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The complex refractive index (CRI) is one of the key parameter driving aerosol spectral optical properties and direct radiative effects (DRE). Its value and spectral variation under different conditions, such as anthropogenic− and biogenic−dominated environments and anthropogenic−biogenic mixing situations, remains not fully understood. As a consequence, oversimplified representations of aerosol optical properties are generally used in climate models. Therefore, measurements of aerosol CRI in different environments and their inclusion in models are needed. The field observations from the ACROSS campaign, performed in June-July 2022 in the Ile de France region, are used in this study to deepen the knowledge of aerosol optical properties, aiming to improve the aerosol representation in the CHIMERE model and provide the best constraint for DRE simulations. Measurements obtained both at the Paris city center and the Rambouilllet rural forest sites during ACROSS are considered, in order to explore the CRI variability from anthropogenic−dominated to biogenic−dominated environments, including anthropogenic−biogenic mixing situations. The CRI retrievals at seven different wavelengths, performed by combining the Mie theory with optical and size distribution measurements, are representative of different atmospheric conditions, aerosol loadings as well as type and chemical compositions. In fact, the June-July 2022 period was characterized by highly diversified weather conditions: 1) two strong heatwaves, promoting SOA build-up and favoring the export of the Paris pollution plume towards the forest site; 2) Saharan dust events transported from the upper atmosphere to the ground; 3) biomass burning episode; 4) periods with reduced anthropogenic influence. The CRI retrievals under these different conditions and their link to particulate chemical composition is investigated. Hence, the CRI dataset presented here constitutes a unique dataset from which models can benefit to validate and constrain simulations and DRE estimations, under both urban and biogenic emissions influence. These data, in conjunction with those from the aircraft observations during ACROSS, are used to initialize and perform sensitivity studies on the aerosol DRE, using the CHIMERE−WRF coupled model, the OPTSIM model for the aerosol optical properties and the Rapid Radiative Transfer Model for GCMs (RRTMG).Keywords: Complex refractive index, direct radiative effect, aerosol mixing, urban, forest

Global population increase has placed pressure on available resources and has resulted in the emission of a variety of trace gases into the troposphere that includes volatile organic compounds (VOCs). This class of molecules plays major roles in the formation of secondary products such as secondary organic aerosol (SOA) and tropospheric ozone, which adversely affect Earth’s climate and human health. Research has continued to reveal more details of complex atmospheric degradation processes involving VOCs of both anthropogenic and biogenic origins, but relatively few have been directly studied including the possible impacts of mixing of air masses of anthropogenic and biogenic origins. The ACROSS (Atmospheric ChemistRy Of the Suburban foreSt) project aims to improve our knowledge of atmospheric chemical processes that occur in such mixed air masses and their impact on air quality. The experimental strategy of ACROSS is based on ground-based and airborne observations during an international, large-scale, comprehensive, multi-platform, multi-site field campaign that took place in the summer of 2022 in the greater Paris and suburban forested areas.As VOCs are processed in the atmosphere, secondary compounds are produced including highly oxygenated organic molecules (HOMs) that are a subset of low volatility organic compounds characterized by their contribution to formation and ageing of SOA. Nitrate ion chemical ionization (CI), coupled with an Atmospheric Pressure Interface−Time-Of-Flight Mass Spectrometer (API-TOF-MS) is an online analytical technique that detects and quantifies gas-phase HOMs (and other compounds) with high sensitivity and mass resolution in the atmosphere or laboratory systems. This instrument provides measurements that help to fill the observational gap between the aerosol and gas phases.The instrument was deployed at the top of a 40 m tower (above the canopy) in the Rambouillet forest site during the ACROSS field campaign to measure and identify HOMs formed mainly under two different composition regimes: biogenic emissions only, and biogenic air/urban air mixtures. The data collected by the instrument will be presented and used to enhance understanding of the chemical formation pathways of HOMs and their contribution to the composition of aerosols.

Cyclic volatile methyl Siloxanes (cVMS) are a group of silicon-based organic compounds of anthropogenic origin that are found ubiquitously in the ambient air. They find wide application in many industrial, automotive products, consumer, and personal care products such as paints, solvents, adhesives, cosmetics, polymers, etc. About 90% of the environmentally released cyclic siloxanes diffuse directly into the atmosphere. They are high–production volume chemicals with some having an annual production rate of 45 to 227 thousand tons worldwide. Siloxanes have been observed in both urban and rural areas. Among the different siloxanes emitted into the atmosphere hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), and decamethylcyclopentasiloxane (D5) are of great importance due to their subsequent concentrations. It should be mentioned that siloxanes are not readily biodegradable which means they can persist in the environment for a long duration. The D4 species has already been identified as a potential persistent organic pollutant (PoPs). D4 and D5 are very persistent and bioaccumulative and have evinced or potential hazards to both humans and the environment.Taking advantage of the Vocus proton-transfer-reaction time-of-flight mass spectrometer (VOCUS PTR–TOF–MS) the D3, D4, and D5 species were measured in real-time downtown Paris in the June–July 2022 period. The measurements were performed during the ACROSS (Atmospheric ChemistRy Of the Suburban foreSt) field campaign at the urban site located at Université Paris Cité (48.83°N, 2.38°E) sampling at about 25 m above the ground level. The data collected during the summer 2022 showed that the mean concentrations were 0.099±0.009, 0.045±0.009, and 0.131±0.089 ppb for D3, D4, and D5, respectively. A strong diurnal cycle was observed for the different siloxanes. Concentrations for the D5 siloxane peaked in the morning with an averaged maximum of 0.298± 0.119 ppb while the 25th and the 75th quantile are 0.221 and 0.377 ppb, respectively. In the afternoon concentrations show a minimum value, followed by a slight increase during the night. The D5 is the most abundant siloxane species and shows the strongest diurnal cycle compared to the other two identified siloxanes. Observations during the campaign and the potential reaction products and sources of siloxanes will be discussed in this work.KEYWORDS: Siloxanes; Cyclic Siloxanes; D3,D4 and D5; Ambient Air; PoPs; ACROSS; HR- Mass Spectrometry; VOCUS PTR-Tof

