R. Sarda-Esteve

Large contribution of water-insoluble secondary organic aerosols in the region of Paris (France) during wintertime

Near real-time measurements of carbonaceous aerosols were performed in fine aerosols for a 10-day period during winter at a suburban site of Paris (France). These measurements were performed using an OCEC Sunset Field instrument for elemental carbon (EC) and organic carbon (OC); a Particle-Into-Liquid-Sampler coupled with a Total Organic Carbon (PILS-TOC) instrument for water-soluble OC (WSOC); and a 7-lambda aethalometer for absorption. A successful comparison was performed with filter sampling performed in parallel for EC, OC, and WSOC, providing further confidence on the results obtained by the online analyzers. A modified version of the aethalometer model was used to derive hourly concentrations of 3 organic aerosol (OA) sources: fossil fuel, wood burning, and secondary. This source apportionment was validated for primary OA (fossil fuel, wood burning) using time-resolved measurements of specific tracers (including levoglucosan, water-soluble potassium and methanol for wood burning) and showed that secondary organic aerosols (SOA) were the most abundant OA species during our study. Water-soluble properties of these different OA sources were investigated from the reconstruction of experimentally determined water-soluble/insoluble OC. About 23% of WSOC was found to be of a secondary (photochemical) origin. A large fraction of SOA was assigned as water-insoluble and could originate from semi-volatile primary OA from wood burning and/or anthropogenic emissions. These results have been obtained at a typical suburban site in France and may be then representative of a larger European area. They bring new light on the commonly accepted idea that SOA is mainly water-soluble.

Total OH reactivity measurements in Paris during the 2010 MEGAPOLI winter campaign

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 10s to 130s, indicating a large loading of chemical reactants. The present study showed that, when clean marine air masses influenced Paris, the purely local OH reactivity (20s) 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) 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. Chapitre 4 : Mesure de la réactivité OH à Paris pendant MEGAPOLI hiver 2010 146 Mesure de la réactivité atmosphérique totale avec les radicaux OH : Développement et applications en Ile-de-France

Volatile organic compounds sources in Paris in spring 2007. Part I: qualitative analysis

Environmental context Megacities are huge hotspots of pollutants that have an impact on atmospheric composition on local to larger scales. This study presents for the first time detailed results of measurements of volatile organic compounds in Paris and shows that, whereas non-methane hydrocarbons are mainly of local and regional origin associated with traffic emissions, a significant part of oxygenated volatile organic compounds originates from continental import. This highlights the importance of measuring volatile organic compounds instead of non-methane hydrocarbons alone in source classification studies. Abstract High-time-resolution measurements of volatile organic compounds (VOCs) were performed in the Paris city centre in spring 2007. The studied region was influenced mainly by air masses of two origins: (1) from the Atlantic Ocean, and (2) from north-eastern Europe. Although the baseline levels (i.e. those not influenced by local emissions) of non-methane hydrocarbons (NMHC) and CO were only slightly impacted by changes in the air-mass origin, oxygenated compounds such as acetone and methanol showed much higher baseline levels in continentally influenced air masses. This suggests that NMHC and CO mixing ratios were mainly influenced by local-to-regional-scale sources whereas oxygenated compounds had a more significant continental-scale contribution. This highlights the importance of measuring VOCs instead of NMHC alone in source classification studies. The period of Atlantic air influence was used to characterise local pollution, which was dominated by traffic-related emissions, although traffic represents the source of only one third of total VOCs emissions in the local inventory. In addition to traffic-related sources, additional sources were identified; in particular, emissions from dry-cleaning activities were identified by the use of a specific tracer (i.e. tetrachloroethylene).

Isoprene emission from phytoplankton monocultures: the relationship with chlorophyll-a, cell volume and carbon content

We report here isoprene emission rates determined from various phytoplankton cultures incubated under PAR light which was varied so as to simulate a natural diel cycle. Phytoplankton species representative of different phytoplankton functional types (PFTs) namely: cyanobacteria, diatoms, coccolithophorides, and chlorophytes have been studied. Biomass normalised isoprene emission rates presented here relative to the chlorophyll-a (Chl-a) content of the cultures showed that the two cyanobacteria (Synechococcus and Trichodesmium) were the strongest emitters with emission rates in the range of 17 to 28 mu g C(5)H(8) g(-1) Chl-a h(-1). Diatoms produced isoprene in a significantly lower emission range: 3 to 7.5 mu g C(5)H(8) g(-1) Chl-a h(-1) and Dunaliella tertiolecta was by far the lowest emitter of our investigated plankton cultures. Despite the group specific differences observed, a high emission rate variance was observed to occur within one phytoplankton group. However, a combination of literature and our own data showed a clear relationship between the actual cell volume and the isoprene emission rates. This relationship could be a valuable tool for future modelling approaches of global isoprene emissions.

