evidence of the impact of ship emissions on the measured VOC distribution. For the latter additional measurements of organic compounds of lower volatility like IVOC would be helpful. The sensitivity of PMF results to input data (time resolution, meteorological period, peak episode, interpolation method) was tested. While some PMF runs do not perform as well statistically as the reference run, sensitivity tests show that the same factors (number and type) are found with slightly different factor contributions (up to 16 % of change). Finally, the emission ratios (ERs) of VOCs relative to carbon monoxide (CO) were established. These ratios are usually higher than the ones of other cities worldwide but in the same range of magnitude. These ERs and the road transport factor from PMF were used to estimate VOC emissions and to evaluate three downscaled global emissions inventories (EDGAR, ACCMIP, and MACCity). It was found that the total annual VOC anthropogenic emissions by global inventories were either within the same range by a factor of 2 to 3 for alkanes and aromatics or underestimated by an order of magnitude, especially for oxygenated VOCs.

A new online gas chromatographic method dedicated to biogenic volatile organic compound (BVOC) analysis was developed for the measurement of a 20 BVOC gaseous mixture (isoprene; β-pinene; α-pinene; limonene; ocimene; myrcene; sabinene; Δ3-carene; camphene; 1,8 cineole; terpinolene; linalool; α-phellandrene; nopinone; citral; α-terpinene; β-caryophyllene; p-cymene; γ-terpinene; and 2-carene) at a time resolution of 90 min. The optimized method includes an online Peltier-cooled thermodesorption system sample trap made of Carbopack B coupled to a gas chromatographic system equipped with a 60 m, 0.25 mm internal diameter (i.d.) BPX5 column. Eluent was analysed using flame ionization detection (FID). Potassium iodide was identified as the best ozone scrubber for the 20 BVOC mixture. In order to obtain an accurate quantification of BVOC concentrations, the development of a reliable standard mixture was also required. Quantification of BVOCs was reported with a detection limit ranging from 4 ppt for α-pinene to 19 ppt for sabinene. The main source of uncertainty was the calibration step, stressing the need for certified gaseous standards for a wider panel of BVOCs. This new method was applied for the first time to measure BVOCs in a pine forest during the LANDEX episode 1 field campaign (summer 2017). All target BVOCs were detected at least once during the campaign. The two major monoterpenes observed were β-pinene and α-pinene, representing 60 % of the measured terpenoid concentration on average, while isoprene represented only 17 %. The uncertainties determined were always below 13 % for the six major terpenes.

In September 2017, we conducted a proton-transfer-reaction mass-spectrometry (PTR-MS) intercomparison campaign at the CESAR observatory, a rural site in the central Netherlands near the village of Cabauw. Nine research groups deployed a total of 11 instruments covering a wide range of instrument types and performance. We applied a new calibration method based on fast injection of a gas standard through a sample loop. This approach allows calibrations on timescales of seconds, and within a few minutes an automated sequence can be run allowing one to retrieve diagnostic parameters that indicate the performance status. We developed a method to retrieve the mass-dependent transmission from the fast calibrations, which is an essential characteristic of PTR-MS instruments, limiting the potential to calculate concentrations based on counting statistics and simple reaction kinetics in the reactor/drift tube. Our measurements show that PTR-MS instruments follow the simple reaction kinetics if operated in the standard range for pressures and temperature of the reaction chamber (i.e. 1–4 mbar, 30–120∘, respectively), as well as a reduced field strength E∕N in the range of 100–160 Td. If artefacts can be ruled out, it becomes possible to quantify the signals of uncalibrated organics with accuracies better than ±30 %. The simple reaction kinetics approach produces less accurate results at E∕N levels below 100 Td, because significant fractions of primary ions form water hydronium clusters. Deprotonation through reactive collisions of protonated organics with water molecules needs to be considered when the collision energy is a substantial fraction of the exoergicity of the proton transfer reaction and/or if protonated organics undergo many collisions with water molecules.