The international ACROSS (Atmospheric ChemistRy Of the Suburban forest) intensive field measurement campaign (supported by the Make Our Planet Great Again initiative) took place from June 13 to July 25 2022 in and around the Ile-de-France during an exceptional hot (more than 3°C above the climatological mean for France) and dry summer season. This work will provide a broad classification of weather conditions that occurred during the campaign, useful for further analysis of observations and simulations. Weather scenarios will be analysed in terms of synoptic weather situations, relating transport patterns (regional advection to the Ile-de-France region, plumes from Paris agglomeration), temperature and relative humidity evolution. During the June-July 2022 period, several distinct weather and pollution patterns occurred, among which: (1) two strong heatwaves, with large photochemical activity promoting secondary pollutants build-up (O3, SOA), (2) advection of relatively clean oceanic air masses, and (3) Saharan dust and intense forest fire events with dust and fire aerosol advection to the Ile-de-France region. The analysis is based on meteorological data from several models (GFS, WRF, ARPEGE, AROME) and observations, pollution forecasts from the French Prev’Air system (http://www2.prevair.org/), and from the AirParif Esmeralda platform (http://www.esmeralda-web.fr/accueil/) that have been used for the airborne campaign support. In addition, dedicated simulations with the CHIMERE model (see companion abstract by Di Antonio et al. for this session), and major pollutant observations by air quality networks, from satellites, or performed within ACROSS will be used to analyse how meteorological conditions and weather patterns impacted the spatial distributions of major primary and secondary chemical species. Especially tracers of anthropogenic and biogenic emissions and photochemical activity (O3, PM2.5, OA, BC, NOx, BVOC) will be analysed. Keywords: Meteorology, pollutant distributions, transport patterns, ACROSS, MOPGA

Organic aerosol (OA) from natural or anthropogenic origin can be directly emitted into the atmosphere (primary organic aerosols, POA) or formed by secondary processes via the oxidation of volatile organic compounds (VOC). However, the formation pathways and their chemical composition of these secondary organic aerosols (SOA), which may contribute up to 90% of the OA mass, are not well understood to date, which is problematic due to the relevance of SOA on climate. To address this issue, this study uses a tracer-based approach to identify and quantify the contribution of different anthropogenic/biogenic VOCs precursors to the SOA formation. To do so, we combine experiments in a large scale atmospheric simulations chamber, CESAM (which means Multiphase Atmospheric Experimental Simulation Chamber), and field measurements during the ACROSS (Atmospheric ChemistRy Of the Suburban foreSt) campaign conducted in the Paris area in summer 2022. This approach provides both a mechanistic study of the oxidation of targeted VOCs in simulated and controlled rural/urban atmospheres and the identification of targeted tracers in the real atmosphere, to quantify their concentrations in ambient air.The ACROSS dataset consists in atmospheric samples of submicron aerosols collected twice a day (day and night) in the urban area of Paris and the Rambouillet forest on the south-west of Paris, as well as samples collected onboard the Safire ATR-42 research aircraft on low-level flights targeting the evolution and dilution of the Paris urban plume. The CESAM chamber dataset consists in samples of SOA generated by the OH oxidation of toluene/ m-xylene in various conditions.Filters are analyzed to provide with the chemical composition at the molecular scale by SFE-GC-MS (Supercritical Fluid Extraction Gas Chromatography- Mass Spectrometry) and UPLC-QTOF-MS (Ultra Performance Liquid Chromatography Time of Flight Mass Spectrometry). The organic mass and chemical speciation are obtained by aerosol mass spectrometry and the organic carbon (OC) concentrations by thermal-optical analysis.The first results of the ambient samples of Paris revealed that the OC concentration varied between 0.69 ± 0.07 and 9.48 ± 0.51 µgC/m3, which correspond to the 28% and 53% of the total mass of the submicron aerosols, for background and polluted (fire) conditions, respectively. These diverse conditions are favorable to trace the compounds identified during the simulation chamber experiments, such as benzoic acid, succinic acid, and 2-methyl-4-nitrophenol. These attempts will be presented and discussed in order to determine the contribution of specific precursors to SOA formation.

The role of relative humidity (RH) in secondary organic aerosol (SOA) formation from high-NOx photooxidation of long-chain alkanes was investigated by performing simulation chamber experiments on n...

Reaction rate constants for the reaction of n-dodecane with hydroxyl radicals were measured as a function of temperature between 283 and 303 K, using the relative rate method in the CESAM chamber (...

It is well known that the high population density of urban regions leads to significant degradation of the quality of the air because of the emissions of pollutants that are by-products of energy production, transportation, and industry. The composition and chemistry of urban air has been studied for many decades and these studies have led to detailed understanding of the factors controlling, for example, the formation of ozone, peroxyacetyl nitrate and other secondary species. In the last 20 to 30 years, significant progress has been made in reducing emissions of volatile organic compounds (VOCs) and oxides of nitrogen (NOx) in urban atmospheres. Substantial reductions in the abundance of secondary compounds, though, have been more elusive.Research has continued to reveal more and more details of the complex processes involved in the atmospheric degradation of wide varieties of volatile organic compounds (VOCs) of anthropogenic and biospheric (BVOCs) origins. BVOCs include isoprene, monoterpenes and sesquiterpenes, and oxygenated VOCs (OVOCs, such as small alcohols). Emissions of BVOCs depend on several factors such as plant or tree species, temperature, and photosynthetically active radiation. They consist almost exclusively of unsaturated compounds with chemistry somewhat different from those of typical urban organic compound emissions. Oxidation of VOCs can lead to molecules of low volatility that are prone to uptake into the aerosol phase.Recent studies conducted in megacities such as Paris, Mexico City, Los Angeles and those in China have led to significant advances in our understanding of the chemical evolution of urban plumes. However, important scientific questions remain on how mixing of anthropogenic and biogenic air masses modifies the composition of urban plumes and hence their impacts. Indeed, the proximity of cites to areas of strong biogenic emissions is not unusual. Many major cities at mid-latitudes are surrounded by forested areas.ACROSS (Atmospheric ChemistRy Of the Suburban foreSt) is an integrative, innovative, multi-scale project awarded under the “Make Our Planet Great Again” (MOPGA) framework that seeks to definitively improve understanding of the impacts of mixing urban and biogenic air masses on the oxidation of atmospheric VOCs. The ACROSS working hypothesis is that this leads to changes in the production of oxygenated VOCs whose properties (e.g. vapor pressures) alter their importance in incorporation into SOA and their roles in production of ozone and other secondary species. Changes are also expected in the efficiency of radical recycling affecting the atmospheric oxidative capacity. Particularly important is NOx transport to suburban biogenic environments and the resulting modification of key chemical processes.A key highlight of ACROSS is an intensive, multi-platform measurement campaign in the summer of 2022. It will use instruments staged on an airborne platform, a tower in the Rambouillet Forest near Paris, and other ground sites. The data collected from this campaign will be analyzed and studied to extract information about tropospheric oxidation chemistry generally, but also changes observed in the situation of mixed urban and biogenic air masses.This presentation will summarize plans for the ACROSS campaign.