Variation of atmospheric volatile organic compounds over the Southern Indian Ocean (30°S-49°S)

Environmental context. Oceans represent 70% of the blue planet, and surprisingly, ocean emission in term of volatile organic compounds is poorly understood. The potential climate impacts on a global scale of various trace organic gases have been established, and the terrestrial inputs are well studied, but little is known about which of these can be emitted from oceanic sources. In the present study, atmospheric samples were taken over the Southern Indian Ocean, while crossing some oceanic fronts and different phytoplankton species. Such a study should aid in understanding oceanic emission, especially from phytoplankton, and will help modellers to determine concentrations of organic traces in the remote marine troposphere. Abstract. Considering its size and potential importance, the ocean is poorly characterised in terms of volatile organic compounds (VOC) that play important roles in global atmospheric chemistry. In order to better understand their potential sources and sinks over the Southern Indian Austral Ocean, shipborne measurements of selected species were made during the MANCHOT campaign during December 2004, on board the research vessel Marion Dufresne. Along the transect La Reunion to Kerguelen Island, air measurements of selected VOC (including dimethylsulfide (DMS) isoprene, carbonyls and organohalogens), carbon monoxide and ozone were performed, crossing subtropical, temperate and sub-Antarctic waters as well as pronounced subtropical and sub-Antarctic oceanic fronts. The remote marine boundary layer was characterised at latitudes 45–50°S. Oceanic fronts were associated with enhanced chlorophyll and biological activity in the seawater and elevated DMS and organohalogens in the atmosphere. These were compared with a satellite-derived phytoplankton distribution (PHYSAT). Diurnal variation for isoprene, terpenes, acetone and acetaldehyde was observed, analogously to recent results observed in mesocosm experiments.

Limitation of the Use of the Absorption Angstrom Exponent for Source Apportionment of Equivalent Black Carbon: a Case Study from the North West Indo-Gangetic Plain

Angstrom exponent measurements of equivalent black carbon (BCeq) have recently been introduced as a novel tool to apportion the contribution of biomass burning sources to the BCeq mass. The BCeq is the mass of ideal BC with defined optical properties that, upon deposition on the aethalometer filter tape, would cause equal optical attenuation of light to the actual PM2.5 aerosol deposited. The BCeq mass hence is identical to the mass of the total light-absorbing carbon deposited on the filter tape. Here, we use simultaneously collected data from a seven-wavelength aethalometer and a high-sensitivity proton-transfer reaction mass spectrometer installed at a suburban site in Mohali (Punjab), India, to identify a number of biomass combustion plumes. The identified types of biomass combustion include paddy- and wheat-residue burning, leaf litter, and garbage burning. Traffic plumes were selected for comparison. We find that the combustion efficiency, rather than the fuel used, determines αabs, and consequently, the αabs can be ∼1 for flaming biomass combustion and >1 for older vehicles that operate with poorly optimized engines. Thus, the absorption angstrom exponent is not representative of the fuel used and, therefore, cannot be used as a generic tracer to constrain source contributions.

Carbon monoxide emissions by phytoplankton: evidence from laboratory experiments

Environmental context. Carbon monoxide (CO) is a key component for atmospheric chemistry and its production in the ocean, although minor at the global scale, could play a significant role in the remote marine atmosphere. Up to now, CO production in the ocean was considered to mainly originate from the photo-production of dissolved organic matter (mainly under UV radiation). In this paper, we show evidence for direct production of CO by phytoplankton and we suggest it as a significant mechanism for CO production in the ocean. Abstract. In order to investigate carbon monoxide (CO) emissions by phytoplankton organisms, a series of laboratory experiments was conducted in Kiel (Germany). Nine monocultures, including diatoms, coccolithophorids, chlorophytes and cyanobacteria have been characterised. This was done by following the CO variations from monoculture aliquots exposed to photosynthetically active radiation during one or two complete diurnal cycles. All the studied cultures have shown significant CO production when illuminated. Emission rates have been estimated to range from 1.4 × 10–5 to 8.7 × 10–4 μg of CO μg chlorophyll–1 h–1 depending on the species. When considering the magnitude of the emission rates from the largest CO emitters (cyanobacteria and diatoms), this biotic source could represent up to 20% of the CO produced in oceanic waters. As global models currently mainly consider CO production from the photo-degradation of dissolved organic matter, this study suggests that biotic CO production should also be taken into account. Whether this biological production might also contribute to some degree to the previous observed non-zero CO production below the euphotic zone (dark CO production) cannot be deduced here and needs to be further investigated.