Several field campaigns were conducted in the framework of the Dynamics-Aerosol-Chemistry-Cloud Interactions in West Africa (DACCIWA) project to measure a broad range of atmospheric constituents. Here we present the analysis of an unprecedented and comprehensive dataset integrating up to 56 volatile organic compounds (VOCs) from ambient sites and emission sources. VOCs were collected on multi-sorbent tubes in the coastal city of Abidjan, Côte d'Ivoire, in winter and summer 2016 and later analysed by gas chromatography coupled with flame ionization and mass spectrometer detectors (GC-FID and GC-MS) at the laboratory. The comparison between VOC emission source profiles and ambient profiles suggests the substantial impact of two-stroke motorized two-wheel vehicles and domestic fires on the composition of Abidjan's atmosphere. However, despite high VOC concentrations near-source, moderate ambient levels were observed (by factors of 10 to 4000 lower), similar to the concentrations observed in northern mid-latitude urban areas. Besides photochemistry, the reported high wind speeds seem to be an essential factor that regulates air pollution levels in Abidjan. Emission ratios (ΔVOC∕ΔCO) were established based on real-world measurements achieved for a selected number of representative combustion sources. Maximum measured molar mass emissions were observed from two-wheel vehicles, surpassing other regional sources by 2 orders of magnitude. Local practices like waste burning also make a significant contribution to VOC emissions, higher than those from light-duty vehicles by 1.5 to 8 orders of magnitude. These sources also largely govern the VOC's atmospheric impacts in terms of OH reactivity, secondary organic aerosol formation (SOAP), and photochemical ozone creation potential (POCP). While the contribution of aromatics dominates the atmospheric impact, our measurements reveal the systematic presence of anthropogenic terpenoids in all residential combustion sectors. Finally, emission factors were used to retrieve and quantify VOC emissions from the main anthropogenic source sectors at the national level. Our detailed estimation of VOC emissions suggests that the road transport sector is the dominant source in Côte d'Ivoire, emitting around 1200 Gg yr−1 of gas-phase VOCs. These new estimates are 100 and 160 times larger than global inventory estimations from MACCity or EDGAR (v4.3.2), respectively. Additionally, the residential sector is largely underestimated in the global emission inventories, by factors of 13 to 43. Considering only Côte d'Ivoire, these new estimates for VOCs are 3 to 6 times higher than the whole of Europe. Given the significant underestimation of VOC emissions from the transport and residential sectors in Côte d'Ivoire, there is an urgent need to build more realistic and region-specific emission inventories for the entire West African region. This might be true not only for VOCs, but also for all atmospheric pollutants. The lack of waste burning, wood fuel burning and charcoal burning, and fabrication representation in regional inventories also needs to be addressed, particularly in low-income areas where these types of activities are ubiquitous sources of VOC emissions.

In this study, the performance of two types of source apportionment models was evaluated by assessing the results provided by 40 different groups in the framework of an intercomparison organised by FAIRMODE WG3 (Forum for air quality modelling in Europe, Working Group 3). The evaluation was based on two performance indicators: z-scores and the root mean square error weighted by the reference uncertainty (RMSEu), with pre-established acceptability criteria. By involving models based on completely different and independent input data, such as receptor models (RMs) and chemical transport models (CTMs), the intercomparison provided a unique opportunity for their cross-validation. In addition, comparing the CTM chemical profiles with those measured directly at the source contributed to corroborate the consistency of the tested model results. The most commonly used RM was the US EPA- PMF version 5. RMs showed very good performance for the overall dataset (91% of z-scores accepted) while more difficulties were observed with the source contribution time series (72% of RMSEu accepted). Industrial activities proved to be the most difficult sources to be quantified by RMs, with high variability in the estimated contributions. In the CTMs, the sum of computed source contributions was lower than the measured gravimetric PM10 mass concentrations. The performance tests pointed out the differences between the two CTM approaches used for source apportionment in this study: brute force (or emission reduction impact) and tagged species methods. The sources meeting the z-score and RMSEu acceptability criteria tests were 50% and 86%, respectively. The CTM source contributions to PM10 were in the majority of cases lower than the RM averages for the corresponding source. The CTMs and RMs source contributions for the overall dataset were more comparable (83% of the z-scores accepted) than their time series (successful RMSEu in the range 25% - 34%). The comparability between CTMs and RMs varied depending on the source: traffic/exhaust and industry were the source categories with the best results in the RMSEu tests while the most critical ones were soil dust and road dust. The differences between RMs and CTMs source reconstructions confirmed the importance of cross validating the results of these two families of models. Keywords: Source apportionment, PM10, Receptor models, Chemical transport models, Intercomparison, Lens

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 ( −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.