We report on applications of ultraviolet light emitted diode based incoherent broadband cavity enhanced absorption spectroscopy (UV-LED-IBBCEAS) technique for optical monitoring of HONO, NO2 and CH2O in a simulation chamber. Performance intercomparison of the UV-LED-IBBCEAS with a wet chemistry-based NitroMAC sensor and a FTIR spectrometer has been carried out on real time simultaneous measurement of HONO, NO2 and CH2O concentrations during the reaction of NO2 with H2O vapor in the CESAM atmospheric simulation chamber. 1-σ (SNR = 1) detection limits of 200 pptv for NO2, 100 pptv for HONO and 5 ppbv for CH2O over 120 s were found for the UV-LED-IBBCEAS measurement. On the contrary to many set-ups where cavities are installed outside the simulation chamber, we describe here an original in-situ permanent installation. The intercomparison results demonstrate that IBBCEAS is a very well suitable technique for in situ simultaneous measurements of multiple chemically reactive species with high sensitivity and high precision even if the absorption bands of these species are overlapped. It offers excellent capacity to non-invasive optical monitoring of chemical reaction without any perturbation. For the application to simulation chamber, it has the advantage to provide a spatially integrated measurement across the reactor and hence to avoid point sampling related artefact.

Trace gas measurements were performed during the LANDEX (the LANDes EXperiment) Episode 1 field campaign in the summer 2017, in one of the largest European maritime pine forests (> 95% Pinus pinaster) located in southwestern France. Efforts have been focused on obtaining a good speciation of 20 major biogenic volatile organic compounds (BVOCs, including pinenes, carenes, terpinenes, linalool, camphene, etc.). This was made possible by the development of a new and specific chromatographic method. In order to assess the role of BVOCs in the local gas phase chemistry budget, their reactivity with the main atmospheric oxidants (hydroxyl radicals (OH), ozone (O3) and nitrate radicals (NO3)) and the corresponding consumption rates were determined. When considering the OH reactivity with BVOCs, isoprene and linalool accounted for 10-47% of the OH depletion during daytime, and monoterpenes for 50-65%, whereas monoterpenes were the main contributors during the night (70-85%). Sesquiterpenes and monoterpenes were the main contributors to the ozone reactivity, especially β-caryophyllene (30-70%), with a maximum contribution during nighttime. Nighttime nitrate reactivity was predominantly due to monoterpenes (i.e. 90-95%). Five specific groups have been proposed to classify the 19 BVOCs measured in the forest, according to their reactivity with atmospheric oxidants and their concentrations. The total amount of BVOCs consumed under and above the forest canopy was evaluated for 7 BVOCs (i.e. isoprene, α-pinene, β-pinene, myrcene, limonene + cis-ocimene and Δ3-carene). The reactivity of atmospheric oxidants and BVOCs at a local level are discussed in order to highlight the compounds (BVOCs, other VOCs), the atmospheric oxidants and the main associated reactive processes observed under the canopy of a maritime pine forest.

SummaryUsing CESAM, an atmospheric simulation chamber (cesam.cnrs.fr), we have developed a totally innovative platform for exposing mice to realistic atmospheric conditions. Here we present the first toxicological analyses of the organs of these mice after 48 hours to several days of exposure, carried out as part of feasibility experiments aimed at testing this experimental concept. This platform has received funding from the European Union’s Horizon 2020 research and innovation programme through the EUROCHAMP-2020 Infrastructure Activity under grant agreement N° 730997, and is now supporting the new REMEDIA H-2020 project (call H2020 “Exposome”) IntroductionThe World Health Organization (WHO) estimated that there were 3.7 million premature deaths due to air pollution in 2014, and confirmed that air pollution is the greatest environmental risk to health (responsible for a loss of more than 3% of productivity).The studies conducted so far show that the effects of air pollution on health depend not only on the quality of the surrounding air, but also on the subjects exposed and their individual vulnerability (asthma, obesity, period of life, etc.). Despite the evidence on the adverse health effects of exposure to air micro-pollutants, there are still uncertainties about the nature of these effects, and progress need to be made on their quantification. This limitation of knowledge is mainly attributed to the complexity of the polluted atmospheres, and to the great difficulty to model the impact of realistic situations of exposure. MethodologyThe innovative approach we set up is to realistically simulate, at the laboratory, the atmospheric mixture in all its complexity, thus keeping the ability to control, reproduce and carefully characterize the experimental conditions. We used the CESAM chamber (4.2 m3 stainless steel atmospheric simulation, evacuable down to a few 10-7 atm, temperature controlled between +15°C and +60°C) in order to study the myriad of products arising from the atmospheric oxidation of primary organic compounds.The experimental protocol consists in the continuous injection of relevant mixtures of primary pollutants (mainly nitrogen oxides, organic compounds from a representative mix of anthropogenic emissions, sulphur dioxide, soot, inorganic salts and potentially mineral dust particles if needed - e.g. to simulate Beijing’s atmosphere) at low concentrations (ppb levels) in air in the CESAM simulation chamber operated as a slow flow reactor. The residence time of simulated air parcels in the experimental volume is fixed to 4 hours, in order to represent air masses of regional scale. During this time the synthetic mixture is exposed to an artificial solar irradiation, allowing secondary pollutants such as ozone, nitric acid, formaldehyde, peroxyacetyl nitrate as well as complex polyfunctional organics including SOA to be produced and to reach their chemical steady state. Mice are exposed to constant flows of such a mixture during time scales of week to address their effects on health. ConclusionsHere we present the first toxicological analyses related to organs/tissue of these mice after exposure of 48h to several day, carried out with a representative atmosphere of Beijing or a representative atmosphere of Paris. ReferencesColl P. et al., 2018, WIT Transactions on Ecology and the Environment, 230.