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

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 αand 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 Published by Copernicus Publications on behalf of the European Geosciences Union. 14298 C. Debevec et al.: Biogenic VOCs at an eastern Mediterranean background site to observe NPF at CAO in March 2015. NPF event days were characterized by either (1) a predominant anthropogenic influence (high concentrations of anthropogenic source 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 oxygenlike 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.

New application of direct analysis in real time high-resolution mass spectrometry for the untargeted analysis of fresh and aged secondary organic aerosols generated from monoterpenes

RATIONALE Secondary organic aerosols (SOAs) represent a significant portion of total atmospheric aerosols. They are generated by the oxidation of volatile organic compounds (VOCs), and particularly biogenic VOCs (BVOCs). The analysis of such samples is usually performed by targeted methods that often require time-consuming preparation steps that can induce loss of compounds and/or sample contaminations. METHODS Recently, untargeted methods using high-resolution mass spectrometry (HRMS) have been successfully employed for a broad characterization of chemicals in SOAs. Herein we propose a new application of the direct analysis in real time (DART) ionization method combined with HRMS to quickly detect several hundred chemicals in SOAs collected on a quartz filter without sample preparation or separation techniques. RESULTS The reproducibility of measurements was good, with several hundred elemental compositions common to three different replicates. The relative standard deviations of the intensities of the chemical families ranged from 6% to 35%, with sufficient sensitivity to allow the unambiguous detection of 4 ng/mm2 of pinic acid. The presence of oligomers and specific tracers was highlighted by MSn (n ≤ 4) experiments, an achievement that is difficult to attain with other ultrahigh-resolution mass spectrometers. Contributions of this untargeted DART-HRMS method were illustrated by the analysis of fresh and aged SOAs from different gaseous precursors such as limonene, a β-pinene/limonene mixture or scots pines emissions. CONCLUSIONS The results show that it is possible to use DART-HRMS for the identification of tracers of specific aging reactions, or for the identification of aerosols from specific biogenic precursors.

Diagnostic Evaluations of the CHIMERE Model: Local Versus Advected Contributions of Fine Particles and Nitrate Formation Regime in the Paris Megacity

Chemistry transport models (CTMs) are a powerful tool to investigate various features of the aerosol pollution in megacities, including its geographical origin or its sensitivity to anthropogenic emissions changes (scenario analysis). However, due to the numerous uncertainties still at stake in CTMs, assessing the reliability of the results obtained in these two common exercises remains a challenging task that usually requires specific observations and methodologies. In our work, we have taken advantage of some recent campaigns in the Paris region—PARTICULES and FRANCIPOL—to run a diagnostic evaluation of the CHIMERE model regarding these two issues. The first substantive point is to assess in what extent the model is able to retrieve the correct share between local production and regional advection of aerosol pollution in the Paris agglomeration. During a whole year, daily measurements of the fine particulate matter (PM2.5) and its main chemical constituents (elemental and organic carbon, nitrate, sulfate and ammonium) are available at various stations both in and around Paris (PARTICULES project). Based on back-trajectory data, we can locate the upwind station, from which the concentration is identified as the import, the local production being deduced from the urban concentration by subtraction. Uncertainties on these contributions are quantified. Small biases in urban background PM2.5 simulations (+16 %) hide significant error compensations between local and advected contributions, as well as in PM2.5 chemical compounds. In particular, wintertime OM imports appear strongly underestimated (potentially explained by uncertain continental woodburning emissions and missing SOA pathways) while local OM and EC production are overestimated all along the year (likely to be related to uncertainties in emissions and dynamics). A statistically significant local formation of nitrate is also highlighted from observations, but missed by the model. Together with the overestimation of nitrate imports, it leads to a bias of +51 % on the local PM2.5 contribution. In parallel to inorganic aerosols measurements, gaseous nitrate precursors (nitric acid and ammonia) have also been measured (FRANCIPOL project), which offers the opportunity to investigate the regime of nitrate formation in Paris and its sensitivity to precursor changes and to assess, again, the ability of the CHIMERE model to retrieve the observed sensitivity. Experimental data clearly point to NH3-rich conditions in the city (as indicated by high gas ratio values), but a quite similar sensitivity of nitrate concentrations to changes in nitric acid and ammonia. However, simulation results indicate that the model highly overestimates the sensitivity of nitrate to ammonia changes. Thus, while overall particulate matter levels are well reproduced by the model, differences with observations are much larger for local versus advected contributions, and the sensitivity of nitrate formation with respect to gaseous precursors.