Methylglyoxal (MGLY) is an important atmospheric α-dicarbonyl species for which photolysis acts as a significant source of peroxy radicals, contributing to the oxidizing capacity of the atmosphere and, as such, the formation of secondary pollutants such as organic aerosols and ozone. However, despite its importance, only a few techniques exhibit time resolutions and detection limits that are suitable for atmospheric measurements.This study presents the first field measurements of MGLY by proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) performed during the ChArMEx SOP2 field campaign. This campaign took place at a Mediterranean site characterized by intense biogenic emissions and low levels of anthropogenic trace gases. Concomitant measurements of MGLY were performed using the 2,4-dinitrophenylhydrazine (DNPH) derivatization technique and high performance liquid chromatography (HPLC) with UV detection. PTR-ToF-MS and DNPH–HPLC measurements were compared to determine whether these techniques can perform reliable measurements of MGLY.Ambient time series revealed levels of MGLY ranging from 28 to 365 pptv, with a clear diurnal cycle due to elevated concentrations of primary biogenic species during the daytime, and its oxidation led to large production rates of MGLY. A scatter plot of the PTR-ToF-MS and DNPH–HPLC measurements indicates a reasonable correlation (R2 = 0.48) but a slope significantly lower than unity (0.58±0.05) and a significant intercept of 88.3±8.0 pptv. A careful investigation of the differences between the two techniques suggests that this disagreement is not due to spectrometric interferences from H3O+(H2O)3 or methyl ethyl ketone (or butanal) detected at m∕z 73.050 and m∕z 73.065, respectively, which are close to the MGLY m∕z of 73.029. The differences are more likely due to uncorrected sampling artifacts such as overestimated collection efficiency or loss of MGLY into the sampling line for the DNPH–HPLC technique or unknown isobaric interfering compounds such as acrylic acid and propanediol for the PTR-ToF-MS.Calculations of MGLY loss rates with respect to OH oxidation and direct photolysis indicate similar contributions for these two loss pathways.

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.

The simulation of fine organic aerosols with CTMs (chemistry–transport models) in the western Mediterranean basin has not been studied until recently. The ChArMEx (the Chemistry-Aerosol Mediterranean Experiment) SOP 1b (Special Observation Period 1b) intensive field campaign in summer of 2013 gathered a large and comprehensive data set of observations, allowing the study of different aspects of the Mediterranean atmosphere including the formation of organic aerosols (OAs) in 3-D models. In this study, we used the CHIMERE CTM to perform simulations for the duration of the SAFMED (Secondary Aerosol Formation in the MEDiterranean) period (July to August 2013) of this campaign. In particular, we evaluated four schemes for the simulation of OA, including the CHIMERE standard scheme, the VBS (volatility basis set) standard scheme with two parameterizations including aging of biogenic secondary OA, and a modified version of the VBS scheme which includes fragmentation and formation of nonvolatile OA. The results from these four schemes are compared to observations at two stations in the western Mediterranean basin, located on Ersa, Cap Corse (Corsica, France), and at Cap Es Pinar (Mallorca, Spain). These observations include OA mass concentration, PMF (positive matrix factorization) results of different OA fractions, and 14C observations showing the fossil or nonfossil origins of carbonaceous particles. Because of the complex orography of the Ersa site, an original method for calculating an orographic representativeness error (ORE) has been developed. It is concluded that the modified VBS scheme is close to observations in all three aspects mentioned above; the standard VBS scheme without BSOA (biogenic secondary organic aerosol) aging also has a satisfactory performance in simulating the mass concentration of OA, but not for the source origin analysis comparisons. In addition, the OA sources over the western Mediterranean basin are explored. OA shows a major biogenic origin, especially at several hundred meters height from the surface; however over the Gulf of Genoa near the surface, the anthropogenic origin is of similar importance. A general assessment of other species was performed to evaluate the robustness of the simulations for this particular domain before evaluating OA simulation schemes. It is also shown that the Cap Corse site presents important orographic complexity, which makes comparison between model simulations and observations difficult. A method was designed to estimate an orographic representativeness error for species measured at Ersa and yields an uncertainty of between 50 and 85 % for primary pollutants, and around 2–10 % for secondary species.

To solve the problem of estimating and verifying stream flow without direct observation data, we estimated stream flow in ungauged zones by coupling a hydrological model with a hydrodynamic model, using the Poyang Lake basin as a test case. To simulate the stream flow of the ungauged zone, we built a soil and water assessment tool (SWAT) model for the entire catchment area covering the upstream gauged area and ungauged zone, and then calibrated the SWAT model using the data in the gauged area. To verify the results, we built two hydrodynamic scenarios (the original and adjusted scenarios) for Poyang Lake using the Delft3D model. In the original scenario, the upstream boundary condition is the observed stream flow from the upstream gauged area, while, in the adjusted scenario, it is the sum of the observed stream flow from the gauged area and the simulated stream flow from the ungauged zone. The experimental results showed that there is a stronger correlation and lower bias (R2 = 0.81, PBIAS = 10.00 %) between the observed and simulated stream flow in the adjusted scenario compared to that (R2 = 0.77, PBIAS = 20.10 %) in the original scenario, suggesting the simulated stream flow of the ungauged zone is reasonable. Using this method, we estimated the stream flow of the Poyang Lake ungauged zone as 16.4 ± 6.2 billion m3 a−1, representing ∼ 11.24 % of the annual total water yield of the entire watershed. Of the annual water yield, 70 % (11.48 billion m3 a−1) is concentrated in the wet season, while 30 % (4.92 billion m3 a−1) comes from the dry season. The ungauged stream flow significantly improves the water balance with the closing error decreased by 13.48 billion m3 a−1 (10.10 % of the total annual water resource) from 30.20 ± 9.1 billion m3 a−1 (20.10 % of the total annual water resource) to 16.72 ± 8.53 billion m3 a−1 (10.00 % of the total annual water resource). The method can be extended to other lake, river, or ocean basins where observation data is unavailable.