The photooxidation and ozonolysis of a wide range of anthropogenic and biogenic compounds results in the formation of polyfunctional oxygenated organic volatile compounds (OVOCs), which are ubiquitous intermediates and important source of radicals, as well as a significant contributor to the organic fraction of aerosol, playing an important role in the air quality and in the health.With the aim of ensuring a good quality of the measurements, an intercomparison campaign on instruments and techniques to measure OVOCs was held at the EUPHORE atmosphere simulation chamber (Valencia, Spain), allowing the simultaneous sampling from the same air mixture under controlled conditions and facilitating the characterization of the instrumental performance. This intercomparison is part of the activities within the EUROCHAMP-2020 project (www.eurochamp.org) and is aligned with the ACTRIS objectives. On-line and off-line techniques were employed. These comprised different approaches of mass spectrometers and optical devices as on-line systems and a suite of commercial and non-commercial cartridges as off-line. Some of the experiments were also modeled. The intercomparison included three types of scenarios, the two later simulating typical urban and semi-urban conditions: 1. Synthetic mixture of carbonyls, 2. Products from photooxidations of biogenic and anthropogenic VOCs and 3. Products from ozonolysis of biogenic VOC and monoterpenes, under different relative humidity conditions.This work represents a step forward in the evaluation and conclusions of the data obtained. An overall good agreement was found among the techniques with good correlations, especially in the synthetic mixtures, as expected, while these parameters worsen under more realistic conditions with complex gas samples. Regarding off-line techniques, good practices on sample storage and use are discussed. Advanced analysis using clusters was also applied to group instruments with similar behaviour, indicating similar performance among the on-line instruments although partitions revealed certain discrepancies. The role of the gas mixture, the calibration set-up and the humidity conditions are discussed in this work.AcknowledgementsThis project/work has received funding from the European Union’s Horizon 2020 research and innovation programme through the EUROCHAMP-2020 Infrastructure Activity under grant agreement No 730997. CAPOX from the Spanish R+D program, Ref RTU2018-097768-B-C21 and PROMETEO from the GVA excellence R&D program, Ref PROMETEO (2019/110) are acknowledged. F. CEAM is partly supported by Generalitat Valenciana.

In order to predict the amount of secondary organic aerosol formed by heterogeneous processing of methylglyoxal, uptake coefficients (γ) and estimates of uptake reversibility are needed. Here, uptake coefficients are extracted from chamber studies involving ammonium sulfate and glycine seed aerosol at high relative humidity (RH ≥ 72%). Methylglyoxal uptake coefficients on prereacted glycine aerosol particles had a strong dependence on RH, increasing from γ = 0.4 × 10–3 to 5.7 × 10–3 between 72 and 99% RH. Continuous methylglyoxal losses were also observed in the presence of aqueous ammonium sulfate at 95% RH (γAS,wet = 3.7 ± 0.8 × 10–3). Methylglyoxal uptake coefficients measured at ≥95% RH are larger than those reported for glyoxal on nonacidified, aqueous aerosol surfaces at 90% RH. Slight curvature in first-order uptake plots suggests that methylglyoxal uptake onto aqueous aerosol surfaces is not entirely irreversible after 20 min. Methylglyoxal uptake by cloud droplets was rapid and largely reversible...

Pyruvic acid is an atmospherically abundant α-keto-acid that degrades efficiently from the troposphere via gas-phase photolysis. To explore conditions relevant to the environment, 2–12 ppm pyruvic acid is irradiated by a solar simulator in the environmental simulation chamber, CESAM. The combination of the long path length available in the chamber and its low surface area to volume ratio allows us to quantitatively examine the quantum yield and photochemical products of pyruvic acid. Such details are new to the literature for the low initial concentrations of pyruvic acid employed here. We determined photolysis quantum yields of ϕobsN2 = 0.84 ± 0.1 in nitrogen and ϕobsAir = 3.2 ± 0.5 in air, which are higher than those reported by previous studies that used higher partial pressures of pyruvic acid. The quantum yield greater than unity in air is due to secondary chemistry, driven by O2, that emerges under the conditions in these experiments. The low concentration of pyruvic acid and the resulting oxygen ef...

Reaction rate constants for the reaction of n-dodecane with hydroxyl radicals were measured as a function of temperature between 283 and 303 K, using the relative rate method in the CESAM chamber (French acronym for "Chamber for Atmospheric Multiphase Experimental Simulation"). The rate constants obtained at 283, 293 and 303 K are (1.27 ± 0.31)×10-11 , (1.33 ± 0.34)×10-11 , (1.27 ± 0.40)×10-11 cm 3 molecule-1 s-1 , respectively. Rate constants measured were in excellent agreement with the few available data in the literature over the studied temperature range (283-340K). Rate constants estimated by the structure-activity relationship and transition state theory methods agreed with our experimental data within 14 %. From these data combined with previous literature measurement, the following Arrhenius expression; + = (9.77 ± 6.19)10 −11 × exp [ −595 ±5580 ] 3 −1 −1 , was found valid over a temperature range (283-340 K) of the tropospheric interest.

Alpha-dicarbonyl compounds are believed to form brown carbon in the atmosphere via reactions with ammonium sulfate (AS) in cloud droplets and aqueous aerosol particles. In this work, brown carbon formation in AS and other aerosol particles was quantified as a function of relative humidity (RH) during exposure to gas-phase glyoxal (GX) in chamber experiments. Under dry conditions (RH 2 and are consistent between AS and AS–glycine aerosol. Dry methylammonium sulfate aerosol browns 4 times more than dry AS aerosol, but deliquesced AS aerosol browns much less than dry AS aerosol. Optical measurements at 405, 450, and 530 nm provide an estimated Ångstrom absorbance coefficient of -16±4. This coefficient and the empirical relationship between GX and albedo are used to estimate an upper limit to global radiative forcing by brown carbon formed by 70 ppt GX reacting with AS (+7.6×10-5 W m−2). This quantity is