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.

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.

The ChArMEx (Chemistry and Aerosols Mediterranean Experiments) SOP2 (special observation period 2) field campaign took place from 15 July to 5 August 2013 in the western Mediterranean Basin at Ersa, a remote site in Cape Corse. During the campaign more than 80 volatile organic compounds (VOCs), including oxygenated species, were measured by different online and offline techniques. At the same time, an exhaustive description of the chemical composition of fine aerosols was performed with an aerosol chemical speciation monitor (ACSM). Low levels of anthropogenic VOCs (typically tens to hundreds of parts per trillion for individual species) and black carbon (0.1–0.9 µg m−3) were observed, while significant levels of biogenic species (peaking at the ppb level) were measured. Furthermore, secondary oxygenated VOCs (OVOCs) largely dominated the VOC speciation during the campaign, while organic matter (OM) dominated the aerosol chemical composition, representing 55 % of the total mass of non-refractory PM1 on average (average of 3.74 ± 1.80 µg m−3), followed by sulfate (27 %, 1.83 ± 1.06 µg m−3), ammonium (13 %, 0.90 ± 0.55 µg m−3) and nitrate (5 %, 0.31 ± 0.18 µg m−3). Positive matrix factorization (PMF) and concentration field (CF) analyses were performed on a database containing 42 VOCs (or grouped VOCs), including OVOCs, to identify the covariation factors of compounds that are representative of primary emissions or chemical transformation processes. A six-factor solution was found for the PMF analysis, including a primary and secondary biogenic factor correlated with temperature and exhibiting a clear diurnal profile. In addition, three anthropogenic factors characterized by compounds with various lifetimes and/or sources have been identified (long-lived, medium-lived and short-lived anthropogenic factors). The anthropogenic nature of these factors was confirmed by the CF analysis, which identified potential source areas known for intense anthropogenic emissions (north of Italy and southeast of France). Finally, a factor characterized by OVOCs of both biogenic and anthropogenic origin was found. This factor was well correlated with submicron organic aerosol (OA) measured by an aerosol chemical speciation monitor (ACSM), highlighting the close link between OVOCs and organic aerosols; the latter is mainly associated (96 %) with the secondary OA fraction. The source apportionment of OA measured by ACSM led to a three-factor solution identified as hydrogen-like OA (HOA), semi-volatile oxygenated OA (SV-OOA) and low volatility OOA (LV-OOA) for averaged mass concentrations of 0.13, 1.59 and 1.92 µg m−3, respectively. A combined analysis of gaseous PMF factors with inorganic and organic fractions of aerosols helped distinguish between anthropogenic continental and biogenic influences on the aerosol- and gas-phase compositions.

The relative importance of eastern Mediterranean emissions is suspected to be largely underestimated compared to other regions worldwide. Here we use detailed speciated measurements of volatile organic compounds (VOCs) to evaluate the spatial heterogeneity of VOC urban emission composition and the consistency of regional and global emission inventories downscaled to Lebanon (European Monitoring and Evaluation Programme, EMEP; Atmospheric Chemistry and Climate Model Intercomparison Project, ACCMIP; and MACCity, Monitoring Atmospheric Composition and Climate and megaCITY Zoom for the Environment). The assessment was conducted through the comparison of the emission ratios (ERs) extracted from the emission inventories to the ones obtained from the hourly observations collected at a suburban site in Beirut, Lebanon, during summer and winter ECOCEM (Emissions and Chemistry of Organic Carbon in the Eastern Mediterranean) campaigns. The observed ERs were calculated using two independent methods. ER values from both methods agree very well and are comparable to the ones of the road transport sector from near-field measurements for more than 80 % of the species. There is no significant seasonality in ER for more than 90 % of the species, unlike the seasonality usually observed in other cities worldwide. Regardless of the season, ERs agree within a factor of 2 between Beirut and other representative cities worldwide, except for the unburned fuel fraction and ethane. ERs of aromatics (except benzene) are higher in Beirut compared to northern post-industrialized countries and even the Middle Eastern city Mecca. The comparison of the observed ER to the ones extracted from the ACCMIP and MACCity global emission inventories suggests that the overall speciation of anthropogenic sources for major hydrocarbons that act as ozone and secondary organic aerosol (SOA) precursors in ACCMIP is better represented than other species. The comparison of the specific road transport ERs, relative to acetylene derived from near-field measurements, to ERs from ACCMIP and EMEP emission inventories for the road transport sector showed that ERs of more reactive species are usually consistent within a factor of 2 with EMEP, while xylenes and toluene are underestimated by over a factor of 2 by ACCMIP. The observed heterogeneity of anthropogenic VOC emission composition between Middle Eastern cities can be significant for reactive VOCs but is not depicted by global emission inventories. This suggests that systematic and detailed measurements are needed in the eastern Mediterranean Basin in order to better constrain emission inventory.

Besides their impacts on health, BTEX play an important role in the formation of secondary organic aerosols and ozone for which limit values are regularly exceeded in Paris megacity and Ile de France region. An enrichment by a factor of 3 in the C7C9 aromatic fraction in the Paris atmosphere compared to other northern mid-latitude cities was shown in 2013. Here, we combined different approaches to investigate the role of transport-related sources in such enrichment (gasoline composition and vehicle fleet composition): a statistical analysis of a large BTEX dataset including multi-year and multi-site measurements (traffic, background, tunnel) and a coupled experimental and modelling analysis of liquid and headspace composition of representative fuels distributed in Ile de France region (SP95, SP95 E10, and SP98). For the latter the experimental set-up was designed to analyze the composition of 87 VOCs from C2 to C17 in both liquid and headspace phases. The model is able to predict the headspace composition at ± 15% and with an R2 > 0.9. First a strong positive spatial gradient in BTEX composition at traffic stations is observed, with higher TEX-to-benzene ratio in Paris center compared to the suburbs and outskirts up to a factor of 2. This gradient reflects differences in fleet composition especially gasoline powered vehicles in Paris with a larger proportion of two-wheelers (15% in 2012). This gradient is also consistent with the inter-annual increase of TEX-to-benzene ratios along with the doubling of two-wheelers use and the decrease in the number of passenger cars. The gasoline evaporation model cannot solely explain the observed spatial variability. Finally, we investigated the potential contribution of two-wheelers to the aromatic enrichment in IdF region by introducing an additional unburned gasoline term to the model. The results support the suggestion that two-wheelers are a potential contributor to this enrichment. Considering the high use of two-wheelers in other European cities such as London or Barcelona if Europe is to decrease transport-related air pollution and inner city traffic, policy makers should consider finding alternatives to the conventionally-powered two-wheelers and supporting electric two-wheelers for example. Keywords: Urban air quality, Megacity, VOC, BTEX, Fuel composition, Two-wheelers, Emission ratios

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).

Previous studies have provided some insight into the Saharan dust deposition at a few specific locations from observations over long time periods or intensive field campaigns. However, no assessment of the dust deposition temporal variability in connection with its regional spatial distribution has been achieved so far from network observations over more than 1 year. To investigate dust deposition dynamics at the regional scale, five automatic deposition collectors named CARAGA (Collecteur Automatique de Retombées Atmosphériques insolubles à Grande Autonomie in French) have been deployed in the western Mediterranean region during 1 to 3 years depending on the station. The sites include, from south to north, Lampedusa, Majorca, Corsica, Frioul and Le Casset (southern French Alps). Deposition measurements are performed on a common weekly period at the five sites. The mean dust deposition fluxes are higher close to the northern African coasts and decrease following a south–north gradient, with values from 7.4 g m−2 year−1 in Lampedusa (35°31′ N, 12°37′ E) to 1 g m−2 year−1 in Le Casset (44°59′ N, 6°28′ E). The maximum deposition flux recorded is of 3.2 g m−2 wk−1 in Majorca with only two other events showing more than 1 g m−2 wk−1 in Lampedusa, and a maximum of 0.5 g m−2 wk−1 in Corsica. The maximum value of 2.1 g m−2 year−1 observed in Corsica in 2013 is much lower than existing records in the area over the 3 previous decades (11–14 g m−2 year−1). From the 537 available samples, 98 major Saharan dust deposition events have been identified in the records between 2011 and 2013. Complementary observations provided by both satellite and air mass trajectories are used to identify the dust provenance areas and the transport pathways from the Sahara to the stations for the studied period. Despite the large size of African dust plumes detected by satellites, more than 80 % of the major dust deposition events are recorded at only one station, suggesting that the dust provenance, transport and deposition processes (i.e. wet vs. dry) of dust are different and specific for the different deposition sites in the Mediterranean studied area. The results tend to indicate that wet deposition is the main form of deposition for mineral dust in the western Mediterranean basin, but the contribution of dry deposition (in the sense that no precipitation was detected at the surface) is far from being negligible, and contributes 10 to 46 % to the major dust deposition events, depending on the sampling site.