International audience; The present work is an extensive laboratory study of organosulfate (OS) formation from the reaction of α-pinene oxidation products or proxies with acidified ammonium sulfate aerosols in three different acidity conditions (NH$_4$)$_2$SO$_4$ 0.06 M; (NH$_4$)$_2$SO$_4$/H$_2$SO$_4$ 0.06 M/0.005 M; (NH$_4$)$_2$SO$_4$/H$_2$SO$_4$ 0.03 M/0.05 M). The kinetics of the reactions of $\alpha$-pinene, $\alpha$-pinene oxide, isopinocampheol, pinanediol, and myrtenal with ammonium sulfate particles were studied using a quasi-static reactor. The reaction of $\alpha$-pinene oxide with the highly acidic ammonium sulfate particles was determined to be 7, 10, 21, and 24 times faster than for isopinocampheol, $\alpha$-pinene, pinanedial, and myrtenal, respectively, for an OS precursor concentration of 1 ppm and after 1 h reaction time. The effective rate coefficients for OS formation from $\alpha$-pinene oxide were determined to be 2 orders of magnitude higher in highly acidic conditions than for the two other acidity conditions. For $\alpha$-pinene oxide reactions with highly acidic ammonium sulfate particles, OS formation was observed to increase linearly with (i) the time of reaction up to 400 min ($r^2$= > 0.95) and (ii) α-pinene oxide gas-phase concentration. However, OS formation from $\alpha$-pinene oxide reactions with slightly acidic or pure ammonium sulfate particles was limited, with a plateau ([OS]max = 0.62 ± 0.03 $\mu$g) reached after around 15–20 min. Organosulfate dimers (m/z 401 and m/z 481) were detected not only with highly acidic particles but also with slightly acidic and pure ammonium sulfate particles, indicating that oligomerization processes do not require strong acidity conditions. Dehydration products of organosulfates ($m/z$ 231 and $m/z$ 383) were observed only under highly acidic conditions, indicating the key role of H$_2$SO$_4$ on the dehydration of organosulfates and the formation of olefins in the atmosphere. Finally, this kinetic study was completed with simulation chamber experiments in which the mass concentration of organosulfates was shown to depend on the available sulfate amount present in the particle phase ($r^2$ = 0.96). In conclusion, this relative comparison between five organosulfate precursors shows that epoxide was the most efficient reactant to form organosulfates via heterogeneous gas–particle reactions and illustrates how gas–particle reactions may play an important role in OS formation and hence in the atmospheric fate of organic carbon. The kinetic data presented in this work provide strong support to organosulfate formation mechanisms proposed in part 1 ( J. Phys. Chem. A 2016, 120, 7909−7923).

Reaction rate constants for the reaction of

The temperature and concentration dependence of secondary organic aerosol (SOA) yields has been investigated for the first time for the photooxidation of n-dodecane (C12H26) in the presence of NOx in the CESAM chamber (French acronym for “Chamber for Atmospheric Multiphase Experimental Simulation”). Experiments were performed with and without seed aerosol between 283 and 304.5 K. In order to quantify the SOA yields, a new parametrization is proposed to account for organic vapor loss to the chamber walls. Deposition processes were found to impact the aerosol yields by a factor from 1.3 to 1.8 between the lowest and the highest value. As with other photooxidation systems, experiments performed without seed and at low concentration of oxidant showed a lower SOA yield than other seeded experiments. Temperature did not significantly influence SOA formation in this study. This unforeseen behavior indicates that the SOA is dominated by sufficiently low volatility products for which a change in their partitioning...

The impact of cloud events on isoprene secondary organic aerosol (SOA) formation has been studied from an isoprene/NOx/light system in an atmospheric simulation chamber. It was shown that the presence of a liquid water cloud leads to a faster and higher SOA formation than under dry conditions. When a cloud is generated early in the photooxidation reaction, before any SOA formation has occurred, a fast SOA formation is observed with mass yields ranging from 0.002 to 0.004. These yields are two and four times higher than those observed under dry conditions. When the cloud is generated at a later photooxidation stage, after isoprene SOA is stabilized at its maximum mass concentration, a rapid increase (by a factor of two or higher) of the SOA mass concentration is observed. The SOA chemical composition is influenced by cloud generation: the additional SOA formed during cloud events is composed of both organics and nitrate containing species. This SOA formation can be linked to water soluble volatile organic compounds (VOCs) dissolution in the aqueous phase and to further aqueous phase reactions. Cloud-induced SOA formation is experimentally demonstrated in this study, thus highlighting the importance of aqueous multiphase systems in atmospheric SOA formation estimations.

Methylamine, a common atmospheric amine species, is found in the gas, particle, and aqueous phases. It has been shown to form light-absorbing, oligomeric species in reactions with methylglyoxal and other aldehyde species in bulk aqueous-phase experiments and when mixed into seed aerosol as a sulfate salt. Here, we explore the influence of multiphase methylamine chemistry on aerosol production, properties, and molecular composition. When methylglyoxal aerosol particles were exposed to ∼2 ppm methylamine gas in a humid chamber, rapid browning was observed, but not growth. Aerosol bounce measurements indicated that particles became slightly more viscous and hydrophobic upon methylamine exposure. Subsequent cloud processing increased both viscosity and hygroscopicity but had little effect on browning, consistent with high-resolution mass spectrometry results showing that aerosol oligomer dicarbonyl functional groups were transformed into cationic imidazole rings. Photolytic cloud processing triggered the inco...

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Aqueous methylglyoxal chemistry has often been implicated as an important source of oligomers in atmospheric aerosol. Here we report on chemical analysis of brown carbon aerosol particles collected from cloud cycling/photolysis chamber experiments, where gaseous methylglyoxal and methylamine interacted with glycine, ammonium, or methylammonium sulfate seed particles. Eighteen N-containing oligomers were identified in the particulate phase by liquid chromatography/diode array detection/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry. Chemical formulas were determined and, for 6 major oligomer products, MS2 fragmentation spectra were used to propose tentative structures and mechanisms. Electronic absorption spectra were calculated for six tentative product structures by an ab initio second order algebraic-diagrammatic-construction/density functional theory approach. For five structures, matching calculated and measured absorption spectra suggest that they are dominant lig...