We applied the positive matrix factorization model to two large data sets collected during two intensive measurement campaigns (summer 2011 and winter 2012) at a sub-urban site in Beirut, Lebanon, in order to identify NMHC (non-methane hydrocarbons) sources and quantify their contribution to ambient levels. Six factors were identified in winter and five factors in summer. PMF-resolved source profiles were consistent with source profiles established by near-field measurements. The major sources were traffic-related emissions (combustion and gasoline evaporation) in winter and in summer accounting for 51 and 74 wt %, respectively, in agreement with the national emission inventory. The gasoline evaporation related to traffic source had a significant contribution regardless of the season (22 wt % in winter and 30 wt % in summer). The NMHC emissions from road transport are estimated from observations and PMF results, and compared to local and global emission inventories. The PMF analysis finds reasonable differences on emission rates, of 20–39 % higher than the national road transport inventory. However, global inventories (ACCMIP, EDGAR, MACCity) underestimate the emissions up to a factor of 10 for the transportation sector. When combining emission inventory to our results, there is strong evidence that control measures in Lebanon should be targeted on mitigating the NMHC emissions from the traffic-related sources. From a global perspective, an assessment of VOC (volatile organic compounds) anthropogenic emission inventories for the Middle East region as a whole seems necessary as these emissions could be much higher than expected at least from the road transport sector.

The French critical zone initiative, called OZCAR (Observatoires de la Zone Critique–Application et Recherche or Critical Zone Observatories–Application and Research) is a National Research Infrastructure (RI). OZCAR-RI is a network of instrumented sites, bringing together 21 pre-existing research observatories monitoring different compartments of the zone situated between “the rock and the sky,” the Earth’s skin or critical zone (CZ), over the long term. These observatories are regionally based and have specific initial scientific questions, monitoring strategies, databases, and modeling activities. The diversity of OZCAR-RI observatories and sites is well representative of the heterogeneity of the CZ and of the scientific communities studying it. Despite this diversity, all OZCAR-RI sites share a main overarching mandate, which is to monitor, understand, and predict (“earthcast”) the fluxes of water and matter of the Earth’s near surface and how they will change in response to the “new climatic regime.” The vision for OZCAR strategic development aims at designing an open infrastructure, building a national CZ community able to share a systemic representation of the CZ , and educating a new generation of scientists more apt to tackle the wicked problem of the Anthropocene. OZCAR articulates around: (i) a set of common scientific questions and cross-cutting scientific activities using the wealth of OZCAR-RI observatories, (ii) an ambitious instrumental development program, and (iii) a better interaction between data and models to integrate the different time and spatial scales. Internationally, OZCAR-RI aims at strengthening the CZ community by providing a model of organization for pre-existing observatories and by offering CZ instrumented sites. OZCAR is one of two French mirrors of the European Strategy Forum on Research Infrastructure (eLTER-ESFRI) project.

Strain engineering is a powerful approach in micro- and optoelectronics to enhance carrier mobility, tune the bandgap of heterostructures, or break lattice symmetry for nonlinear optics. The dielectric stressors and bonding interfaces used for strain engineering in photonics can however limit thermal dissipation and the maximum operation temperature of devices. We demonstrate a new approach for enhanced thermal dissipation with stressor layers by combining metals and dielectrics. The method is applied to the germanium semiconductor. All-around tensile-strained germanium microdisks have been fabricated with metallic pedestals. The transferred tensile strain leads to a germanium thin film with a direct bandgap. Under continuous wave optical pumping, the emission of the whispering gallery modes is characterized by a threshold and an abrupt linewidth narrowing by a factor larger than 2. The occurrence of stimulated emission is corroborated by modeling of the optical gain. This demonstrates lasing with pure germanium microdisks.

The performance of 18 European institutions involved in long-term non-methane hydrocarbon (NMHC) measurements in ambient air within the framework of the Global Atmosphere Watch (GAW) and the European Monitoring and Evaluation Programme (EMEP) was assessed with respect to data quality objectives (DQOs) of ACTRIS (Aerosols, Clouds, and Trace gases Research InfraStructure Network) and GAW. Compared to previous intercomparison studies the DQOs define a novel approach to assess and ensure a high quality of the measurements. Having already been adopted by GAW, the ACTRIS DQOs are demanding with deviations to a reference value of less than 5 % and a repeatability of better than 2 % for NMHC mole fractions above 0.1 nmol mol−1. The participants of the intercomparison analysed two dry gas mixtures in pressurised cylinders, a 30-component NMHC mixture in nitrogen (NMHC_N2) at approximately 1 nmol mol−1 and a whole air sample (NMHC_air), following a standardised operation procedure including zero- and calibration gas measurements. Furthermore, participants had to report details on their instruments and assess their measurement uncertainties. The NMHCs were analysed either by gas chromatography–flame ionisation detection (GC-FID) or by gas chromatography–mass spectrometry (GC-MS). For the NMHC_N2 measurements, 62 % of the reported values were within the 5 % deviation class corresponding to the ACTRIS DQOs. For NMHC_air, generally more frequent and larger deviations to the assigned values were observed, with 50 % of the reported values within the 5 % deviation class. Important contributors to the poorer performance in NMHC_air compared to NMHC_N2 were a more complex matrix and a larger span of NMHC mole fractions (0.03–2.5 nmol mol−1). The performance of the participating laboratories were affected by the different measurement procedures such as the usage of a two-step vs. a one-step calibration, breakthroughs of C2–C3 hydrocarbons in the focussing trap, blank values in zero-gas measurements (especially for those systems using a Nafion® Dryer), adsorptive losses of aromatic compounds, and insufficient chromatographic separation.