Aerosol-cloud interaction contributes to the largest uncertainties in the estimation and interpretation of the Earth's changing energy budget. The present study explores experimentally the impacts of water condensation-evaporation events, mimicking processes occurring, in atmospheric clouds, on the molecular composition of secondary organic aerosol (SOA) from the photooxidation of methacrolein. A range of on and off-line mass spectrometry techniques were used to obtain a detailed chemical characterization of SOA formed in control experiments in dry conditions, in triphasic experiments simulating gas-particle-cloud droplet interactions (starting from dry conditions and from 60% relative humidity (RH)), and in bulk aqueous-phase experiments. We observed that cloud events trigger fast SOA formation accompanied by evaporative losses. These evaporative losses decreased SOA concentration in the simulation chamber by 25-32% upon RH increase, while aqueous SOA was found to be metastable and slowly evaporated after cloud dissipation. In the simulation chamber, SOA composition measured with a high-resolution time-of flight aerosol mass spectrometer, did not change during cloud events compared with high RH conditions (RH > 80%). In all experiments, off-line mass spectrometry techniques emphasize the critical role of 2-methylglyceric acid as a major product of isoprene chemistry, as an important contributor to the total SOA mass (15-20%) and as a key building block of oligomers found in the particulate phase. Interestingly, the comparison between the series of oligomers obtained from experiments performed under different conditions show a markedly different reactivity. In particular, long reaction times at high RH seem to create the conditions for aqueous-phase processing to occur in a more efficient manner than during two relatively short cloud events.

The effects of methylglyoxal uptake on the physical and optical properties of aerosol containing amines or ammonium sulfate were determined before and after cloud processing in a temperature- and RH-controlled chamber. The formation of brown carbon was observed upon methylglyoxal addition, detected as an increase in water-soluble organic carbon mass absorption coefficients below 370 nm and as a drop in single-scattering albedo at 450 nm. The imaginary refractive index component k450 reached a maximum value of 0.03 ± 0.009 with aqueous glycine aerosol particles. Browning of solid particles occurred at rates limited by chamber mixing (

Aerosol and molecular processing in the atmosphere occurs in a complex and variable environment consisting of multiple phases and interfacial regions. To explore the effects of such conditions on the reactivity of chemical systems, we employ an environmental simulation chamber to investigate the multiphase photolysis of pyruvic acid, which photoreacts in the troposphere in aqueous particles and in the gas phase. Upon irradiation of nebulized pyruvic acid, acetic acid and carbon dioxide are rapidly generated, which is consistent with previous literature on the bulk phase photolysis reactions. Additionally, we identify a new C6 product, zymonic acid, a species that has not previously been reported from pyruvic acid photolysis under any conditions. Its observation here, and corresponding spectroscopic signatures, indicates it could be formed by heterogeneous reactions at the droplet surface. Prior studies of the aqueous photolysis of pyruvic acid have shown that high-molecular-weight compounds are formed via...

The temperature and concentration dependence of secondary organic aerosol (SOA) yields has been investigated for the first time for the photooxidation of n-dodecane (C

Nowadays, more than 50% of the global population leave in urban centers which activities generate large anthropogenic emissions of CO2 (more than 70% of fossil fuel CO2 comes from urbanized/industrialized areas) and reactive gases that endanger our climate, the health of human beings and surrounding ecosystems. The worst situations are encountered during urban pollution events that usually form under anticyclonic conditions. Analyzing the contribution of the local and regional sources of urban CO2 and co-emitted species vs the remote ones, as well as the nature of these sources and the dynamical processes that lead to the building of such events can provide interesting knowledge for helping urban policy makers to better identify the role of anthropogenic/biogenic sources on the urban air composition and to take proper decisions in matter of CO2 and pollutants sources mitigation. With 12 million of people, Paris (France) is the second megacity in Europe. In 2016, two pollution events occured in the Paris region during which the instrumental platform OCAPI (http://observations.ipsl.fr/composition-atmospherique-en-idf.html) from IPSL (Institut Pierre Simon Laplace) was mobilized in collaboration with air quality governing actors (AIRPARIF, INERIS) to collect a bunch of observations. Five sites located in the urban, peri-urban and rural areas of Paris were equiped with in-situ analyzers (CO2, CO, black carbon, 13CO2, COS) ; Fourier transform spectrometers for column measurements (XCO2, XCO, XCOS), particle filters (for aerosols size and content analysis) ; air samples (levoglucosan, 14CO2, VOCs) ; and Lidar profilers (boundary layer height ; wind profiles). These data, combined with a backtrajectories analysis, give information about the dynamical processes that lead to the formation of the pollution events and on the contribution of local, regional and remote sources. The analysis of the correlations between the trace species and of the isotopic content of carbon in CO2 provides further clues on the nature of the anthropogenic and biogenic sources involved in the urban pollution events. Especially, the role of agricultural spreading through the observation of ammonium nitrate particles and the contribution of biomass burning through levoglucosan and black carbon measurements will be discussed.

In the present study, quasi-static reactor and atmospheric simulation chamber experiments were performed to investigate the formation of α-pinene-derived organosulfates. Organosulfates (R–OSO3H) were examined for the reactions between acidified ammonium sulfate particles exposed to an individual gaseous volatile organic compound, such as α-pinene and oxidized products (α-pinene oxide, isopinocampheol, pinanediol and myrtenal). Molecular structures were elucidated by liquid chromatography interfaced to high-resolution quadrupole time-of-flight mass spectrometry equipped with electrospray ionization (LC/ESI-HR-QTOFMS). New organosulfate products were detected and identified for the first time in the present study. Reaction with α-pinene oxide was found to be a favored pathway for organosulfate formation (C10H18O5S) and to yield organosulfate dimers (C20H34O6S and C20H34O9S2) and trimers (C30H50O10S2) under dry conditions (RH < 1%) and high particle acidity and precursor concentrations (1 ppm). The role of r...

Knowing the ozone absorption cross sections in the ultraviolet and infrared spectral range, with an accuracy of better than 1%, is of the utmost importance for atmospheric remote-sensing applications. For this reason, various ozone intensity intercomparisons and measurements have been published these last years. However, the corresponding results proved not to be consistent and thus have raised a controversial discussion in the community of atmospheric remote-sensing. This study, where great care has been taken to avoid any possible error, reports a new laboratory intercomparison of the ozone absorption coefficients in the mid-infrared (10 μm) and ultraviolet (300-350 nm) spectral regions. It gives a new piece of information to the puzzling problem concerning the ozone IR and UV cross sections and confirms that the IR and UV cross sections recommended in the literature are in disagreement of about 4%.

Nitrous acid, HONO, is an important trace gas in tropospheric photochemistry, because it is a source of OH radicals. In order to obtain HONO concentrations from spectroscopic measurements, the knowledge of accurate absorption cross-sections is essential. Furthermore, the ultraviolet absorption cross-sections of HONO determine its atmospheric photolysis rates, which are still being debated. In particular, in a recent field study focusing on the photolysis frequency of HONO, the absolute values of the ultraviolet absorption cross-sections have been proposed as a potential source for systematic errors. For these reasons, we have compared the absorption cross-sections for HONO in the infrared (IR) and ultraviolet (UV) by performing simultaneous measurements in both spectral regions. Assuming that the IR cross-sections (that show good agreement between different studies) are correct, our study shows a good agreement between the consistent infrared studies and some selected accurate UV spectra published previously (about 6%) while a rather large disagreement (about 22%) is observed when using other UV data sets.

The activity “Absorption Cross-Sections of Ozone” (ACSO) started in 2008 as a joint initiative of the International Ozone Commission (IO3C), the World Meteorological Organization (WMO) and the IGACO (“Integrated Global Atmospheric Chemistry Observations”) O3/UV subgroup to study, evaluate, and recommend the most suitable ozone absorption cross-section laboratory data to be used in atmospheric ozone measurements. The evaluation was basically restricted to ozone absorption cross-sections in the UV range with particular focus on the Huggins band. Up until now, the data of Bass and Paur published in 1985 (BP, 1985) are still officially recommended for such measurements. During the last decade it became obvious that BP (1985) cross-section data have deficits for use in advanced space-borne ozone measurements. At the same time, it was recognized that the origin of systematic differences in ground-based measurements of ozone required further investigation, in particular whether the BP (1985) cross-section data might contribute to these differences. In ACSO, different sets of laboratory ozone absorption cross-section data (including their dependence on temperature) of the group of Reims (France) (Brion et al., 1993, 1998, 1992, 1995, abbreviated as BDM, 1995) and those of Serdyuchenko et al. (2014), and Gorshelev et al. (2014), (abbreviated as SER, 2014) were examined for use in atmospheric ozone measurements in the Huggins band. In conclusion, ACSO recommends: (a) The spectroscopic data of BP (1985) should no longer be used for retrieval of atmospheric ozone measurements. (b) For retrieval of ground-based instruments of total ozone and ozone profile measurements by the Umkehr method performed by Brewer and Dobson instruments data of SER (2014) are recommended to be used. When SER (2014) is used, the difference between total ozone measurements of Brewer and Dobson instruments are very small and the difference between Dobson measurements at AD and CD wavelength pairs are diminished. (c) For ground-based Light Detection and Ranging (LIDAR) measurements the use of BDM (1995) or SER (2014) is recommended. (d) For satellite retrieval the presently widely used data of BDM (1995) should be used because SER (2014) seems less suitable for retrievals that use wavelengths close to 300 nm due to a deficiency in the signal-to-noise ratio in the SER (2014) dataset. The work of ACSO also showed: • The need to continue laboratory cross-section measurements of ozone of highest quality. The importance of careful characterization of the uncertainties of the laboratory measurements. • The need to extend the scope of such studies to other wavelength ranges (particularly to cover not only the Huggins band but also the comparison with the mid-infrared region). • The need for regular cooperation of experts in spectral laboratory measurements and specialists in atmospheric (ozone) measurements.

First- and higher order-generation products formed from the oxidation of isoprene and methacrolein with OH radicals in the presence of NOx have been studied in a simulation chamber. Significant oxidation rates have been maintained for up to 7 h, allowing the study of highly oxidized products. Gas-phase product distribution and yields were obtained, and show good agreement with previous studies. Secondary organic aerosol (SOA) formation has also been investigated. SOA mass yields from previous studies show large discrepancies. The mass yields obtained here were consistent with the lowest values found in the literature, and more specifically in agreement with studies carried out with natural light or artificial lamps with emission similar to the solar spectrum. Differences in light source are therefore proposed to explain partially the discrepancies observed between different studies in the literature for both isoprene- and methacrolein-SOA mass yields. There is a high degree of similarity between the SOA mass spectra from isoprene and methacrolein photooxidation, thus strengthening the importance of the role of methacrolein in SOA formation from isoprene photooxidation under our experimental conditions (i.e., presence of NOx and long term oxidation). According to our results, SOA mass yields from both isoprene and methacrolein in the atmosphere could be lower than suggested by most of the current chamber studies.

Aromatic hydrocarbons are important components of polluted ambient air. The reaction of OH radicals with hexamethylbenzene (HMB) is a prototype system to study ipso addition leading eventually to dealkylation. We have investigated the OH + HMB and OD + HMB reactions between 323 and 433 K using a discharge fast-flow reactor coupled to a time-of-flight mass spectrometer with single-photon VUV photoionization (10.54 eV). The H atom abstraction channel has been found to be equal to (13.7 ± 4.4) % at 330 K leading to (11.1 ± 3.6) % at 298 K, higher than predicted by commonly used structure-reactivity relationships. The back dissociation rate constant has also been measured and has been found to be smaller than the rate of other aromatic hydrocarbons, in good agreement with density functional theoretical calculations. The dealkylation channel, leading to pentamethylphenol (PMP) + CH(3), is always found to be the minor channel, estimated inferior to 2% at 298 K.

Anthropogenic sources release into the troposphere a wide range of volatile organic compounds (VOCs) including aromatic hydrocarbons, whose major sources are believed to be combustion and the evaporation of fossil fuels. An important question is whether there are other sources of aromatics in air. We report here the formation of p-cymene [1-methyl-4-(1-methylethyl) benzene, C6H4(CH3)(C3H7)] from the oxidation of α-pinene by OH, O3, and NO3 at 1 atm in air and 298 K at low (5%) and high (70%) relative humidities (RH). Loss of α-pinene and the generation of p-cymene were measured using GC-MS. The fractional yields of p-cymene relative to the loss of α-pinene, Δ [p-cymeme]/Δ [α-pinene], were measured to range from (1.6±0.2)×10(-5) for the O3 reaction to (3.0±0.3)×10(-4) for the NO3 reaction in the absence of added water vapor. The yields for the OH and O3 reactions increased by a factor of 4-8 at 70% RH (uncertainties are ±2s). The highest yields at 70% RH for the OH and O3 reactions, ∼15 times higher than for dry conditions, were observed if the walls of the Teflon reaction chamber had been previously exposed to H2SO4 formed from the OH oxidation of SO2. Possible mechanisms of the conversion of α-pinene to p-cymene and the potential importance in the atmosphere are discussed.