Measurements of gaseous and particulate organic carbon were performed during the MEGAPOLI experiments, in July 2009 and January–February 2010, at the SIRTA observatory in suburban Paris. Measurements comprise primary and secondary volatile organic compounds (VOCs), of both anthropogenic and biogenic origins, including C12–C16 n-alkanes of intermediate volatility (IVOCs), suspected to be efficient precursors of secondary organic aerosol (SOA). The time series of gaseous carbon are generally consistent with times series of particulate organic carbon at regional scale, and are clearly affected by meteorology and air mass origin. Concentration levels of anthropogenic VOCs in urban and suburban Paris were surprisingly low (2–963 ppt) compared to other megacities worldwide and to rural continental sites. Urban enhancement ratios of anthropogenic VOC pairs agree well between the urban and suburban Paris sites, showing the regional extent of anthropogenic sources of similar composition. Contrary to other primary anthropogenic VOCs (aromatics and alkanes), IVOCs showed lower concentrations in winter (< 5 ppt) compared to summer (13–27 ppt), which cannot be explained by the gas-particle partitioning theory. Higher concentrations of most oxygenated VOCs in winter (18–5984 ppt) suggest their dominant primary anthropogenic origin. The respective role of primary anthropogenic gaseous compounds in regional SOA formation was investigated by estimating the SOA mass concentration expected from the anthropogenic VOCs and IVOCs (I / VOCs) measured at SIRTA. From an integrated approach based on emission ratios and SOA yields, 38 % of the SOA measured at SIRTA is explained by the measured concentrations of I / VOCs, with a 2% contribution by C12–C16 n-alkane IVOCs. From the results of an alternative time-resolved approach, the average IVOC contribution to SOA formation is estimated to be 7%, which is half of the average contribution of the traditional aromatic compounds (15%). Both approaches, which are based on in situ observations of particular I / VOCs, emphasize the importance of the intermediate volatility compounds in the SOA formation, and support previous results from chamber experiments and modeling studies. They also support the need to make systematic the IVOCs' speciated measurement during field campaigns.

Beirut, the capital of Lebanon, which is located on the eastern shore of the Mediterranean basin, experiences high air pollution episodes. Annual average concentrations of coarse and fine particulate matter (PM2.5) as well as nitrogen oxides (NOx) often exceed the World Health Organization (WHO) guidelines. Therefore, improving air quality in this region is essential. The Polyphemus/Polair3D modeling system is used here to investigate air pollution episodes in Beirut during 2 to 18 July 2011. The modeling domain covers two nested grids of 1 and 5 km horizontal resolution over greater Beirut and Lebanon, respectively. The anthropogenic emission inventory was developed earlier (Waked et al., 2012). The Weather and Research Forecasting (WRF) model is used to generate the meteorological fields and the Model of Emissions of Gases and Aerosols from Nature (MEGAN) is used for biogenic emissions. The results of the study are compared to measurements from a field campaign conducted in the suburb of Beirut during 2–18 July 2011. The model reproduces satisfactorily the concentrations of most gaseous pollutants, the total mass of PM2.5 as well as PM2.5 elemental carbon (EC), organic carbon (OC), and sulfate. Ozone concentrations are overestimated and it appears that this overestimation results mainly from the boundary conditions.

Chemical Ionisation Mass Spectrometer measurements of hydroxyl radical (OH) and the sum of hydroperoxy and organic peroxy (HO2+RO2) radicals were conducted during the MEGAPOLI summer field campaign at the SIRTA observatory near Paris, France, in July 2009. OH and (HO2+RO2) showed a typical diurnal variation with averaged daytime maxima values around 5×106 and 1.2×108 molecule cm−3, respectively. Simultaneously, a large number of ancillary measurements, such as NOx, O3, HONO, HCHO and other VOCs were also conducted. These data provide an opportunity to assess our understanding of the radical chemistry in a suburban environment by comparing the radical observations to calculations. First, OH mixing ratios were estimated by a simple Photo Stationary State (PSS) calculation. PSS calculations overestimate the OH mixing ratio by 50%, especially at NOx mixing ratios lower than 10 ppb, suggesting that some loss processes were missing in the calculation at low NOx. Then, a photochemical box model simulation based on the Master Chemical Mechanism (MCM) and constrained by ancillary measurements was run to calculate radical concentrations. Three different modelling procedures were tested, varying the way the unconstrained secondary species were estimated, to cope with the unavoidable lack of their measurements. They led to significant differences in simulated radical concentrations. OH and (HO2+RO2) concentrations estimated by two selected model version were compared with measurements. These versions of the model were chosen because they lead, respectively, to the higher and lower simulated radical concentrations and are thus the two extremes versions. The box model showed better results than PSS calculations, with a slight overestimation of 12% and 5%, for OH and (HO2+RO2) respectively, in average for the reference model, and an overestimation of approximately 20% for OH and an underestimation for (HO2+RO2) for the other selected model version. Thus, we can conclude from our study that OH and (HO2+RO2) radical levels agree on average with observations within the uncertainty range. Finally, an analysis of the radical budget, on a daily basis (06:00–18:00 UTC), indicates that HONO photolysis (~35%), O3 photolysis (~23%), and aldehydes and ketones photolysis (~16% for formaldehyde and 18% for others) are the main radical initiation pathways. According to the MCM modelling, the reactions of RO2 with NO2 (~19%), leading mainly to PAN formation, is a significant termination pathway in addition to the main net loss via reaction of OH with NO2 (~50%).

Hydroxyl radicals play a central role in the troposphere as they control the lifetime of many trace gases. Measurement of OH reactivity (OH loss rate) is important to better constrain the OH budget and also to evaluate the completeness of measured VOC budget. Total atmospheric OH reactivity was measured for the first time in an European Megacity: Paris and its surrounding areas with 12 million inhabitants, during the MEGAPOLI winter campaign 2010. The method deployed was the Comparative Reactivity Method (CRM). The measured dataset contains both measured and calculated OH reactivity from CO, NOx and VOCs measured via PTR-MS, GC-FID and GC-MS instruments. The reactivities observed in Paris covered a range from 10 s−1 to 130 s−1, indicating a large loading of chemical reactants. The present study showed that, when clean marine air masses influenced Paris, the purely local OH reactivity (20 s−1) is well explained by the measured species. Nevertheless, when there is a continental import of air masses, high levels of OH reactivity were obtained (120–130 s−1) and the missing OH reactivity measured in this case jumped to 75%. Using covariations of the missing OH reactivity to secondary inorganic species in fine aerosols, we suggest that the missing OH reactants were most likely highly oxidized compounds issued from photochemically processed air masses of anthropogenic origin.

A tracer test to examine in situ denitrification in shallow groundwater by a piezometer with a packer system used bromide as a tracer of dilution and acetylene (10%) to block the denitrification process at the nitrous oxide stage. During the test, dissolved oxygen, nitrate (NO3‾), bromide (Br‾), nitrous oxide (N2O) and dissolved organic carbon (DOC) were measured. To calibrate the experimental method, comparison with numerical simulations of the groundwater transfer were carried out, taking into account the environmental characteristics. The method was tested by measurements undertaken in different environmental conditions (geology, land use and hydrology) in two riparian wetlands. Denitrification rates measured by this method ranged from 5.7 10-6 g N-NO3‾L-1 h-1 to 1.97 10-3 g N-NO3‾L-1 h-1 The method is applicable in shallow aquifers with a permeability from 10-2 to 10-4m s-1. Keywords: denitrification, shallowaquifer, groundwater modelling, wetlands, nitrate-nitrogen, packer system

This study highlights the role of interactions between surface and sub-surface water of the riparian zone of a large river (the Garonne, SW France). Information is given about the role of surface water in supplying Dissolved Organic Carbon (DOC ) to the riparian zone for nitrate removal processes. The densities of bacteria (up to 3.3 106 cell m L-1) in groundwater are strongly conditioned by the water moving during flood events. Total bacterial densities in groundwater were related to surface water bacterial densities. In sediment, total bacteria are attached mainly to fine particles (90% in the fraction < 1 mm). Spatial variations in organic carbon and nitrate content in groundwater at the site studied are correlated with exchanges between the groundwater and the river, from the upstream to the downstream part of the meander. Total bacterial densities, nitrate and decressing organic carbon concentrations follow the same pattern. These results suggest that, in this kind of riparian wetland, nitrate from alluvial groundwater influenced by agricultural practices may be denitrified by bacteria in the presence of organic carbon from river surface water. Keywords: riparian zone, nitrate removal, spatial variations, alluvial groundwater