[1] Formaldehyde plays a key role in atmospheric photochemistry and is particularly important for the production of HOx species. For measuring atmospheric formaldehyde concentrations, both midinfrared and ultraviolet (UV) absorption techniques are used by ground-, air- or satellite-based instruments. In order to obtain accurate formaldehyde concentrations, the knowledge of the absorption cross sections is of utmost importance. In this study, we report the first laboratory intercomparison of the absorption coefficients of formaldehyde using simultaneous measurements in both spectral regions. The intercomparison shows good agreement between selected accurate UV spectra published previously and different infrared data. On the contrary, a rather large disagreement (about 20%) is observed when using other UV data sets, such as those recommended currently by the HITRAN database.

Optical measurements of atmospheric minor constituents are performed using spectrometers working in the UV-visible, infrared and microwave spectral ranges. In particular recently the satellite ENVISAT has been launched with three spectrometers on board, SCIAMACHY and GOMOS working in the UV-visible spectral region and MIPAS working in the thermal infrared. The analysis and interpretation of the atmospheric spectra require good knowledge of the molecular parameters of the species of interest as well as of the interfering species. This is true not only in the spectral domain used to retrieve the species (Thermal infrared for MIPAS for example) but also in the other spectral domains used by other instruments: Meaningful comparisons of profiles retrieved by various instruments using different spectral domains require indeed that the spectral parameters are consistent in these spectral domains. To illustrate these points we will concentrate on three molecules namely nitric acid, formaldehyde and ozone. For HNO3 we will show the difficulty to measure line intensities in the laboratory and we will describe how a comparison of MIPAS profiles with those obtained by another instrument operating in a different spectral range (Far infrared) may be used to validate the HNO3 line parameters in the mid-infrared. For the measurement of atmospheric formaldehyde concentrations, mid-infrared and ultraviolet absorptions are both used by ground, air or satellite instruments. It is then of the utmost importance to have consistent spectral parameters in these various spectral domains. Consequently the aim of the study performed at LISA was to intercalibrate formaldehyde spectra in the infrared and ultraviolet regions. The experiments were performed by acquiring simultaneously UV and IR spectra at room temperature and atmospheric pressure using a common optical cell. The reactor contains two multiple reflection optical systems interfaced to a Fourier transform infrared spectrometer and to an UV-visible absorption spectrometer. The results are discussed and compared with previous ones. In the mid-infrared range, the 10 µm ozone band is very strong and is the most widely used to derive concentration profiles. In the UV region, various bands are currently used for spectroscopic remote-sensing of ozone. In this paper we present two sets of results: First a careful comparison of four sets of ozone line intensities measured independently in the 10 µm region has been achieved. From them new and more accurate transition moment constants for the ν1 and ν3 bands of 16O3 were derived and used to generate new line positions and intensities. These new spectroscopic parameters allowed one to simulate atmospheric spectra better than the previous spectroscopic parameters showing that on a relative basis the new spectral parameters are of better quality. Second, we present intercomparisons of ozone absorption cross sections in the UV and mid-infrared regions, using the absorption of ozone at 254 nm and in the Huggins region. In the case of the Huggins region the comparison has been performed by acquiring simultaneously UV and infrared spectra at room temperature and atmospheric pressure using the same reactor as for H2CO.

UV (240-370 nm) and IR (3200-1500 cm(-1)) absorption cross-sections of HCHO, HCDO, and DCDO in a bath gas of N(2) at atmospheric pressure and 296 K are reported from simultaneous measurements in the two spectral regions. Cross-sections were placed on an absolute scale through quantitative conversion of formaldehyde to CO and HCOOH by titration with Br atoms, also monitored by FTIR. The integrated UV absorption cross-sections of HCHO, HCDO, and DCDO are equal to within the experimental uncertainty.

As emphasized by the Intergovernmental Panel for Climate Change (IPCC), aerosols contribute the largest uncertainty to global radiative forcing budget estimates. The uncertainty stems largely from the lack of information related to global aerosol distributions, composition, and aging effects in the atmosphere, all of which affect aerosol radiative properties.Of the two major categories of aerosols, natural and anthropogenic, natural aerosols remain the largest source of the uncertainty. This limits our capacity to measure and attribute total climate forcings. Without a firm understanding of total climate forcing, our ability to predict its evolution over time diminishes and limits the development of adaptation strategies for future climate change.Aerosolized mineral dust is the largest single component of the global aerosol mass budget, making up nearly half of annual particle emissions to the atmosphere. Mineral dust aerosols influence the global climate through both direct interactions with radiation (scattering and absorption in the visible and IR regions) as well as indirect interactions with radiation (by serving as cloud condensation nuclei (CCN) or ice nuclei (IN)). One potentially important aspect of dust aerosols is that they are able to uptake and heterogeneously react with gases. Henceforth, mineral dust may also play a significant but mostly unknown role in secondary organic aerosol (SOA) formation in the atmosphere.While the combination of the complex reaction pathways and processing mechanisms inherent to the dust/organic system is hampering our understanding of dust and organic aerosols on global climate, and despite a great number of progresses on climate-relevant properties of mineral dust and SOA in these past ten years, studies of the heterogeneous chemistry occurring between dust and organic species are sparse.The CLImate relevant processing of Mineral Dust by volatile Organic compounds (CLIMDO) project tackles this under-explored science question by proposing the first comprehensive process-driven project addressing the reactivity of complex and realistic mineral dust/organic systems to better understand how dust and VOCs influence the global climate system.CLIMDO will investigate the heterogeneous interaction of mineral dust with two of the most common organic SOA precursors: glyoxal and methylglyoxal from ubiquitous anthropogenic and biogenic sources, thought combination of innovative laboratory experiments in a well-controlled and characterized environment (the atmospheric simulation chamber CESAM) and advanced flow reactors and optical cells), the development of novel modelling schemes of both the reaction mechanisms and the resulting optical properties of mineral dust, and new simulations of the global direct radiative effect and SOA distribution using the LMDzOR-INCA.This presentation describes the strategy and workplan of the CLIMDO project, including dissemination of results and open data, to inform the science community and foster and cluster new collaborations.